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Going beyond currently reported two electron transformations that formed the core backdrop of asymmetric catalytic site-selective carbohydrate polyol functionalizations, we herein report a seminal demonstration of an enantioconvergent copper catalyzed site-selective etherification of minimally protected saccharides through a single-electron radical pathway. Further, this strategy paves a rare strategy, through which a carboxamide scaffold that is present in some glycomimetics of pharmacological relevance, can be selectively introduced. In light of the burgeoning interest in chiral radical catalysis, and the virtual absence of such stereocontrol broadly in carbohydrate synthesis, our strategy showcased the unknown capability of chiral radical copper catalysis as a contemporary tool to address the formidable site-selectivity challenge on a remarkable palette of naturally occurring saccharides. When reducing sugars were employed, a further dynamic kinetic resolution type glycosylation can be activated by the catalytic system to selectively generate the challenging β-O-glycosides., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Engineering of extracellular vesicles (EVs) towards more efficient targeting and uptake to specific cells has large potentials for their application as therapeutics. Carbohydrates play key roles in various biological interactions and are essential for EV biology. The extent to which glycan modification of EVs can be achieved through genetic glycoengineering of their parental cells has not been explored yet. Here we introduce targeted glycan modification of EVs through cell-based glycoengineering via modification of various enzymes in the glycosylation machinery. In a "simple cell" strategy, we modified major glycosylation pathways by knocking-out (KO) essential genes for N-glycosylation (MGAT1), O-GalNAc glycosylation (C1GALT1C1), glycosphingolipids (B4GALT5/6), glycosaminoglycans (B4GALT7) and sialylation (GNE) involved in the elongation or biosynthesis of the glycans in HEK293F cells. The gene editing led to corresponding glycan changes on the cells as demonstrated by differential lectin staining. Small EVs (sEVs) isolated from the cells showed overall corresponding glycan changes, but also some unexpected differences to their parental cell including enrichment preference for certain glycan structures and absence of other glycan types. The genetic glycoengineering did not significantly impact sEVs production, size distribution, or syntenin-1 biomarker expression, while a clonal influence on sEVs production yields was observed. Our findings demonstrate the successful implementation of sEVs glycoengineering via genetic modification of the parental cell and a stable source for generation of glycoengineered sEVs. The utilization of glycoengineered sEVs offers a promising opportunity to study the role of glycosylation in EV biology, as well as to facilitate the optimization of sEVs for therapeutic purposes., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

A deprotected biantennary high mannose heptasaccharide N-glycan comprising two mannose-6-phosphate residues was synthesised as a putative ligand for the mannose 6-phosphate receptors, using a convergent [3 + 4] glycosylation strategy., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Antony Fairbanks reports financial support was provided by New Zealand Ministry of Business Innovation and Employment. Antony Fairbanks reports financial support was provided by Royal Society of New Zealand Marsden Fund. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

High molecular weight (HMW; >1 kDa) carbohydrates are a major component of dissolved organic matter (DOM) released by benthic primary producers. Despite shifts from coral to algae dominance on many reefs, little is known about the effects of exuded carbohydrates on bacterioplankton communities in reef waters. We compared the monosaccharide composition of HMW carbohydrates exuded by hard corals and brown macroalgae and investigated the response of the bacterioplankton community of an algae-dominated Caribbean reef to the respective HMW fractions. HMW coral exudates were compositionally distinct from the ambient, algae-dominated reef waters and similar to coral mucus (high in arabinose). They further selected for opportunistic bacterioplankton taxa commonly associated with coral stress (i.e., Rhodobacteraceae , Phycisphaeraceae , Vibrionaceae , and Flavobacteriales ) and significantly increased the predicted energy-, amino acid-, and carbohydrate-metabolism by 28%, 44%, and 111%, respectively. In contrast, HMW carbohydrates exuded by algae were similar to those in algae tissue extracts and reef water (high in fucose) and did not significantly alter the composition and predicted metabolism of the bacterioplankton community. These results confirm earlier findings of coral exudates supporting efficient trophic transfer, while algae exudates may have stimulated microbial respiration instead of biomass production, thereby supporting the microbialization of reefs. In contrast to previous studies, HMW coral and not algal exudates selected for opportunistic microbes, suggesting that a shift in the prevalent DOM composition and not the exudate type (i.e., coral vs algae) per se , may induce the rise of opportunistic microbial taxa., Importance: Dissolved organic matter (DOM) released by benthic primary producers fuels coral reef food webs. Anthropogenic stressors cause shifts from coral to algae dominance on many reefs, and resulting alterations in the DOM pool can promote opportunistic microbes and potential coral pathogens in reef water. To better understand these DOM-induced effects on bacterioplankton communities, we compared the carbohydrate composition of coral- and macroalgae-DOM and analyzed the response of bacterioplankton from an algae-dominated reef to these DOM types. In line with the proposed microbialization of reefs, coral-DOM was efficiently utilized, promoting energy transfer to higher trophic levels, whereas macroalgae-DOM likely stimulated microbial respiration over biomass production. Contrary to earlier findings, coral- and not algal-DOM selected for opportunistic microbial taxa, indicating that a change in the prevalent DOM composition, and not DOM type, may promote the rise of opportunistic microbes. Presented results may also apply to other coastal marine ecosystems undergoing benthic community shifts., Competing Interests: The authors declare no conflict of interest.

In the present work, bacterial glycosyltransferases are utilized to construct ganglioside glycans in a convergent approach via a sugar‒nucleotide regeneration system and one-pot multienzyme reactions. Starting from β-lactoside enables the diversification of both the glycan moieties and the linkages in the lower α-arm and upper β-arm. Overall, a comprehensive panel of 24 natural a-series (GM3, GM2, GM1a, GD1a, GT1a, and fucosyl-GM1), b-series (GD3, GD2, GD1b, GT1b, and GQ1b), c-series (GT3, GT2, GT1c, GQ1c, and GP1c), α-series (GM1α, GD1aα, and GT1aα), and o-series (GA2, GA1, GM1b, GalNAc-GM1b, and GD1c) ganglioside glycans are prepared, which are suitable for biological studies and further applications. Moreover, a microarray is constructed with these synthesized ganglioside glycans to investigate their binding specificity with recombinant Fc-fused Siglec-7 and Siglec-9, which are immune checkpoint-like glycan recognition proteins on natural killer cells. The microarray binding results reveal that GD3 and GT1aα are specific ligands for Siglec-7 and Siglec-9, respectively, and this discovery can lead to the identification of appropriate ligands for investigating the roles of these Siglecs in immunomodulation., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

The present study was aimed at investigating the source, quality, and quantity of organic matter and labile fraction of biochemical constituents in the surficial sediments of Arabian Sea Shoreline at Kollam, India, which gives an input into the processes associated with the subsurface geochemistry pattern. About 15 surface sediment samples were collected from the five beaches for this study during January 2021. The samples were analyzed for CHN, total organic carbon (TOC), and labile fraction such as carbohydrates (CHO), proteins (PRO), and lipids (LIP). The TOC/TN ratio revealed that the source organic matter (OM) in the samples was primarily of marine origin and autochthonous, except TM3 at Thirumullavaram. Thirumullavaram is a sheltered beach, and it has low hydrodynamic process. The high organic matter content in TM3 (13.9) may be the originated from the terrestrial input. The hierarchical cluster analysis revealed that TM3 indicate that unique character to other stations. Principal component analysis revealed that three components accounted for 78% of the total variance. PC1 variance was associated with carbon-based organic compounds. PC2 was predominantly influenced by CHO and LOM, suggesting that PC2 may encompass variability associated with these nutritional profiles. PC3 was influenced by LIP and LIP/CHO, showing it may be a lipid-related component. The PRO to CHO ratio is < 1, exhibiting old aged organic matter deposited in sediments and the meso-oligotrophic status. The LIP to CHO ratio, recorded as < 1, exhibits the poor quality of energetic (food) OM in sediments. The sediment samples exhibit the following trend CHO > PRO > LIP., Competing Interests: Declarations Competing Interests The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

The increasing complexity and ubiquity of food processing and the emergence of fraudulent practices have made effective and reliable methods to authenticate food products of utmost importance. Carbohydrates, with various nutritional functions, are abundant in foods and can serve as potential markers for food authentication. However, the complex and diverse structures and properties of carbohydrates, especially polysaccharides, pose challenges. Nonetheless, significant progress has been made in this area. This paper provides an overview of the utilization of carbohydrates in food authentication since 2000, focusing on strategies involving carbohydrate-based markers, carbohydrate profiles, and carbohydrate-protein interaction-based assays. The analytical techniques, applications, challenges and limitations of these strategies are reviewed and discussed. The findings demonstrate that these strategies offer origin verification, quality assessment, adulteration detection, process control, and food species identification. Notably, oligosaccharide analysis has proven effective in food authentication and remains a promising marker, especially for analyzing intricate matrices. The advances in chromatography separation and mass spectrometry identification of isomers and trace amounts of these compounds have facilitated the discovery of such markers. In conclusion, carbohydrate analysis can play a crucial role in food authentication. Future research and development will make the authentication of carbohydrate-rich foods ever more accurate and efficient., Competing Interests: Declaration of competing interest The authors declare no competing financial interests., (Copyright © 2024. Published by Elsevier Ltd.)

Indigo, indirubin, and isoindigo derivatives have been used for centuries as pigments. Since the 1990s, a new aspect of the chemistry of this type of compounds is their activity against various types of cancer. N -Glycosides of indigo, indirubin, and isoindigo, blue, red, and yellow sugars, turned out to be of special interest because of their high cancerostatic activity and structural novelty. The present article provides an account on the synthesis and anticancer activity of these compounds., (Copyright © 2024, Langer.)

Sialic acids are monosaccharide residues involved in several biological processes. Controlling the stereoselectivity of sialylation reactions is challenging and mechanistic studies on the structure of its intermediate, the sialyl cation, are scarce. Here it is shown that a sialyl cation can be generated and isolated from an ionized sialic acid precursor. This short-lived species is structurally characterized for the first time using cryogenic infrared spectroscopy. In combination with quantum chemical calculations, the results reveal that the positive charge at the anomeric carbon of the sialyl cation is stabilized by remote participation of the C5-NHAc group leading to the formation of a bridged structure. In this structure, the β-side is shielded from nucleophilic attack, potentially explaining the α-selectivity of this building block in S N 1-type sialylation reactions. Other modes of participation are energetically unfavored and cannot be observed experimentally., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

Background: Magnetic capsule gastroscopy (MCG) is a non-invasive diagnostic method for the digestive tract. However, its efficiency in visualizing the gastric cardia is often compromised due to the capsule's rapid passage. This study introduces a novel sugar-glued tether-assisted technique inspired by a traditional Chinese snack-making process to enhance cardia visualization and patient comfort during MCG., Methods: This pilot, open-label, single-center, randomized controlled, non-inferiority study was conducted at Binzhou Medical University Hospital. Seventy-eight patients were enrolled and divided into three groups: conventional MCG, suction cup tether-assisted MCG, and sugar-glued tether-assisted MCG. The primary outcomes included safety, comfort level, and gastric cardia visualization quality. Secondary outcomes assessed technique-associated performance and clinical factors., Results: The sugar-glued tether-assisted MCG demonstrated comparable cardia visualization quality to the suction cup method, with significantly better results than conventional MCG. Comfort levels were significantly higher in the sugar-glued group compared to the suction cup group. The number of swallow attempts was significantly lower in the sugar-glued group, with no adverse events reported. Secondary outcomes showed no significant differences in MCG assembly time and ingestion-to-detachment period between the suction cup and sugar-glued groups., Conclusion: The sugar-glued tether-assisted MCG is a feasible and safe modification that enhances gastric cardia visualization while improving patient comfort. This technique provides a cost-effective alternative to the suction cup method, warranting further investigation in larger, multi-center studies., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Background & Aims: The quantity and quality of maternal nutrition in the periconception period is an important determinant for embryonic and foetal development and subsequent pregnancy course and outcome. The intake of ultra-processed foods (UPF) has increased worldwide and adverse health outcomes have been reported. However, the impact of UPF intake on the placenta, essential for prenatal nourishment, is unknown. Therefore, we aim to investigate associations between the periconceptional maternal intake of UPF, energy and related macronutrients, and first-trimester utero-placental vascular development., Methods: We included 214 ongoing pregnancies in the Virtual Placenta study, a subcohort of the Rotterdam periconception cohort. At enrollment, participants filled out a food frequency questionnaire from which we calculated the average daily energy from UPF, total energy intake and macronutrient intake from UPF. At 7-9-11 weeks of gestation, we performed sequential three-dimensional power Doppler ultrasounds of the first-trimester utero-placental vasculature. Virtual Organ Computer-aided AnaLysis (VOCAL) software, Virtual Reality segmentation and a skeletonization algorithm were applied to measure placental volume (PV), utero-placental vascular volume (uPVV) and generate the utero-placental vascular skeleton (uPVS). Absolute vascular morphology was quantified by assigning a morphologic characteristic to each voxel in the uPVS (end-, bifurcation-, crossing- or vessel point) and used to calculate density of vascular branching. Linear mixed models adjusted for confounders were used to investigate associations between maternal intake of UPF, total energy and macronutrients from UPF and PV, uPVV and uPVS characteristics., Results: Energy intake from UPF and total energy intake were not consistently associated with imaging markers of utero-placental vascular development. Higher carbohydrate intake of 10 g/day from UPF was associated with increased uPVS trajectories (end points (β = 0.34, 95%CI = 0.07; 0.61), bifurcation points (β = 0.38, 95%CI = 0.05; 0.70), vessel points (β = 0.957, 95%CI = 0.21; 1.71). No associations were observed with PV., Conclusions: Against our hypothesis, periconceptional maternal intake of UPF and total energy were not convincingly associated with impaired first-trimester utero-placental vascular development. Remarkably, the increased intake of carbohydrates from UPF, which is often considered 'unhealthy', is positively associated with first-trimester utero-placental vascular development. Given the complexity of diet, further research should elucidate what underlies these findings to be able to interpret how nutrition may impact utero-placental vascular development in early pregnancy., Clinical Trial Number: This study is registered at the Dutch Trial Register (NTR6854)., Competing Interests: Conflict of interest None., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The volatile fatty acids (VFAs) productions, as well as particulate organics decomposition, soluble chemical oxygen demand (SCOD) yield, and the VFAs production pathways from mesophilic and thermophilic anaerobic fermentation in waste activated sludge were investigated. Batch experiments showed that the decomposition rate of volatile suspended solids (VSS), particulate carbohydrate (P-C) and particulate protein (P-P) followed the first-order kinetic model at different temperatures. However, the intermediates, accumulated in the process of protein or carbohydrate digestion had a more significant inhibitory effect on the production of VFAs during the mesophilic anaerobic acidification process. The production of VFAs by thermophilic anaerobic fermentation is 2086.05 mg COD/L, which is about twice the production under mesophilic conditions. Among them, the concentration and proportion of high molecular weight organic acids such as isobutyric acid (320.29 mgCOD/L) and isovaleric acid (745.75 mgCOD/L) are relatively high. Then 13 C stable isotope labelling experiment demonstrated that, the decomposition of carbohydrates yields 77% acetic acid and 86% butyric acid, while protein breakdown produces 85% propionic acid and 99% valeric acid. This confirms that carbohydrates are more favourable for the formation of even-carbon organic acids, while proteins tend to yield odd-carbon organic acids. Additionally, this helps refine the pathway for valeric acid formation during anaerobic acidogenesis.

Objective: The study explored food items that contribute most toward increased fermentable carbohydrate (FC) intake and its association with diet quality in college students., Method: This cross-sectional study included 571 consented college students (≥18 years) with reported energy intakes (500-3500 kcal/day for women; 800-4000 kcal/day for men). FC intake and healthy eating index-2015 (HEI-2015) scores were assessed by diet history questionnaire-II. Data were analyzed by unadjusted bivariate linear regression and Pearson correlation tests., Results: The mean intakes of total FC (β = 1.24; 95% Confidence Interval: 1.02, 1.47) significantly predicted HEI-2015 scores. Positive correlations were found between FC intake and red and orange vegetables (r = 0.62), whole fruits (r = 0.63), and dark green vegetables (r = 0.58). Conclusions: Higher FC intake was associated with higher diet quality; vegetables and fruits are primary contributors to FC content. Efforts are required to promote these food items to improve diet quality and FC intake to shape eating choices in college students.

Background: The objective of this systematic review is to analyze the influence of carbohydrate (CHO) intake on physical and technical aspects, glucose and muscle glycogen levels, fatigue, cognition, and gastrointestinal comfort involved in the performance of soccer players, as well as to examine whether there are any differences between men and women., Methods: A bibliographic search was conducted in PubMed, Web of Science, Scopus, and SportDiscus, resulting in 61 selected articles. The PRISMA recommendations and the Cochrane Handbook for Systematic Reviews guidelines were followed., Results: The results indicate that CHO intake before and during the match improves speed and the number of sprints, attenuates the decrease in shooting accuracy and speed, increases time to fatigue, and enhances cognitive function. There is no consensus on passing, dribbling, jumping, or agility improvements. Glucose levels drop during the first 15 min of the second half without affecting performance., Conclusions: It is recommended that players ingest 6-8 g/kg/d of CHO the day before, a meal with 1-3 g/kg 3-4 h before, and 30-60 g/h during the match. Muscle glycogen drops drastically at the end of the match, remaining low at 48 h. Hence, 1-1.5 g/kg/h is recommended during the first 4 h, starting from the first 20 min. Female soccer players have a similar physical demand to men, and energy availability is low, especially in the post-match periods, as they underestimate their energy expenditure and do not consume enough CHO. Therefore, the recommended guidelines should be followed, individualized, and periodized according to each athlete's energy needs.

Background/objectives: Carbohydrate counting is recommended to improve glycemic control in type 1 diabetes (T1D), but the most effective educational methods are unclear. Despite its benefits, many individuals struggle with mastering carbohydrate counting, leading to inconsistent use and suboptimal glycemic outcomes. This study aimed to compare the effectiveness of two group-based programs with individual dietary counseling (standard care) for glycemic control., Methods: The trial was a randomized, controlled, open-label, parallel-group design. Adults with T1D on multiple daily insulin injections (MDIs) and with glycated hemoglobin A1c (HbA1c) 53-97 mmol/mol were randomly assigned (1:1:1) to basic (BCC), advanced carbohydrate counting (ACC), or standard care. Primary outcomes were the changes in HbA1c or mean amplitude of glycemic excursions (MAGEs) in BCC and ACC versus standard care after six months. Equivalence testing was performed to compare BCC and ACC., Results: Between November 2018 and August 2021, 63 participants were randomly assigned to BCC (N = 20), ACC (N = 21), or standard care (N = 22). After 6 months, HbA1c changed by -2 mmol/mol (95% CI -5 to 0 [-0.2%, -0.5 to 0]) in BCC, -4 mmol/mol (-6 to -1 [-0.4%, -0.6 to -0.1]) in ACC, and -3 mmol/mol (-6 to 0 [-0.3%, -0.6 to 0]) in standard care. The estimated difference in HbA1c compared to standard care was 1 mmol/mol (-3 to 5 [0.1%, -0.3 to 0.5]); p = 0.663 for BCC and -1 mmol/mol (-4 to 3 [-0.1%, -0.4 to 0.3]); p = 0.779 for ACC. For MAGEs, changes were -0.3 mmol/L (-1.5 to 0.8) in BCC, -0.0 mmol/L (-1.2 to 1.1) in ACC, and -0.7 mmol/L (-1.8 to 0.4) in standard care, with differences of 0.4 mmol/L (-1.1 to 1.9); p = 0.590 for BCC and 0.7 mmol/L (-0.8 to 2.1); p = 0.360 for ACC versus standard care. An equivalence in effect between BCC and ACC was found for HbA1c, but not for MAGEs., Conclusions: Group-based education in BCC and ACC did not demonstrate a clear advantage over individualized dietary counseling for overall glycemic control in adults with T1D. Healthcare providers should consider flexible, patient-centered strategies that allow individuals to choose the format that best suits their learning preferences when selecting the most suitable dietary educational approach.

Objective: To evaluate the effectiveness of chewing sugarless gum (SG) after water-rinsing in removing retained Oreo chocolate cookies (CC) from occlusal surfaces of teeth with and without fissure-sealant (FS)., Methods: A prospective study was performed on healthy children receiving prophylaxis at the paediatric-dentistry department. Immediately afterward, they chewed two CC. The occlusal surfaces of their posterior teeth were photographed 3 times: after 10 min, after 1 min of water-rinsing and after 4 min of chewing SG. An independent dentist screened all photos for the presence (partial or complete) or the absence of retained CC., Results: Participants included 28 children 7-14-year-old, with 100 primary and 214 permanent molars, of which, 150 teeth had FS. After chewing two CC, 290 (92.4%) teeth had retained CC. Water-swishing removed all, partial or none of the CC in 23%, 72.4% and 4.6% of the teeth, respectively. The effectiveness of chewing SG in completely removing retained CC was significantly higher than water-rinsing (p < 0.001), OR = 43.83, Cramer's V value = 0.871, suggesting a very strong correlation. The presence of FS raised the probability of completely removing retained CC after SG or water-rinsing (p < 0.001, OR = 107.7 and 25.9), with Cramer's V = 0.66 and 0.57, respectively, means a very strong association, as compared to teeth without (For both p < 0.001)., Conclusion: Chewing gum for 4 min was significantly more effective than water-rinsing for 1 min in removing retained CC. Moreover, FS considerably decreased the probability of retained CC on occlusal surfaces and increased the effectiveness of SG in removing it., (© 2024 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

Background: The dietary glycemic index (GI) and load (GL) reflect carbohydrate quality and quantity, potentially impacting fertility through modulation of insulin sensitivity and generation of oxidative stress. While fertility is influenced by both women and men, reproductive research often emphasizes maternal factors. We first examined periconception dietary intake in both women and male partners, and subsequent associations of dietary GI and GL with fecundability and subfertility., Methods: Among 830 women and 651 male partners, participating in a population-based prospective cohort study from preconception onwards, we assessed periconception dietary intake and calculated GI and GL, using a food frequency questionnaire (FFQ) at median 12.4 weeks gestation (95% range 10.9, 18.4). Information on time to pregnancy was obtained through questionnaires, with subfertility defined as a time to pregnancy ≥ 12 months or use of assisted reproductive technology., Results: In the periconception period, mean energy intake in women was 1870 kcal (SD: 500; 46% carbohydrates, 16% protein, 33% fat; dietary GI 56.2 (SD: 3.5) and GL 141.4 (SD: 67.4)). Mean energy intake in men was 2350 kcal (SD: 591; 43% carbohydrates, 16% protein, 33% fat; dietary GI 56.8 (SD: 3.2) and GL 156.7 (SD: 75.4)). Median time to pregnancy was 4.8 months (IQR: 1.2, 16.4), with 30.6% of 830 women experiencing subfertility. Dietary GI and GL were not associated with fertility outcomes in women. In men, higher dietary GI and GL across the full range were associated with decreased fecundability, after adjusting for socio-demographic and lifestyle factors, as well as dietary GI or GL of female partners [FR: 0.91, 95% CI 0.83, 0.99; FR: 0.90, 95% CI 0.81, 0.99, per SDS increase in dietary GI and GL, respectively]. When assessing the combined influence of dietary GI clinical categories in women and men, both partners adhering to a low GI diet tended to be associated with increased fecundability, but not with subfertility risk., Conclusions: Suboptimal periconception carbohydrate intake may be negatively associated with male fertility, but not with fertility outcomes in women. Further studies are needed to assess whether a lower GI and GL diet is a feasible lifestyle intervention to improve couples fertility., (© 2024. The Author(s).)

Gluconolactone serves as a readily available and inexpensive starting material for synthesizing the potential platform chemical (Z)-3-deoxy-1,2 : 5,6-di-O-isopropylidene-D-erythro-hex-3-enolactone in two steps. In this work, the selective elimination of triacetone gluconolactone was optimized. The resulting product is a versatile molecule, capable of being transformed into various compound classes in one or a few steps, i. e. potentially a new biomass-based platform chemical. This study demonstrates how it can be transformed into furanics, rare sugars, β-ketoamides, and amino furanones., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

Main Conclusion: Rice exudation patterns changed in response to P deficiency. Higher exudation rates were associated with lower biomass production. Total carboxylate exudation rates mostly decreased under P-limiting conditions. Within the rhizosphere, root exudates are believed to play an important role in plant phosphorus (P) acquisition. This could be particularly beneficial in upland rice production where P is often limited. However, knowledge gaps remain on how P deficiency shapes quality and quantity of root exudation in upland rice genotypes. We therefore investigated growth, plant P uptake, and root exudation patterns of two rice genotypes differing in P efficiency in semi-hydroponics at two P levels (low P = 1 µM, adequate P = 100 µM). Root exudates were collected hydroponically 28 and 40 days after germination to analyze total carbon (C), carbohydrates, amino acids, phenolic compounds spectrophotometrically and carboxylates using a targeted LC-MS approach. Despite their reported role in P solubilization, we observed that carboxylate exudation rates per unit root surface area were not increased under P deficiency. In contrast, exudation rates of total C, carbohydrates, amino acids and phenolics were mostly enhanced in response to low P supply. Overall, higher exudation rates were associated with lower biomass production in the P-inefficient genotype Nerica4, whereas the larger root system with lower C investment (per unit root surface area) in root exudates of the P-efficient DJ123 allowed for better plant growth under P deficiency. Our results reveal new insights into genotype-specific resource allocation in rice under P-limiting conditions that warrant follow-up research including more genotypes., (© 2024. The Author(s).)

The SnRK1, hexokinase, and TORC1 (TOR, LST8, RAPTOR) are three pivotal kinases at the core of sugar level sensing, significantly impacting plant metabolism and development. We retrieved and analyzed protein sequences of these three kinase pathways from seven sugarcane transcriptome and genome datasets, identifying protein domains, phylogenetic relationships, sequence ancestry, and in silico expression levels. Additionally, we predicted HXK subcellular localization and assessed its enzymatic activity in sugarcane leaves and culms along development in the field. We retrieved 11 TOR, 23 RAPTOR, 55 LST8, 95 SnRK1α, 98 HXK, and 14 HXK-like putative full-length sequences containing all the conserved domains. Most of these transcripts seem to share a common origin with the three ancestral species of sugarcane: Saccharum officinarum, Saccharum spontaneum, and Saccharum barberi. We accessed the expression profile of sequences from one sugarcane transcriptome. We found the highest enzymatic activity of HXK in culms in the first month, which, at this stage, provides carbon (sucrose) and nitrogen (amino acids) for initial plant development. Our approach places novel sugar sensing sequences that work as a guideline for further research into the underlying signaling mechanisms and biotechnology applications in sugarcane., (© 2024. The Author(s).)

[Cp*Ir(R-pica)Cl] (Cp*=pentamethylcyclopentadienyl anion, pica=2-picolineamidate) complexes bearing carbohydrate substituents on the amide nitrogen atom (R=methyl-β-D-gluco-pyranosid-2-yl, 1; methyl-3,4,6-tri-O-acetyl-β-D-glucopyranosid-2-yl, 2) were tested as catalysts for formic acid dehydrogenation in water. TOF MAX values over 12000 h -1 and 50000 h -1 were achieved at 333 K for 1 and 2, respectively, with TON values over 35000 for both catalysts. Comparison with the simpler cyclohexyl-substituted analogue (3) indicated that glucosyl-based complexes are much better performing under the same experimental conditions (TOF MAX =5144 h -1 , TON=5000 at pH 2.5 for 3) owing to a lower tendency to isomerize to the less active k 2 -N,O isomer upon protonation. The 5-fold increase in TOF MAX observed for 2 with respect to 1 is reasonably due to an optimal steric protection by the acetyl substituent, which may prevent unproductive inner-sphere reactivity. These results showcase a powerful strategy for the inhibition of the common deactivation pathways of [Cp*Ir(R-pica)X] catalysts for FA dehydrogenation, paving the way for the development of better performing hydrogen storage systems., (© 2024 Wiley-VCH GmbH.)

The flexible acquisition of substrates from nutrient pools is critical for microbes to prevail in competitive environments. To acquire glucose from diverse glycoside and disaccharide substrates, many free-living and symbiotic bacteria have developed, alongside hydrolysis, a non-hydrolytic pathway comprised of four biochemical steps and conferred from a single glycoside utilization gene locus (GUL). Mechanistically, this pathway integrates within the framework of oxidation and reduction at the glucosyl/glucose C3, the eliminative cleavage of the glycosidic bond and the addition of water in two consecutive lyase-catalyzed reactions. Here, based on study of enzymes from the phytopathogen Agrobacterium tumefaciens, we reveal a conserved Mn 2+ metallocenter active site in both lyases and identify the structural requirements for specific catalysis to elimination of 3-keto-glucosides and water addition to the resulting 2-hydroxy-3-keto-glycal product, yielding 3-keto-glucose. Extending our search of GUL-encoded putative lyases to the human gut commensal Bacteroides thetaiotaomicron, we discover a Ca 2+ metallocenter active site in a putative glycoside hydrolase-like protein and demonstrate its catalytic function in the eliminative cleavage of 3-keto-glucosides of opposite (α) anomeric configuration as preferred by the A. tumefaciens enzyme (β). Structural and biochemical comparisons reveal the molecular-mechanistic origin of 3-keto-glucoside lyase stereo-complementarity. Our findings identify a basic set of GUL-encoded lyases for glucoside metabolism and assign physiological significance to GUL genetic diversity in the bacterial domain of life., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Background/objectives: Traditional glycemic monitoring in type 2 diabetes is limited, whereas continuous glucose monitoring (CGM) offers better insights into glucose fluctuations. This study aimed to determine the correlations and relative contributions of fasting plasma glucose (FPG) and postprandial plasma glucose (PPG) levels to hyperglycemia., Methods: We utilized CGM and recorded carbohydrate intake data from lifestyle diaries of 59 patients enrolled in the Diabetes and Lifestyle Cohort Twente (DIALECT-2). Correlations between FPG and the glucose management indicator (GMI), FPG and Time Above Range (TAR), PPG and GMI, and PPG and TAR were conducted. Daily and mealtime relative contributions of PPG and FPG to glycated hemoglobin (HbA 1c ) and GMI were determined, considering two ranges: on target (<7.0%, 53 mmol/mol) and not on target (≥7.0%, 53 mmol/mol). Correlations between mealtime PPG and carbohydrate consumption were examined., Results: FPG and PPG correlated with GMI (r = 0.82 and 0.41, respectively, p < 0.05). The relative contribution of PPG in patients with HbA 1c , GMI, and TAR values not on target was lower than in patients with HbA 1c , GMI, and TAR values on target. When analyzing different mealtimes, patients with target GMI values had a higher PPG (73 ± 21%) than FPG after breakfast (27 ± 21%, p < 0.001). Individuals with elevated GMI levels had lower PPG after lunch (30 ± 20%), dinner (36 ± 23%), and snacks (34 ± 23%) than FPG. PPG after breakfast positively correlated (r = 0.41, p < 0.01) with breakfast carbohydrate intake., Conclusions: Both PPG and FPG contribute to hyperglycemia, with PPG playing a larger role in patients with better glycemic control, especially after breakfast. Targeting PPG may be crucial for optimizing glucose management.

Background: Due to the increasing prevalence of obesity and type 2 diabetes, effective dietary recommendations are needed. Previously, we developed the low-insulin method: by avoiding insulinogenic, i.e., insulin-release-triggering foods, insulin secretion becomes reduced, lipolysis is stimulated, and energy production is shifted to ketosis with excess ketone bodies exhaled in the form of acetone. Now, we investigate how quickly stable ketosis (defined as fasting breath acetone concentration ≥ 7.0 ppm) is achieved, whether and for how long a carbohydrate meal inhibits ketosis, and whether the responses differ in healthy adults with different insulin levels., Methods: An oral glucose tolerance test was conducted, and body composition and fasting insulin were determined at the beginning and end of the 14-day study. Participants ( n = 10) followed a ketogenic diet and performed continuous glucose monitoring. Ketosis levels were determined by measuring breath acetone concentrations. On day 8, two white bread rolls with jam (72 g carbohydrates) were consumed for breakfast., Results: After seven days, all participants achieved stable ketosis (defined as fasting breath acetone concentration ≥ 7.0 ppm), which dropped from 8.2 to 5.7 ppm ( p = 0.0014) after the carbohydrate meal. It took five days to achieve stable ketosis again. The stratification of participants into tertiles according to their fasting insulin levels demonstrated that individuals with low fasting insulin levels achieved stable ketosis again after two days and those with medium insulin levels after five days, while those with high baseline values did not reach stable ketosis by the end of the study., Conclusions: By carbohydrate restriction, stable ketosis can be achieved within one week. However, a single carbohydrate meal inhibits ketosis for several days. This effect is pronounced in individuals with elevated fasting insulin levels.

Objective: In addition to recent discussions of low-carbohydrate, high-fat diets (LCHF) from a performance perspective, there is a paucity of knowledge regarding influence of the combined effect of an exercise and nutritional intervention, which varies in carbohydrate (CHO) intake and glycemic indices, on blood lipid levels in recreationally active men., Methods: A total of 65 male runners (VO 2 peak = 55 ± 8 mL·min -1 ·kg -1 ) completed a 10-week ad libitum nutritional regimen (LOW-GI: ≥ 65% low GI CHO per day, n = 24; HIGH-GI: ≥ 65% high GI CHO per day, n = 20; LCHF: ≤ 50 g CHO daily, n = 21) with a concurrent prescribed endurance training intervention. Fasting total cholesterol (TC), triglycerides (TG), low-density lipoprotein cholesterol (LDL-C) and high-density lipoprotein cholesterol (HDL-C) were determined before and after the intervention. Additionally, 24-h dietary recalls were completed twice weekly., Results: Following the intervention, TC was significantly higher in LCHF (196 ± 37 mg·dL -1 ) compared to both LOW-GI (171 ± 41 mg·dL -1 ) and HIGH-GI (152 ± 28 mg·dL -1 , p  < 0.001). Additionally, LDL-C levels increased in LCHF (+17 ± 21 mg·dL -1 , p  = 0.001), while they decreased in both CHO groups ( p  < 0.05, respectively). Only the HIGH-GI group demonstrated a significant reduction in HDL-C (-3 ± 9 mg·dL -1 , p  = 0.006), while a decrease in TG was only significant in LOW-GI (-18 ± 36 mg·dL -1 , p  = 0.008)., Conclusion: Although mean blood lipid levels remained within the normal range, the data indicate that a low-carbohydrate, high-fat (LCHF) diet leads to unfavorable changes in individual blood lipid profiles compared to carbohydrate-rich diets. Therefore, it is recommended that the impact of a low-carbohydrate diet on blood lipids be considered when counseling active and healthy individuals., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2024 Kripp, Feichter and König.)

Objectives: The aim of this research was to evaluate changes in body composition, adipokine levels, and dyslipidemia parameters in males with abdominal obesity following two distinct interventions: exercise alone and exercise combined with an ad libitum diet., Methods: This study included 44 males with abdominal obesity (mean age 34.7 ± 5.5 years, waist circumference [WC] 110.3 ± 8.5, BMI 32.0 ± 3.9), who were randomly assigned to three groups: an experimental group engaging in aerobic-resistance exercise (II, n = 16), an experimental group engaging in aerobic-resistance exercise combined with an ad libitum high-protein, low-glycemic index carbohydrate diet (III, n = 16), both interventions lasting 6 weeks, and a control group without interventions (I, n = 12). Body composition metrics (body mass index [BMI], waist circumference [WC], body fat [BF], abdominal fat [ABD]) and fat-free mass [FFM], along with biochemical blood analyses (irisin [IR], omentin [OMEN], glucose [GLU], insulin [INS], LDL- and HDL-cholesterol), were measured at baseline and after the 6-week intervention. The effects of the interventions on the analyzed variables across groups were assessed using mixed ANOVA tests with post-hoc comparisons. Effect size (ES) was also calculated using partial eta squared ( η p 2 )., Results: The intervention in group III resulted in a significant decrease in IR ( p < 0.01, η p 2 = 0.03) by 41% and LDL-C ( p < 0.01, η p 2 = 0.02) by 14%. These effects were associated with a reduction in BF ( p < 0.01, η p 2 = 0.02) by 14%, ABD ( p < 0.01, η p 2 = 0.03) by 31%, and WC ( p < 0.01, η p 2 = 0.01) by 3%. In group II, decreases after 6 weeks of intervention were noted only in WC ( p = 0.02, η p 2 = 0.01) by 1% and in INS ( p < 0.01, η p 2 = 0.04) by 47%. No differences were found between groups. The use of low-glycemic index carbohydrates ( p < 0.01, η p 2 = 0.06) and increased protein intake ( p < 0.01, η p 2 = 0.30) led to changes in the fiber-to-energy value of the diet ratio ( p < 0.01, η p 2 = 0.18) and a reduction in dietary energy value ( p < 0.01, η p 2 = 0.13) by 23%, resulting in a greater energy deficit than in the II group., Conclusions: These findings highlight the effect of combining dietary and exercise interventions to achieve significant changes in body composition and metabolic parameters, even over a short period of intervention.

Reported herein is a new reaction for glycosylation with thioglycosides in the presence of iron(III) chloride. Previously, FeCl 3 was used for the activation of thioglycosides as a Lewis acid co-promoter paired with NIS. In the reported process, although 5.0 equiv of FeCl 3 are needed to activate thioglycosides most efficiently, no additives were used, and the reactions with reactive glycosyl donors smoothly proceeded to completion in 1 h at 0 °C. This work showcases a new direction in developing glycosylation methods using greener and earth-abundant activators.

Lipophosphoglycans (LPGs) are found on the surface of Leishmania, a protozoan parasite, and are immunologically important. Herein, disaccharide 1-phosphate repeating units of LPGs were successfully synthesized on a solid support with high anomeric purity using a disaccharide α-1-phosphoramidite building block. To enhance solubility in the reaction solvent, hydroxy-protecting groups in the form of para-t-butylbenzoyl were introduced to the building block. The saccharide chain was elongated via stable glycosyl boranophosphate linkages, followed by the conversion of inter-sugar linkages to phosphodiester counterparts using an oxaziridine derivative. The addition of a silylating reagent post-reaction with the oxaziridine derivative efficiently facilitated the conversion of boranophosohodiesters to phosphodiesters. This method enabled the α-selective synthesis of up to 15 repeating units, marking the longest homogeneous repeating units of LPGs synthesized chemically. Given the chain length equivalence to native LPGs, the method developed herein holds promise for advancing anti-Leishmanial pharmaceuticals and vaccines., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

The prevalence of lactose intolerance is one of the factors driving consumers toward plant-based milk alternatives (PBMA). This study aimed to analyze the carbohydrate profile of cows' milk (regular and lactose-free from both pasteurized and UHT milks; n = 80) and PBMA (n = 60) by HPLC. The study revealed that there was no significant difference in the energy content and total carbohydrate content between regular milk and lactose-free milk. Although milk and PBMA are entirely different food matrices, some PBMA types, as soya and coconut, may have energy contents and total carbohydrate contents comparable to those of milk. Furthermore, the variability observed in total carbohydrate content, as well as in carbohydrate profile, both between PBMA types and within samples of the same type, arises not only from variations in raw materials but also from the number of dilutions of the vegetable extract and the addition of different types and levels of carbohydrates, such as sucrose, fructose, or sorbitol, during PBMA manufacture. Although, milk presents a regular carbohydrate composition, differing solely between presentations (regular/lactose-free), the PBMA differs significantly between types and among the same type, not being for that reason regarded as a milk substitute., (© 2025, The Authors. Published by Elsevier Inc. on behalf of the American Dairy Science Association®. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).)

Carbohydrates constitute the largest source of biomass on Earth, but their synthetic modification is challenging due to their high content in oxygen functionalities. The site- and stereoselective modification of native sugars is a definite goal of glycochemistry research. Recent efforts to bypass the need for protecting groups, leveraging selective activation through photochemical mechanisms for site-selective C-C bond formation from native sugars, are likely to largely impact all glycochemistry-related areas. Davis, Koh, and co-workers have recently presented their use of photocatalysis to develop a "cap and glycosylate" approach for the site- and stereoselective C-glycosylation of native sugars. A modernized direct radical functionalization of in situ formed thioglycoside using photocatalysis was used in the synthetic manipulation of unprotected carbohydrates. This allowed reaching complex saccharides, and post-translational modification of proteins., (© 2024 Wiley-VCH GmbH.)

Aim: To investigate how delayed post-exercise carbohydrate intake affects muscle glycogen, metabolic- and mitochondrial-related molecular responses, and subsequent high-intensity interval exercise (HIIE) capacity., Methods: In a double-blind cross-over design, nine recreationally active men performed HIIE (10 × 2-min cycling, ~94% W˙ peak ) in the fed state, on two occasions. During 0-3 h post-HIIE, participants drank either carbohydrates ("Immediate Carbohydrate" [IC], providing 2.4 g/kg) or water ("Delayed Carbohydrate" [DC]); total carbohydrate intake over 24 h post-HIIE was matched (~7 g/kg/d). Skeletal muscle (sampled pre-HIIE, post-HIIE, +3 h, +8 h, +24 h) was analyzed for whole-muscle glycogen and mRNA content, plus signaling proteins in cytoplasmic- and nuclear-enriched fractions. After 24 h, participants repeated the HIIE protocol until failure, to test subsequent HIIE capacity; blood lactate, heart rate, and ratings of perceived effort (RPE) were measured throughout., Results: Muscle glycogen concentrations, and relative changes, were similar between conditions throughout (p > 0.05). Muscle glycogen was reduced from baseline (mean ± SD mmol/kg dm; IC: 409 ± 166; DC: 352 ± 76) at post-HIIE (IC: 253 ± 96; DC: 214 ± 82), +3 h (IC: 276 ± 62; DC: 269 ± 116) and + 8 h (IC: 321 ± 56; DC: 269 ± 116), returning to near-baseline by +24 h. Several genes (PGC-1ɑ, p53) and proteins (p-ACC Ser79 , p-P38 MAPK Thr180/Tyr182 ) elicited typical exercise-induced changes irrespective of condition. Delaying carbohydrate intake reduced next-day HIIE capacity (5 ± 3 intervals) and increased RPE (~2 ratings), despite similar physiological responses between conditions., Conclusion: Molecular responses to HIIE (performed in the fed state) were not enhanced by delayed post-exercise carbohydrate intake. Our findings support immediate post-exercise refueling if the goal is to maximize next-day HIIE capacity and recovery time is ≤24 h., (© 2024 Commonwealth of Australia and The Author(s). Acta Physiologica published by John Wiley & Sons Ltd on behalf of Scandinavian Physiological Society.)

Introduction: Preoperative carbohydrate intake is essential to enhance postoperative recovery. However, its safety for individuals with obesity remains unclear. This study investigated the safety of preoperative carbohydrate consumption compared to water intake in obese populations through gastric volume assessment., Methods: A prospective randomized crossover study enrolled 30 healthy volunteers aged 18-65 years with a body mass index ≥ 30 kg/m 2 , following a minimum 6-h fast. The participants received either 400 ml of a carbohydrate drink (group C) or water (group W). Gastric ultrasonography, blood glucose level, hunger, and thirst assessments were conducted at baseline (T) and various time points (T2 to T6). The protocol was repeated with reverse interventions at least 1 week later., Results: Group C had significantly higher gastric volume at T3, T4, and T5 compared to group W, with a prolonged time to empty the gastric antrum (94.4 ± 28.5 vs. 61.0 ± 33.5 min, 95% CI 33.41 [17.06,24.69]). However, glucose levels, degrees of hunger, and thirst showed no significant differences between the groups., Conclusion: Administering 400 ml of preoperative carbohydrates to healthy obese individuals 2 h preoperatively is safe and comparable to water intake. These findings support the integration of carbohydrate loading into perioperative care for obese individuals, consistent with the enhanced recovery after surgery protocols. Further research is warranted to refine preoperative fasting protocols and improve surgical outcomes in this population., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Reported herein is the synthesis of benzyl β-d-glucopyranoside and its derivatives that provide straightforward access to 3,4-branched glycans. Modes to diversify the synthetic intermediates via introduction of various temporary protecting groups have been demonstrated., Competing Interests: Declaration of competing interest The authors declare no competing financial interests., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Background: Many studies have reported the use of preoperative oral carbohydrates (CHO) in children, but the results are inconsistent. The aim of this meta-analysis is to assess the effectiveness and safety of oral CHO administration in children prior to surgery, with the goal of offering a dependable reference for clinical nursing practices and surgical interventions. Methods: Two authors searched PubMed, Clinical trials, Web of Science, Embase, Cochrane Library, China national knowledge infrastructure (CNKI), Wanfang and Weipu databases for randomized controlled trial (RCT) on the effects of preoperative oral CHO in children up to April 12, 2024. We used RevMan 5.4 software for data analysis. Results: Nine RCTs involving a total of 1279 children were included. The meta-analysis showed that there was statistical difference in the pH of gastric juice (MD = 1.54, 95%CI: 1.40-1.67, p < .001), intraoperative sedation score (MD = 0.62, 95%CI: 0.27-0.97, p < .001), and the incidence of postoperative nausea and vomiting (OR = 0.40, 95%CI: 0.20-0.80, p = .009) between the CHO and control groups. There was no statistical difference in the RGV (MD = -0.23, 95%CI: -0.47-0.01, p = .06) and the postoperative blood glucose level (MD = -0.91, 95%CI: -5.03-3.21, p = .67) between the CHO and control groups. Egger regression analysis showed that there were no publication biases amongst the synthesized outcomes (all p > .05). Conclusion: The administration of oral CHO to children before surgery is safe and practicable. There is a need for additional, well-conducted studies with more participants to further elucidate the role of preoperative CHO administration., Competing Interests: Declaration of Conflicting InterestsThe author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Background & Aims: The double burden of malnutrition compels us to reconsider macronutrients from a diet quality perspective. The Macronutrient Quality Index (MQI) has been designed to reflect overall macronutrient quality and is based on three sub-indexes: the carbohydrate quality index (CQI), the healthy plate protein quality index (HPPQI) and the fat quality index (FQI). Nutritional adequacy is an essential aspect of diet quality that should be captured by reliable dietary indexes., Methods: We analyzed the association between the Macronutrient Quality Index (MQI) and micronutrient adequacy. Participants were children aged 4 and 5 years, recruited in the SENDO cohort. Baseline information was collected through a self-administered online questionnaire, which included information on sociodemographic, dietary, and lifestyle variables. Dietary information was obtained using a 147-item validated semi-quantitative food frequency questionnaire. Participants were categorized into tertiles based on their MQI score. We evaluated the intake of 20 micronutrients and assessed the probability of micronutrient adequacy using the Estimated Average Requirement cut-off point., Results: Children in the highest tertile of MQI had 0.33-fold lower odds (95%CI 0.17-0.66) of having ≥3 inadequate micronutrient intakes than their peers in the lowest tertile, after adjusting for potential confounders. The adjusted proportions of children with inadequate intake of ≥3 micronutrients were 18%, 14% and 11% in the first, second, and third tertiles of MQI respectively. The MQI appears to be capable of capturing nutrient adequacy in children, although our results suggest that a modified MQI, with eggs and dairy products weighted positively, might be more adequate for the pediatric population., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Men generally favor carbohydrate metabolism, while women lean towards lipid metabolism, resulting in significant sex-based differences in energy oxidation across various metabolic states such as fasting and feeding. These differences are influenced by body composition and inherent metabolic fluxes, including increased lipolysis rates in women. However, understanding how sex influences organ-specific metabolism and systemic manifestations remains incomplete. To address these gaps, we developed a sex-specific, whole-body metabolic model for feeding and fasting scenarios in healthy young adults. Our model integrates organ metabolism with whole-body responses to mixed meals, particularly high-carbohydrate and high-fat meals. Our predictions suggest that differences in liver and adipose tissue nutrient storage and oxidation patterns drive systemic metabolic disparities. We propose that sex differences in fasting hepatic glucose output may result from the different handling of free fatty acids, glycerol, and glycogen. We identified a metabolic pathway, possibly more prevalent in female livers, redirecting lipids towards carbohydrate metabolism to support hepatic glucose production. This mechanism is facilitated by the TG-FFA cycle between adipose tissue and the liver. Incorporating sex-specific data into multi-scale frameworks offers insights into how sex modulates human metabolism., Competing Interests: Declaration of competing interest None Declared, (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Microcrystalline cellulose (MCC) is a crucial component in various industries, including pharmaceuticals, culinary, and cosmetics. The growing demand for MCC has spurred research into extraction methods. This study focused on extracting MCC from Ficus benghalensis using acid hydrolysis to convert the alpha-cellulose content of its leaves into MCC. The solvent used in this process was recyclable for further use. The extracted MCC was characterized by its physicochemical properties, including density, yield percentage, and structural characteristics. The yield was approximately 39.68 %, and the density was low at 1.518 g/cm 3 , making it suitable for filler applications. Fourier transform spectroscopy and UV-visible analysis identified functional groups of cellulose. X-ray diffraction analysis revealed a crystallite size of 1.560 nm and a crystallinity index of 66.43 %, indicating suitability for related applications. ImageJ determined a mean particle size of 36.545 μm, while scanning electron microscopy showed distinct surface orientations. Atomic force microscopy revealed surface roughness, root mean square, ten-point average roughness, skewness, and kurtosis. Elemental analysis indicated high concentrations of carbon (20.1 %) and oxygen (34 %). Based on these physicochemical features, the extracted MCC could be a valuable source for applications such as filler in reinforcement technology and coating material in pharmaceutical products., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper, (Copyright © 2024 Elsevier B.V. All rights reserved.)

Pancreatic cancer is a lethal disease with limited effective treatments. A deeper understanding of its molecular mechanisms is crucial to reduce incidence and mortality. Epidemiological evidence suggests a link between diet and disease risk, though dietary recommendations for at-risk individuals remain debated. Here, we propose that cell-intrinsic nutrient sensing pathways respond to specific diet-derived cues to facilitate oncogenic transformation of pancreatic epithelial cells. This review explores how diet influences pancreatic cancer predisposition through nutrient sensing and downstream consequences for (pre-)cancer cell biology. We also examine experimental evidence connecting specific food intake to pancreatic cancer progression, highlighting nutrient sensing as a promising target for therapeutic development to mitigate disease risk., (© 2024 Federation of European Biochemical Societies.)

Measurements of stable isotope ratios in organic compounds are widely used tools for plant ecophysiological studies. However, the complexity of the processes involved in shaping hydrogen isotope values (δ 2 H) in plant carbohydrates has limited its broader application. To investigate the underlying biochemical processes responsible for 2 H fractionation among water, sugars, and cellulose in leaves, we studied the three main CO 2 fixation pathways (C 3 , C 4 , and CAM) and their response to changes in temperature and vapor pressure deficit (VPD). We show significant differences in autotrophic 2 H fractionation (ε A ) from water to sugar among the pathways and their response to changes in air temperature and VPD. The strong 2 H depleting ε A in C 3 plants is likely driven by the photosynthetic H + production within the thylakoids, a reaction that is spatially separated in C 4 and strongly reduced in CAM plants, leading to the absence of 2 H depletion in the latter two types. By contrast, we found that the heterotrophic 2 H-fractionation (ε H ) from sugar to cellulose was very similar among the three pathways and is likely driven by the plant's metabolism, rather than by isotopic exchange with leaf water. Our study offers new insights into the biochemical drivers of 2 H fractionation in plant carbohydrates., (© 2024 The Author(s). New Phytologist © 2024 New Phytologist Foundation.)

Purpose: Infertility is a global health issue and nutrition plays a significant role in fertility outcomes. We aimed to investigate the cross-sectional and prospective associations of glycemic index (GI) and glycemic load (GL) with semen quality parameters in a cohort of healthy young men., Materials and Methods: The study included 106 men aged 18-35 years from the FERTINUTS trial. Dietary intake was estimated through 3-day dietary records and several semen parameters were assessed. Multivariable linear regression analysis with the Least Absolute Shrinkage and Selection Operator (LASSO) approach was employed., Results: The cross-sectional analysis revealed positive associations between GI and GL and total sperm count, sperm concentration, and total motility. In the prospective analysis, baseline GI was associated with increases in pH, vitality, immotile sperm or abnormal midpiece and decreases in total sperm count and motility. Conversely, GL was positively associated with changes in vitality and total sperm count., Conclusions: While these findings suggest that GI may have adverse effects on several sperm quality parameters, the results were not consistently observed in the cross-sectional analysis. However, GL was consistently associated with better sperm quality in both analyses. The impact of carbohydrate quality and quantity on fertility remains uncertain and larger prospective studies are needed., Competing Interests: The authors have nothing to disclose., (Copyright © 2024 Korean Society for Sexual Medicine and Andrology.)

Innate immune defense mechanisms against infection and cancer encompass the modulation of pattern recognition receptor (PRR)-mediated inflammation, including upregulation of various transcription factors and the activation of pro-inflammatory pathways important for immune surveillance. Dysfunction of PRRs-mediated signaling has been implicated in cancer and autoimmune diseases, while the overactivation of PRRs-driven responses during infection can lead to devastating consequences such as acute lung injury or sepsis. We used crystal structure-based design to develop immunomodulatory lipopolysaccharide (LPS) mimetics targeting one of the ubiquitous PRRs, Toll-like Receptor 4 (TLR4). Taking advantage of an exo-anomeric conformation and specific molecular shape of synthetic nonreducing β,β-diglucosamine, which was investigated by NMR, we developed two sets of lipid A mimicking glycolipids capable of either potently activating innate immune responses or inhibiting pro-inflammatory signaling. Stereoselective 1,1'-glycosylation towards fully orthogonally protected nonreducing GlcNβ(1↔1')βGlcN followed by stepwise assembly of differently functionalised phosphorylated glycolipids provided biologically active molecules that were evaluated for their ability to trigger or to inhibit cellular innate immune responses. Two LPS mimetics, identified as potent TLR4-specific inducers of the intracellular signaling pathways, serve as vaccine adjuvant- and immunotherapy candidates, while anionic glycolipids with TLR4-inhibitory potential hold therapeutic promise for the management of acute or chronic inflammation., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

para-Nitrophenyl (PNP) ethers of glycosides are important building blocks en route to functional carbohydrates. They are stable in neutral media, however, under basic conditions such as during the Zemplén deacylation of sugars, aryl migration is frequently observed. We have employed a library of O-PNP-substituted methyl glycosides of the manno-, galacto-, gluco- and altro-series to study the kinetics of aryl migration in MeOH/sodium methoxide using NMR spectroscopy revealing that migration between cis-oriented OH groups is faster than between trans-oriented ones. The rate constants of migration decrease in the order of Alt>Man>Gal>Glc and are related to the energy barriers of chair conformation inversion. The energy profile of the 3 to 4-PNP migration in methyl mannoside was calculated using DFT methods suggesting the Meisenheimer complex is an intermediate of PNP migration and that coordination of the sodium cation has a major impact on the energy profile., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

Drylands cover more than 40% of global land surface and will continue to expand by 10% at the end of this century. Understanding the resistance mechanisms of native species is of particular importance for vegetation restoration and management in drylands. In the present study, metabolome of a dominant shrub Campylotropis polyantha in a dry-hot valley were investigated. Compared to plants grown at the wetter site, C. polyantha tended to slow down carbon (C) assimilation to prevent water loss concurrent with low foliar reactive oxygen species and sugar concentrations at the drier and hotter site. Nitrogen (N) assimilation and turn over were stimulated under stressful conditions and higher leaf N content was kept at the expense of root N pools. At the drier site, roots contained more water but less N compounds derived from the citric acid cycle. The site had little effect on metabolites partitioning between leaves and roots. Generally, roots contained more C but less N. Aromatic compounds were differently impacted by site conditions. The present study, for the first time, uncovers the apparent metabolic adaptations of C. polyantha to hostile dryland conditions. However, due to the limited number of samples, we are cautious about drawing general conclusions regarding the resistance mechanisms. Further studies with a broader spatial range and larger time scale are therefore recommended to provide more robust information for vegetation restoration and management in dryland areas under a changing climate.

Boron Neutron Capture Therapy (BNCT) is a cancer treatment which combines tumor-selective boron delivery agents with thermal neutrons in order to selectively eradicate cancer cells. In this work, we focus on the early-stage development of carbohydrate delivery agents for BNCT. In more detail, we expand upon our previous GLUT-targeting approach by synthesizing and evaluating the potential embedded in a representative set of fluorinated carbohydrates bearing a boron cluster. Our findings indicate that these species may have advantages over the boron delivery agents in current clinical use, e.g., significantly improved boron delivery capacity at the cellular level. Simultaneously, the carbohydrate delivery agents were found to bind strongly to plasma proteins, which may be a concern requiring further action before progression to in vivo studies. Altogether, this work brings new insights into factors which need to be accounted for if attempting to develop theranostic agents for BNCT based on carbohydrates in the future.

A 34-year-old Asian woman arrived at the emergency department (ED) with complaints of sharp, cramping abdominal pain followed by stabbing chest pain that radiated to her back. She also reported numbness, tingling in both hands and feet, and a burning sensation. Upon examination, she exhibited tachycardia and persistently elevated blood pressure. Her lab results revealed low potassium and sodium levels. Despite testing negative for pregnancy, normal hepatic function test, and nerve conduction study, her symptoms persisted, and she was admitted to the intensive care unit for the monitoring and correction of her electrolyte imbalances. She was later discharged but continued to experience symptoms, prompting multiple ED visits. The patient reported the symptoms following a calorie-restricted ketogenic diet and receiving human chorionic gonadotropin (hCG) injections for weight loss, which led the providers to initially diagnose her with "keto flu" due to inadequate nutrient intake. Despite receiving this diagnosis, her symptoms worsened, and she experienced pain throughout her whole body, along with muscle pain and abnormal sensations. Further assessment revealed that her urine was brown and showed abnormal levels of porphyrins, indicating acute intermittent porphyria. A genetic test confirmed the presence of a pathogenic mutation in hydroxymethylbilane synthase (HMBS), leading to a diagnosis of late-onset acute intermittent porphyria., Competing Interests: Human subjects: Consent was obtained or waived by all participants in this study. Conflicts of interest: In compliance with the ICMJE uniform disclosure form, all authors declare the following: Payment/services info: All authors have declared that no financial support was received from any organization for the submitted work. Financial relationships: All authors have declared that they have no financial relationships at present or within the previous three years with any organizations that might have an interest in the submitted work. Other relationships: All authors have declared that there are no other relationships or activities that could appear to have influenced the submitted work., (Copyright © 2024, Ali et al.)

A key challenge in oligosaccharide synthesis is the stereoselective installation of glycosidic bonds. Each glycosidic linkage has one of two possible stereo-chemical geometries, α/β or 1,2-cis/trans. An established approach to install 1,2-trans glycosidic bonds is neighboring group participation (NGP), mediated by a 2-O-acyl group. Extension of this intramolecular stabilization to nucleophilic groups located at more remote positions has also been suggested, but remains poorly understood. Previously, we employed infrared ion spectroscopy to characterize the molecular ions of monoacetylated sugar donors and showed how the strength of the stabilizing effect depends on the position of the participating ester group on the glycosyl donor ring as well as on its relative stereochemistry. In this work, we investigated glycosyl donors carrying two acyl groups. Using isotope labelling and isomer population analysis we were able to resolving spectra of isomeric mixtures and establish the relative contribution of individual species. We conclude that 3,4-diacetyl mannosyl donors exclusively form a dioxanium ion as a result of C-3 acyl stabilization. In contrast, the glucosyl and galactosyl cations form mixtures of C-3 and C-4 acyl participation products. Hence, the combination of isotope labeling and population analysis allows for the study of increasingly complex glycosyl cations., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

Background and Aims: The time paediatric patients should resume oral intake after surgery is still ill-defined. No specific evidence suggests that the usual practice of postoperative fasting of 4-6 h to reduce postoperative nausea and vomiting (PONV) is beneficial. The primary objective of this study was to assess the occurrence of PONV with early oral feeding compared to conventional feeding in children undergoing daycare surgery under general anaesthesia., Methods: A randomised controlled trial was conducted in 300 children undergoing daycare surgery under general anaesthesia. Children were randomised into the early feeding group (Group EF, n = 150) or the conventional feeding group (Group CF, n = 150). Group EF received carbohydrate-containing oral fluids when the child demanded feed in the postoperative period. Group CF received oral fluids 4 h post-anaesthesia. All patients were monitored for occurrence of PONV, postoperative pain, duration of hospital stay and parental satisfaction. The incidence of PONV was compared using the Chi-squared test, while other continuous variables were compared using the Student's t -test., Results: Both groups were comparable regarding PONV (12% in Group EF vs. 18.7% in Group CF, P = 0.109). The Face, Legs, Activity, Cry, Consolability scores were significantly lower in Group EF at 0 min ( P = 0.011), 30 min ( P = 0.001) and 1 h ( P < 0.001). Patients in Group EF had a significantly shorter duration of hospital stay, that is, 6.31 [standard deviation (SD): 3.52] [95% confidence interval (CI): 1.45-12.24] h in EF versus 10.13 (SD: 2.99) (95% CI: 5.12-16.33) h in CF ( P < 0.001). Parents of the children in Group EF had significantly better parental satisfaction scores ( P < 0.001)., Conclusion: Early postoperative feeding in children undergoing lower abdominal, non-gastrointestinal surgery under general anaesthesia does not increase the incidence of PONV., Competing Interests: There are no conflicts of interest., (Copyright: © 2024 Indian Journal of Anaesthesia.)

Importance: Porcine epidemic diarrhea virus (PEDV) binds to particular cell surface receptors to penetrate cells. The virus specifically identifies certain carbohydrate structures present on the surface of the cell to facilitate the binding process. Nevertheless, the influence of viral infections on specific alterations of glycoconjugates in the small intestines remains unexplored., Objective: This work aimed to examine the alterations in glycoconjugates in the small intestines of piglets naturally infected with PEDV using lectin histochemistry., Methods: Six piglets including three PEDV-infected and three non-infected piglets were evaluated. Small intestinal samples were histopathologically examined, and lectin histochemistry was performed., Results: Piglets infected with PEDV had significant histological abnormalities in their small intestines, such as pronounced villous atrophy, varying degrees of villous fusion, and diverse mucosal alterations. Specific regions of the duodenum, jejunum, and ileum showed discernible variations in glycoconjugate distribution, as determined by lectin histochemistry. Compared with the controls, the PEDV-infected piglets showed significant changes in N-acetylglucosamine- and galactose-binding lectins (particularly wheat germ agglutinin and Arachis hypogaea (peanut) agglutinin) in multiple intestinal regions., Conclusions and Relevance: These findings can enhance understanding of how viruses such as PEDV impact the glycoconjugate composition of the small intestines and emphasize the potential connection between the pathogenesis of PEDV and glycoconjugate., Competing Interests: The authors declare no conflicts of interest., (© 2024 The Korean Society of Veterinary Science.)

Agricultural activities produce large quantities of organic byproducts and waste rich in lignocellulosic materials, which are not sufficiently utilized. In this study, alternative agricultural waste products, namely, spent mushroom substrate (SMS) from the cultivation of edible Pleurotus ostreatus mushrooms and the roots of leafy vegetables from hydroponic cultivation (HRL), were evaluated for their potential to be used as substrates for the cultivation of Pleurotus citrinopileatus and their effects on the quality, the nutritional value, the chemical properties (lipid, protein, carbohydrate, ash, fatty acid and carbohydrate composition) and the bioactive content (total phenolic compounds and antioxidant activity) of produced mushrooms. SMS and HRL (in different ratios with and without additives) and wheat straw with additives (WS-control) were used. During incubation, the linear growth rate of the mycelium (Kr, mm/day) was measured and used for screening. Mushroom cultivation took place in bags, where several characteristics were examined: earliness (duration between the day of substrate inoculation and the day of first harvest) and biological efficiency (B.E. %, the ratio of the weight of fresh mushrooms produced per dry weight of the substrate × 100). Furthermore, this study aimed to investigate the effect of the protein extract (PE) and carbohydrate extract (CE) of P. citrinopileatus after in vitro digestion (fraction less than 3kDa: PE-DP-3; digestate fraction: CE-D, respectively) on the expression of antioxidant-related genes in the THP-1 cell line. The results showed that mushrooms grown on SMS 50%-HRL 40% had the fastest growth (6.1 mm/d) and the highest protein and lipid contents (34.7% d.w.; 5.1% d.w.). The highest B.E. (73.5%), total carbohydrate (65.7%) and total phenolic compound (60.2 mg GAE/g d.w.) values were recorded on the control substrate. Antioxidant activity was observed in all extracts; the total flavonoid content was low in the samples, and the maximum total triterpene value was detected in SMS 80%-HRL 20% (9.8 mg UA/g d.w.). In all mushrooms, linoleic acid (C18:2) was the main fatty acid (above 60%), and fructose was the dominant individual saccharide. In the investigation of the regulation pathway, NFE2L2 gene expression was upregulated only in the SMS 60%-HRL 40% intervention during incubation with CE-D samples. Additionally, the transcription levels of antioxidant-related genes, SOD1, CAT, HMOX1 and GSR, were increased in the SMS 60-30% intervention. Compared to WS, the alternative substrates are observed to trigger a pathway concerning CE that may resist oxidative stress. This study supports the utilization of agricultural byproducts through sustainable and environmentally friendly practices while simultaneously producing high-value-added products such as mushrooms. Therefore, alternative substrates, particularly those containing HRL, could serve as natural sources of antioxidant potential.

The study aims to evaluate the effect of an acute meal and long-term intake of Mediterranean Diet (MD) on different parameters such as strength, physical performance, body composition and blood markers in a group of non-professional athletes who practice a strength activity. Thirteen volunteers completed two 8-week dietary interventions in a randomised, cross-over design. Also an acute study was performed. Subjects received a MD High in carbohydrates, characterised by at least five portions of pasta/week and an average 55-60% of daily energy derived from carbohydrates, versus an MD reduced in carbohydrates, with less than two portions of pasta/week and an average of 40-45% of daily energy provided by carbohydrates. Mainly, data did not show significant differences for the parameters analysed, except for Elbow Flexor maximum voluntary contraction ( p  = .039). Results enlighten that increasing total carbohydrates intake, as typically in the MD, does not negatively affect physical performance, body composition and strength.