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Summary: An expanding list of marine species has been identified and evaluated for their potential bioactivity and nutritional values. Most attention is directed toward utilising protein‐rich by‐products of fish processing for their bioactive functionalities, which can aid in minimising waste and add value to underutilised resources. Milt and roe, the reproductive constituents of fish, are known to contain a high concentration of nutritional content. Bioactive peptides derived from these constituents have shown several biological activities including antihypertensive, antibacterial, anticoagulant, anti‐inflammatory, anti‐obesity, anti‐cancer, and antioxidant activities. These peptides are commonly extracted by enzymatic hydrolysis and purified by different chromatographic methods according to their mass, molecular size, and composition. This review discusses the approaches to produce, purify, and characterise the protein hydrolysates from fish milt and roe and delves into the compositions of the nutraceutical compounds derived from milt and roe. The review also highlights the bioactive properties of the milt and roe‐derived peptides that can have potential applications in the food, nutraceutical, pharmaceutical, and cosmeceutical industries. [ABSTRACT FROM AUTHOR]

Cationic starch (CatS) coating of cellulose fabrics enables salt‐free reactive dyeing. However, the relation of the degree of substitution and CatS concentration in the dyeing procedure are open issues. Accordingly, three cationic starches of increasing degree of substitution were used at different concentrations for the coating of cotton fabrics. Fabrics were evaluated for stiffness, dye uptake, dye exhaustion, wash fastness and nitrogen content. With an increasing degree of substitution coating solutions become more viscous, resulting in increased wet pick‐up and less stiff coated fabrics. These fabrics show increasing dye absorption and color generation. Due to the molecular size of the cationic starch, yarn/fiber ring dyeing is supposed present. Specifically, color generation can be adjusted by initial cationic starch coating concentration. Above 5 % CatS concentration ceases to have an increasing coloration effect. Pre‐treating a cellulose fabric with approximately 2.2 % CatS (Ds=0.7) enables similar coloration to a standard reactive dyeing protocol. Light fastness is reduced by 1–1.5 compared to salt‐based reactive dyeing. Rub fastness decreases by 1–2 only for higher substituted cationic starches (Ds=0.7). Nitrogen analysis reveals that a share of the CatS elutes off the fabrics into the dye bath. [ABSTRACT FROM AUTHOR]

The current state of reticular chemistry enables the synthesis of a wide range of highly porous nanomaterials for gas separation, including metal‐organic frameworks (MOFs), covalent organic frameworks (COFs), porous organic cages (POCs), metal‐organic cages (MOCs), and polyhedra (MOPs). This perspective focuses on membrane technology, a key player in energy‐efficient gas separations. It explores the world of reticular materials, taking a glance at tiny pore windows with narrow openings, which are ideal for high‐resolution molecular sieving, and how to design them. Promising concepts in this field are membranes consisting of neat materials, but also mixed matrix membranes, where polymeric films incorporate reticular fillers, creating cost‐efficient membranes. This article sheds light on the potential use of reticular materials as membrane components. The reticular synthesis of MOFs offers the ability to separate gas molecules with minimal size differences effectively. For COFs, the crucial factor lies in reducing their pore size, preferably through functional group modifications. Porous cage compounds can achieve fine distribution from homogeneous dispersions into polymers making them excellent candidates for mixed matrix membranes. This perspective provides strategies and guiding principles for the future of reticular nanomaterials‐based membranes, addressing the pressing need for advanced and efficient separation technologies. [ABSTRACT FROM AUTHOR]

Graphene‐like molecules with multiple zigzag edges are emerging as promising gain materials for organic lasers. Their emission wavelengths can vary widely, ranging from visible to near‐infrared (NIR), as the molecular size increases. Specifically, rhombus‐shaped molecular graphenes with two pairs of parallel zigzag edges, known as [n]rhombenes, are excellent candidates for NIR lasers due to their small energy gaps. However, synthesizing large‐size rhombenes with emission beyond 800 nm in solution remains a significant challenge. In this study, we present a straightforward synthesis of an aryl‐substituted [4]rhombene derivative, [4]RB‐Ar, using a method that combines intramolecular radical‐radical coupling with Bi(OTf)3‐mediated cyclization of vinyl ethers. The structure of [4]RB‐Ar was confirmed through X‐ray crystallographic analysis. Bond length analysis and theoretical calculations indicate that aromatic sextets are predominantly localized along the molecule's long axis. Significantly, [4]RB‐Ar demonstrates narrow amplified spontaneous emission at around 834 nm when dispersed in polystyrene thin films. Moreover, solution‐processed distributed feedback lasers employing [4]RB‐Ar as the active gain material display tunable narrow emissions in the range of 830 to 844 nm. [ABSTRACT FROM AUTHOR]

Protein therapeutics are emerging as essential technologies due to their functional and chemical properties. However, their application is currently limited to delivery by oral and injection methods—the former being inefficient and the latter invasive and potentially tissue damaging. Researchers are, therefore, exploring noninvasive delivery systems for proteins through the skin, including transdermal and topical delivery. The large molecular size of proteins presents a key challenge for skin penetration, hindering their ability to penetrate the dense skin lamellar structure. This review focuses on using nanoparticles as carriers to increase protein stability and enhance skin penetration. The use of noninvasive or minimally invasive enhancers for controlling and improving penetration depth is also examined. Furthermore, the physical properties of nanoparticles that affect delivery are evaluated, aiming to propose ways to advance transdermal and topical delivery methods in the future. [ABSTRACT FROM AUTHOR]

Most albumin in blood plasma is thought to be monomeric with some 5% covalently dimerized. However, many reports in the recent biophysics literature find that albumin is reversibly dimerized or even oligomerized. We review data on this from X‐ray crystallography and diverse biophysical techniques. The number‐average molecular weight of albumin would be increased by dimerization, affecting size‐dependent filtration processes of albumin such as at the glycocalyx of the capillary endothelium and the podocyte slit‐diaphragm of the renal glomerulus. If correct, and depending on characteristics of the process, such as Kd, reversible dimerization of albumin in plasma would have major implications for normal physiology and medicine. We present quantitative models of the impact of dimerization on albumin molecular forms, on the number‐average molecular weight of albumin, and estimate the effect on the colloid osmotic pressure of albumin. Dimerization reduces colloid osmotic pressure as total albumin concentration increases below that expected in the absence of dimerization. Current models of albumin filtration by the renal glomerulus would need revision to account for the dynamic size of albumin molecules filtered. More robust biophysical data are needed to give a definitive answer to the questions posed and we suggest possible approaches to this. What is the central question of this study?Is there reversible dimerization of albumin in blood plasma? Albumin in blood plasma is generally considered monomeric apart from a small proportion of covalent dimer, but recent reports suggest it may actually be reversibly dimerized: is this physiologically significant?What is the main finding and its importance?There is some evidence that fatty acid‐free albumin dimerizes but less for native albumin. Dimerization, if proven, requires revision of the current molecular concepts underlying observed colloid osmotic pressures of plasma and renal ultrafiltration of albumin. Biophysical evidence for dimerization in plasma is currently weak. [ABSTRACT FROM AUTHOR]

Multivalency is a fundamental principle in nature that leads to high‐affinity intermolecular recognition through multiple cooperative interactions that overcome the weak binding of individual constituents. For example, multivalency plays a critical role in lectin‐carbohydrate interactions that participate in many essential biological processes. Designing high‐affinity multivalent glycoconjugates that engage lectins results in systems with the potential to disrupt these biological processes, offering promising applications in therapeutic design and bioengineering. Here, a versatile and tunable synthetic platform for the synthesis of metallosupramolecular glycoassemblies is presented that leverages subcomponent self‐assembly, which employs metal ion templates to generate complex supramolecular architectures from simple precursors in one pot. Through ligand design, this approach provides precise control over molecular parameters such as size, shape, flexibility, valency, and charge, which afforded a diverse family of well‐defined hybrid glyconanoassemblies. Evaluation of these complexes as multivalent binders to Concanavalin A (Con A) by isothermal titration calorimetry (ITC) demonstrates the optimal saccharide tether length and the effect of electrostatics on protein affinity, revealing insights into the impact of synthetic design on molecular recognition. The presented studies offer an enhanced understanding of structure‐function relationships governing lectin‐saccharide interactions at the molecular level and guide a systematic approach towards optimizing glyconanoassembly binding parameters. [ABSTRACT FROM AUTHOR]

Robust high‐valence metal–organic framework (MOF) membranes for CO2 separations show great promise for achieving carbon neutrality. Herein, the elegant fabrication of tetravalent zirconium Materials of Institute Lavoisier‐140A (MIL‐140A) membranes are pioneered and validated the intriguing dual role for both CO2‐selective and CO2‐rejective separations by combining structural regulation with the exploitation of the appropriate anisotropic ultramicropores. This inimitable separation ability of "hitting two targets with one arrow" with distinctive molecular size cut‐offs, which originated from the significant orientation transformation, enables the membranes to satisfy multiscenario CO2 capture requirements. The preferred (h0h)‐oriented MIL‐140A membranes exhibit superior mixed CO2/CH4 separation capacities (a separation factor of ≈30), while the highly (200)‐oriented MIL‐140A membranes exhibit remarkable mixed H2/CO2 separation capacities (a separation factor of ≈540), and they both ranked at the top among the present MOF membranes. This work highlights the promising prospects of the fresh MIL‐140 series for a given membrane‐based multiscenario CO2 separation application through microstructure customization and manipulation. [ABSTRACT FROM AUTHOR]

Layer‐stacking behaviors are crucial for two‐dimensional covalent organic frameworks (2D COFs) to define their pore structure, physicochemical properties, and functional output. So far, fine control over the stacking mode without complex procedures remains a grand challenge. Herein, we proposed a "key‐cylinder lock mimic" strategy to synthesize 2D COFs with a tunable layer‐stacking mode by taking advantage of ionic liquids (ILs). The staggered (AB) stacking (unlocked) COFs were exclusively obtained by incorporating ILs of symmetric polarity and matching molecular size; otherwise, commonly reported eclipsed (AA) stacking (locked) COFs were observed instead. Mechanistic study revealed that AB stacking was induced by a confined interlocking effect (CIE) brought by anions and bulky cations of the ILs inside pores ("key" and "cylinder", respectively). Excitingly, this strategy can speed up production rate of crystalline powders (e.g. COF‐TAPT‐Tf@BmimTf2N in merely 30 minutes) under mild reaction conditions. This work highlights the enabling role of ILs to tailor the layer stacking of 2D COFs and promotes further exploration of their stacking mode‐dependant applications. [ABSTRACT FROM AUTHOR]

2D Dion–Jacobson (DJ) perovskites show structural stability and tunability and are regarded as promising photovoltaic materials. The spacer cations play an important impact on exciton separation and charge transport of 2D perovskites. Herein, a novel spacer with thiazole as core, 2‐thiazolemethanammonium (AMT), owning characters of small molecular size, delocalized π‐electrons, and strong electron‐withdrawing ability, is introduced to construct 2D DJ perovskites. Owing to the strong orbital coupling between AMT spacer and inorganic layers, the AMT‐based perovskite exhibits type II quantum well structure, which is favorable for exciton separation. On contrary, such interaction does not appear in the DJ perovskite when aliphatic propyldiammonium (PDA), with a similar length, is used as spacer. The AMT spacer can also induce better crystallinity, resulting in reduced defect density and improved charge transport ability. The optimized device based on (AMT)MA3Pb4I13 exhibits a power conversion efficiency (PCE) of 19.69%, which is a record for 2D DJ perovskite solar cells (PSCs) (n ≤ 4). This work provides deep understanding of the impact of aromatic spacer on the electronic structure of 2D DJ perovskites and the corresponding photovoltaic performance and provides a new opportunity toward highly efficient and stable PSCs. [ABSTRACT FROM AUTHOR]

The grain size of rice (Oryza sativa) plays a pivotal role in determining yield. It is crucial to explore the genes related to grain size and analyze their molecular mechanisms to enhance rice yield further. This study identified a small‐grain mutant small grain 12 (sg12), from the ethyl methanesulfonate‐induced mutant library of Shuhui 498, a backbone parent of heavy‐panicle hybrid rice. We found that sg12 rice mutant exhibits a decrease in grain size and 1000‐grain weight, but an increase in grain number per panicle. Genetic analysis indicated that the small grain of sg12 is controlled by a pair of semi‐dominant genes. Furthermore, cytological analysis showed that the number of longitudinal cells in the spikelet hull of sg12 decreased, indicating that SG12 regulates grain size by affecting cell proliferation. In this study, we also identified a candidate gene of SG12 as OsPPKL3, which encodes a putative protein phosphatase with Kelch‐like repeat domains. A single‐nucleotide polymorphism substitution (G/A) occurred in the conserved Kelch domain of OsPPKL3 in the sg12, resulting in the mutation of the 176th amino acid from Ala to Thr, and this amino acid substitution led to significant differences in the three‐dimensional structure of the OsPPKL3 protein. Finally, genetic analysis indicated that OsPPKL3 regulates grain size independent of Oryza sativa BRI1‐associated receptor kinase 1 (OsBAK1) and Oryza sativa Brassinosteroid‐signaling kinase 2 (OsBSK2). Overall, this study identified a new allelic mutant of OsPPKL3, clarified the cytological basis of OsPPKL3 regulating grain size, and emphasized the crucial role of the 176th amino acid in the Kelch domain of OsPPKL3 for its biological function. Our results provided important resources for further studying the molecular mechanisms of OsPPKL3 regulating grain size in rice. [ABSTRACT FROM AUTHOR]

BACKGROUND RESULTS CONCLUSION Natural emulsifiers are increasingly preferred by the food industry to meet consumers' demand for ‘clean‐label’ emulsion products. In the present study, 10 short‐term retrograded starches with unique molecular structures were explored to examine the relationships between starch structures and their ability to form stable oil‐in‐water emulsions.Waxy maize starch showed the largest value of contact angle and conductivity of emulsion, whereas potato and lentil starch showed the lowest value of contact angle and conductivity of emulsion, respectively. Emulsion prepared by rice starch showed the lowest, whereas that of sweet potato starch showed the highest value of viscosity. Consequentially, the emulsion stabilized with waxy maize and tapioca starch showed the smallest and less polydisperse droplets, resulting in a much higher emulsifying index. On the other hand, emulsion prepared with potato starch showed the highest stability compared to other starches. Correlation analysis suggested that starches with larger molecular size, a lower amylose content and shorter amylopectin short chains had a higher emulsification ability, whereas the amount of starch molecular interactions formed during short‐term retrogradation revealed no obvious linking to emulsion performances.These findings provided food industry with exciting opportunities to develop ‘clean‐label’ emulsions with desirable properties. © 2024 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

Cyclic polymers, which are found in the field of biopolymers, exhibit unique physical properties such as suppressed molecular mobility. Considering thermodynamics, the suppressed molecular mobility of cyclic polymers is expected to prevent unfavorable entropy loss in molecular interactions. In this study, we synthesized cyclic glycopolymers carrying galactose units and investigated the effects of their molecular mobility on the interactions with a lectin (peanut agglutinin). The synthesized cyclic glycopolymers exhibited delayed elution time on size exclusion chromatography and a short spin‐spin relaxation time, indicating typical characteristics of cyclic polymers, including smaller hydrodynamic size and suppressed molecular mobility. The hemagglutination inhibition assay revealed that the cyclic glycopolymers exhibited weakened interactions with peanut agglutinin compared to the linear counterparts, attributable to the suppressed molecular mobility. Although the results are contrary to our expectations, the impact of polymer topology on molecular recognition remains intriguing, particularly in the context of protein repellent activity in the biomedical field. [ABSTRACT FROM AUTHOR]

The heterogeneous selective hydrogenation of nitrile butadiene rubber (NBR) is an efficient method to generate high value‐added hydrogenated NBR. Nevertheless, the inherent large molecular size and high spatial hindrance of polymers lead to poor activity and metal loss. Herein, we report a simple support ammonia pretreatment strategy for the synthesis of efficient N‐doped Pd catalyst and applied for the NBR hydrogenation. The results reveal that N doping enhances electron transfer from the support to Pd more effectively than oxygen‐rich vacancy support, thereby substantially enhancing the electron cloud density and stability of the Pd sites. The formation of more electron‐rich Pd sites not only significantly enhances the adsorption‐activation ability of C=C and H2, but also lowers the apparent activation energy of the reaction. As a result, the Pd/N‐TiO2‐R demonstrates best activity with a hydrogenation degree (HD) of 98 % and a TOF value of 335 h−1, significantly higher than that of Pd/TiO2−R (HD=83 %, 282 h−1) and Pd/TiO2 (HD=74 %, 204 h−1). This strategy will provide new inspiration to improve the activity and stability of Pd/TiO2 catalysts for the hydrogenation of unsaturated polymers. [ABSTRACT FROM AUTHOR]

Background: Peach gum (PG) is an exudate of the peach tree (Prunus persica of the Rosaceae family), which consists primarily of polysaccharides with a large molecular weight and branching structure. Consequently, PG can only swell in water and does not dissolve easily, which severely limits its application. Current conventional extraction methods for PG polysaccharide (PGPS) are time consuming and inefficient. This study investigated the impact of ultrasonic‐assisted extraction (UAE) on PGPS structure and conformation, and their relationship to hypoglycemic activity in vitro. Results: In comparison with conventional aqueous extraction, UAE enhanced PGPS yielded from 28.07–32.83% to 80.37–84.90% (w/w) in 2 h. It drastically decreased the molecular size and conformational parameters of PGPS, including weight‐average molecular weight (Mw), number‐average molecular weight (Mn), z‐average radius of gyration (Rg), hydrodynamic radius (Rh) and instrinsic viscosity ([η]) values. Peach gum polysaccharide conformation converted extended molecules to flexible random coil chains or compact spheres with no obvious primary structure alteration. Furthermore, UAE altered the flow behavior of PGPS solution from that of a non‐Newtonian fluid to that of a Newtonian fluid. As a result, PGPS treated with UAE displayed weaker inhibitory activity than untreated PGPS, mostly because UAE weakens the binding strength of PGPS to α‐glucosidase. However, this negative effect of UAE on PGPS activity was compensated by the increased solubility of polysaccharide. This enabled PGPS to achieve a wider range of doses. Conclusion: Ultrasonic‐assisted extraction is capable of degrading PGPS efficiently while preserving its primary structure, resulting in a Newtonian fluid solution. The degraded PGPS conformations displayed a consistent correlation with their inhibitory effect on α‐glucosidase activity. © 2024 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

Due to the intrinsic porosity and photo‐regulated pore environment, azobenzene (Azo) functionalized covalent organic frameworks (COFs) show great potential for contaminant removal. However, the stability and degree of functionality of the COFs greatly affect the porosity and subsequent adsorption capacity and selectivity. Herein, a highly stable thiazole‐linked COF containing phenolic hydroxyl groups (OH‐COF) is constructed by using 4,4′,4′‐(1,3,5‐triazine‐2,4,6‐triyl)trianiline and 2,5‐dihydroxyterephthalaldehyde in the presence of sulfur, which shows high crystallinity and specific surface. Azo‐functionalized COFs ((Azo)x‐COFs) are prepared by grafting different amounts azobenzene groups onto OH‐COF through post‐modification, whose aperture is conveniently tuned by the grafted azobenzene amount. The pore size of (Azo)x‐COFs also can be reversibly adjusted under UV and visible light irradiation without affecting the crystallinity. Appropriate amount of Azo‐grafted (Azo)0.1‐COF possessed a high adsorption capacity (1216.93 mg g−1) to Congo red (CR). While the adsorption capacity of (Azo)1.0‐COF to CR significantly increased 2.9 times to reach 1489.96 mg g−1 after UV irradiation. (Azo)1.0‐COF also can selectively separate dye molecules with different sizes based on photo‐regulated pore size, showing excellent reversibility and reusability. As such, the ability to photo‐regulate the adsorption and interception of (Azo)x‐COFs highlights their significance in functioning as smart porous nanomaterials for pollutant removal and water purification. [ABSTRACT FROM AUTHOR]

Separating helium (He) and hydrogen (H2), two gases that are extremely similar in molecular size and condensation properties, presents a formidable challenge in the helium industry. The development of membranes capable of precisely differentiating between these gases is crucial for achieving large‐scale, energy‐efficient He/H2 separation. However, the limited selectivity of current membranes has hindered their practical application. In this study, we propose a novel approach to overcome this challenge by engineering submicroporous membranes through the fluorination of partially carbonized hollow fibers. We demonstrate that the fluorine substitution on the inner rim of the micropore walls within the carbon hollow fibers enables tunability of the microporous architecture. Furthermore, it enhances interactions between H2 molecules and the micropore walls through the polarization and hydrogen bonding induced by C−F bonds, resulting in simultaneous improvements in both He/H2 diffusivity and solubility selectivities. The fluorinated HFM‐550‐F‐1 min membrane exhibits exceptional mixed‐gas separation performance, with a binary mixed‐gas He/H2 selectivity of 10.5 and a ternary mixed‐gas He/(H2+CO2) selectivity of 20.8, at 40 bar feed pressure and 35 °C, surpassing all previously reported polymer‐based gas separation membranes, and remarkable plasticization resistance and long‐term continuous stability over 30 days. [ABSTRACT FROM AUTHOR]

Conventional wastewater treatment plants (WWTPs) are not designed for the abatement of antibiotics, and their effluents are one of the main entry ways of these emerging contaminants to the aquatic environment, causing major concern due to their toxicity, persistence, and bioaccumulation. When wastewater containing antibiotics enters the bioreactor, they can impact microbial communities of the activated sludge, affecting biodegradation processes of organic matter and nutrients. There is scarce information about the effect of activated carbon on the activated sludge within the bioreactor in presence of antibiotics. In light of this, the effect of representative antibiotics, ciprofloxacin (CIP), nalidixic acid (NAL), and erythromycin (ERY), on the performance of a conventional activated sludge of a WWTP was analyzed by respirometry with and without activated carbon. NAL and ERY negatively affected the net heterotrophic biomass growth rate (r′x,H), with reduction percentages of 26%–90% and 31%–81%, respectively. The addition of activated carbon mitigated this effect, especially for ERY, with increments of even 8% in the r′x,H for the hybrid process when working with 5 ppm of ERY and 80 ppm of activated carbon compared with the value in the absence of antibiotic and activated carbon. This effect was attributed to the enhanced retention of ERY, in comparison to NAL, on the surface of the activated carbon, probably due to its higher molecular size and affinity towards the activated carbon (log Kow = 3.06). This effect was more marked at low sludge retention times (below 8 days). Practitioner points: Ciprofloxacin (CIP), nalidixic acid (NAL), and erythromycin (ERY) were studied.NAL and ERY exerted negative impact on heterotrophic growth rate.Effect of antibiotics on microorganisms in the presence of activated carbon was studied.Activated carbon was mainly relevant for ERY due to its adsorption retention.Enhancement by activated carbon was more significant at low sludge retention times. [ABSTRACT FROM AUTHOR]

Until the end of the 70s of the last century, the major tool for fractionating complex polymers regarding molecular size is gel permeation chromatography (GPC) (more accurately size exclusion chromatography, SEC). A milestone in fractionating polymers with regard to chemical composition is achieved when it is shown that random copolymers can be separated according to copolymer composition using solvent gradient HPLC. Another important step toward selective fractionation is taken when liquid chromatography at the critical point of adsorption is introduced as an efficient way to separate functional polymers with regard to their functionality type distribution. Another milestone is the discovery that temperature gradients can also be used for the selective separation of complex polymers with regard to composition. The combination of different LC methods in comprehensive 2D HPLC setups is another milestone. As of today, a toolbox of HPLC methods is in place that enables the fractionation of complex polymers according to all molecular parameters including tacticity and branching. Here, an overview on the different techniques and some major applications is presented. The most important developments in the field are discussed, and different techniques, experimental protocols, and applications are highlighted. In conclusion, challenges for future developments are outlined. [ABSTRACT FROM AUTHOR]

Discrete dimer or multimer acceptors have enhanced the stability of organic solar cells (OSCs) due to their slow diffusion kinetics resulting from their large molecular sizes. However, development of multimer acceptors with chain length longer than trimers has been challenging, which often require multistep reactions with low synthetic yield. In this study, a new discrete tetramer acceptor (TetA) using one‐pot reaction and subsequent purification processes is developed. During the purification, dimer (DA) and trimer acceptor (TA) are also obtained. The OSCs for TetA demonstrate a higher power conversion efficiency (PCE) of 16.14% than those for the discrete acceptors with shorter chain lengths, such as monomer acceptor (MA, 12.85%), DA (14.31%), and TA (15.10%). Additionally, despite having a similar number‐average molecular weight, TetA‐based OSCs exhibit a significantly higher PCE (16.14%) compared to OSCs based on a mixture of the acceptors (MixA) with dispersity (10.72%). Furthermore, the TetA‐based OSCs have the highest photostability and mechanical robustness among the series. For example, TetA‐based OSCs demonstrate superior photostability (t70% lifetime = 2180 h under 1‐sun illumination) and mechanical robustness (crack‐onset strain (COS) = 8%) compared to those based on MA (t70% = 220 h, and COS = 2%), or MixA (t70% = 745 h, and COS = 6%). [ABSTRACT FROM AUTHOR]

Hydrogen with small molecule size under high pressure can permeate most materials, being a challenge for rubber sealing materials used in hydrogen storage. The volume expansion of rubber materials due to high‐pressure hydrogen is an important indicator of their degradation and failure. Here, both microscopic calculations and experimental investigations of the nitrile rubber were conducted to evaluate the relation between the structure features and the expansion performance. Three factors, the acrylonitrile amount, the chain length, and the crosslinking degree, were considered to impact on the expansion of the nitrile rubber. Current study indicates that the increasing of acrylonitrile amount can result in the reduction of the volume expansion, owing to the preferential interactions between hydrogen and the butadiene group of nitrile rubber. Both of the chain length and the crosslinking degree are positively proportional to the chain elongation and then the volume of the nitrile rubber. Especially, the amount of acrylonitrile was found to be a key factor for evaluating the expansion of nitrile rubber under high‐pressure hydrogen. This study performs microscopic calculations and macroscopic experiments to investigate the expansion of nitrile rubber, which is expected to be used in designing the sealing rubber material for high‐pressure hydrogen storage applications. Highlights: Acrylonitrile determines the expansion performance of NBR within high‐pressure hydrogen.Short chain and low crosslinking density suppressed the expansion of NBR.Evaluating the expansion of nitrile rubber exposed to high‐pressure hydrogen. [ABSTRACT FROM AUTHOR]

Semiochemicals can be used to manipulate insect behaviour for sustainable pest management strategies, but their high volatility is a major issue for their practical implementation. Inclusion of these molecules within porous materials is a potential solution to this issue, as it can allow for a slower and more controlled release. In this work, we demonstrate that a series of Zr(IV) and Al(III) metal‐organic frameworks (MOFs) with channel‐type pores enable controlled release of three semiochemicals over 100 days by pore size design, with the uptake and rate of release highly dependent on the pore size. Insight from grand canonical Monte Carlo simulations indicates that this is due to weaker MOF‐guest interactions per guest molecule as the pore size increases. These MOFs are all stable post‐release and can be reloaded to show near‐identical re‐release profiles. These results provide valuable insight on the diffusion behaviour of volatile guests in MOFs, and for the further development of porous materials for sustainable agriculture applications. [ABSTRACT FROM AUTHOR]

Adsorption kinetics of three organic phosphate compounds (OPs) with varying molecular sizes and structures and inorganic phosphate (Pi) were investigated on α‐Al2O3 and poorly crystalline goethite. The organic phosphates were inositol hexaphosphate (IHP), glycerol phosphate (GlyP) and glucose‐6‐phosphate (G6P), and the inorganic phosphate was KH2PO4. Batch adsorption experiments were performed at 25°C. We tested the sorption kinetic data using various non‐linear models/equations and on their transformed linear forms by applying appropriate statistics. Besides, we also used a modified non‐linear equation having four parameters to this effect. Data were found to fit best with the modified equation and described the whole sorption process satisfactorily. For sorption of compounds on to the surface of these minerals, the equation with four parameters may be used in contrast with many standard equations applied for kinetic studies in soils. Sorption was described to take place in two processes: a fast one that takes place in less than 45 min and a slow one that takes place in several hours or more. The rate of the slow process did not depend directly on the concentration of phosphate compounds in solution, but depended linearly on the amount of phosphate that was adsorbed during the fast process. These initially adsorbed ions carrying some amount of negative charge likely hindered the movement of subsequent adsorbate ions to the solid surface due to decreased surface potential. This caused the variation in fast and slow sorption rate constants. Sorption densities increased in the order, Pi >Gly P >G6P >IHP, which revealed that the sorption density and initial sorption rate of OPs decreased with increasing molecular weights of OPs. [ABSTRACT FROM AUTHOR]

A novel boron‐containing novolac (triphenyl borate‐formaldehyde resin, TPBF) was synthesized. The structure, thermoplasticity, molecular weight, and molecular weight distribution of TPBF have been characterized with FT‐IR, melt viscosity, 13C NMR and GPC. The thermal stability of TPBF was investigated by TGA, indicating the thermal stability of TPBF was much better than that of normal novolac (phenol‐formaldehyde resin, PF). TPBFs with different molar ratios of formaldehyde to benzene ring in triphenyl borate (TPB) were also synthesized and compared for molecular size, polydispersity and thermal stability. Further, the thermal degradation kinetics of TPBFs and PF were studied by TGA using Madhusdanan‐Krishnan‐Ninan method and the activation energies were calculated at different degradation stages. It was found that the thermal degradations of TPBFs and PF are a multistage reaction and the degradation reactions in every stage follow the first order reaction mechanism. Finally, the activation energies of thermal degradations of novolac increase with the introduction of boron, the progress of degradation reaction as well as the increase of molar ratios. [ABSTRACT FROM AUTHOR]

Persistent organic pollutants pose a great threat to amphibian populations, but information on the bioaccumulation of contaminants in amphibians remains scarce. To examine the tissue distribution and maternal transfer of organic halogenated pollutants (OHPs) in frogs, seven types of tissues from black‐spotted frog (muscle, liver, kidney, stomach, intestine, heart, and egg) were collected from an e‐waste–polluted area in South China. Among the seven frog tissues, median total OHP concentrations of 2.3 to 9.7 μg/g lipid weight were found (in 31 polychlorinated biphenyl [PCB] individuals and 15 polybrominated diphenyl ether [PBDE], dechlorane plus [syn‐DP and anti‐DP], bexabromobenzene [HBB], polybrominated biphenyl] PBB153 and ‐209], and decabromodiphenyl ethane [DBDPE] individuals). Sex‐specific differences in contaminant concentration and compound compositions were observed among the frog tissues, and eggs had a significantly higher contaminant burden on the whole body of female frogs. In addition, a significant sex difference in the concentration ratios of other tissues to the liver was observed in most tissues except for muscle. These results suggest that egg production may involve the mobilization of other maternal tissues besides muscle, which resulted in the sex‐specific distribution. Different parental tissues had similar maternal transfer mechanisms; factors other than lipophilicity (e.g., molecular size and proteinophilic characteristics) could influence the maternal transfer of OHPs in frogs. Environ Toxicol Chem 2024;43:1557–1568. © 2024 SETAC [ABSTRACT FROM AUTHOR]

This article explores the issue of wastage in the extraction and injection of botulinum toxin, a popular non-surgical cosmetic treatment. It discusses various techniques that have been proposed to minimize wastage, such as using specialized vials and syringes, rolling the vial between the palms of the hands, and removing the vial cap. The article provides recommendations and guidelines for accurate dosing, dilution, and administration of botulinum toxin, as well as the safe and effective use of this medication in cosmetic procedures. It also discusses the use of botulinum toxin for seborrheic dermatitis and the need for further research to determine its therapeutic potential. The article emphasizes the importance of reducing wastage to ensure cost-effective and safe treatment for patients. [Extracted from the article]

The stable ferrocene‐based N‐heterocyclic silylenes fc[(N{B})2Si] (A; fc=1,1'‐ferrocenylene, {B}=(HCNDipp)2B, Dipp=2,6‐diisopropylphenyl) and fc[(NDipp)2Si] (B) are compared in a study focussing on their reactivity towards a range of small to moderately sized molecular substrates, viz. P4, S8, Se8, MesN3 (Mes=mesityl), RC≡CH, and RC≡CR (R=Ph, SiMe3). The Dipp‐substituted congener B exhibits a more pronounced ambiphilicity and is sterically less congested than its 1,3,2‐diazaborolyl‐substituted relative A, in line with the higher reactivity of the former. The difference in reactivity is obviously due more to electronic than to steric reasons, as is illustrated by the fact that both A and B react with the comparatively bulky substrate MesN3 under mild conditions to afford the corresponding silanimine fc[(N{B})2Si=NMes] and fc[(NDipp)2Si=NMes], respectively. The heavier ketone analogues fc[(N{B})2Si=E] (E=S, Se, Te) are readily available from A and the corresponding chalcogen. In contrast, the reaction of the more reactive silylene B with elemental sulfur or selenium is unspecific, affording product mixtures. However, fc[(NDipp)2Si=Se] is selectively prepared from B and (Et2N)3PSe; the Te analogue is also accessible, but crystallises as head‐to‐tail dimer. [ABSTRACT FROM AUTHOR]

The stable ferrocene‐based N‐heterocyclic silylenes fc[(N{B})2Si] (A; fc=1,1'‐ferrocenylene, {B}=(HCNDipp)2B, Dipp=2,6‐diisopropylphenyl) and fc[(NDipp)2Si] (B) are compared in a study focussing on their reactivity towards a range of small to moderately sized molecular substrates, viz. P4, S8, Se8, MesN3 (Mes=mesityl), RC≡CH, and RC≡CR (R=Ph, SiMe3). The Dipp‐substituted congener B exhibits a more pronounced ambiphilicity and is sterically less congested than its 1,3,2‐diazaborolyl‐substituted relative A, in line with the higher reactivity of the former. The difference in reactivity is obviously due more to electronic than to steric reasons, as is illustrated by the fact that both A and B react with the comparatively bulky substrate MesN3 under mild conditions to afford the corresponding silanimine fc[(N{B})2Si=NMes] and fc[(NDipp)2Si=NMes], respectively. The heavier ketone analogues fc[(N{B})2Si=E] (E=S, Se, Te) are readily available from A and the corresponding chalcogen. In contrast, the reaction of the more reactive silylene B with elemental sulfur or selenium is unspecific, affording product mixtures. However, fc[(NDipp)2Si=Se] is selectively prepared from B and (Et2N)3PSe; the Te analogue is also accessible, but crystallises as head‐to‐tail dimer. [ABSTRACT FROM AUTHOR]

Macrocycles offer an attractive format for drug development due to their good binding properties and potential to cross cell membranes. To efficiently identify macrocyclic ligands for new targets, methods for the synthesis and screening of large combinatorial libraries of small cyclic peptides were developed, many of them using thiol groups for efficient peptide macrocyclization. However, a weakness of these libraries is that invariant thiol‐containing building blocks such as cysteine are used, resulting in a region that does not contribute to library diversity but increases molecule size. Herein, we synthesized a series of structurally diverse thiol‐containing elements and used them for the combinatorial synthesis of a 2,688‐member library of small, structurally diverse peptidic macrocycles with unprecedented skeletal complexity. We then used this library to discover potent thrombin and plasma kallikrein inhibitors, some also demonstrating favorable membrane permeability. X‐ray structure analysis of macrocycle‐target complexes showed that the size and shape of the newly developed thiol elements are key for binding. The strategy and library format presented in this work significantly enhance structural diversity by allowing combinatorial modifications to a previously invariant region of peptide macrocycles, which may be broadly applied in the development of membrane permeable therapeutics. [ABSTRACT FROM AUTHOR]

Step‐growth polymerized systems of type “A3 + A1” are considered. The monomers bear, respectively, 3 or 1 reactive A group. During the reaction, an A group on one monomeric unit might react with an A group on another such unit, thus chemically coupling the two units involved. Complexly structured polymeric molecules are formed. The A3's act as branching points; the A1's as end cappers. At the end of the reaction, the population of molecules present in the reactor vessel varies in size and branching structure. A method is presented to calculate the bivariate (molecular size) × (square radius of gyration) number distribution. It is shown that within the class of molecules of the same size, their square radius of gyration follows a shifted gamma distribution. Two new molecular parameters are introduced: the D index and the G index. The method uses bivariate generating functions. [ABSTRACT FROM AUTHOR]

Membranes are important in the pharmaceutical industry for the separation of antibiotics and salts. However, its widespread adoption has been hindered by limited control of the membrane microstructure (pore architecture and free‐volume elements), separation threshold, scalability, and operational stability. In this study, 4,4′,4′′,4′′′‐methanetetrayltetrakis(benzene‐1,2‐diamine) (MTLB) as prepared as a molecular building block for fabricating thin‐film composite membranes (TFCMs) via interfacial polymerization. The relatively large molecular size and rigid molecular structure of MTLB, along with its non‐coplanar and distorted conformation, produced thin and defect‐free selective layers (~27 nm) with ideal microporosities for antibiotic desalination. These structural advantages yielded an unprecedented high performance with a water permeance of 45.2 L m−2 h−1 bar−1 and efficient antibiotic desalination (NaCl/adriamycin selectivity of 422). We demonstrated the feasibility of the industrial scaling of the membrane into a spiral‐wound module (with an effective area of 2.0 m2). This module exhibited long‐term stability and performance that surpassed those of state‐of‐the‐art membranes used for antibiotic desalination. This study provides a scientific reference for the development of high‐performance TFCMs for water purification and desalination in the pharmaceutical industry. [ABSTRACT FROM AUTHOR]

The self‐assembly of amphiphilic molecules produces structures of diverse dimensions, encompassing micelles, tubules, lamellae, and vesicles. This study focuses on elucidating the controllability of amphiphilic lipid molecule self‐assembly in size and uniformity to facilitate our understanding of the molecular characteristics that correlate with the functions and attributes of the assembled structures. Electrospray deposition allows micropatterning of lipid molecules in conjunction with a conductive–nonconductive patterned substrate. The solvent in the sprayed mist undergoes evaporation during flight, leading to the deposition of dry lipids exclusively on the conductive regions of the substrate. This process enables homogeneous lipid micropatterning, effectively circumventing the coffee‐ring effect. Subsequent hydration of the lipid pattern triggers the spontaneous formation of a size‐controlled, unilamellar vesicle array on the substrate, spanning an area of a few square millimeters. The vesicles exhibits monodispersity, with a coefficient of variation below 8% for sizes ranging from 5 to 20 μm. The size‐controlled self‐assembly process is adaptable to various lipid compositions, thereby demonstrating that the molecular characteristics manifest in the morphological features appear as phase separation, budding, and curvature of vesicle membranes. The approach further validates its suitability for conducting time‐resolved analyses of molecular transport and ligand binding on the monodispersed vesicle array. [ABSTRACT FROM AUTHOR]

Dissolved organic carbon (DOC) in the global oceans is an important long‐term carbon sink. Connections between molecular size, reactivity, and isotopic characteristics show that DOC exists on a continuum from biologically reactive to recalcitrant. The driving mechanisms behind the creation and persistence of recalcitrant DOC remain unknown. We show mean recalcitrant DOC (isolated via solid‐phase extraction; SPE‐DOC) δ13C values are 1.3 ± 0.6‰ lower than mean total DOC δ13C between depth ranges 0–200 m and 2–4 km on three GO‐SHIP Repeat Hydrography cruises. Lowest observed δ13C values correlate with low ∆14C and proximity to deep ocean hydrothermal systems. These data support the hypothesis that reworking of DOC through the microbial carbon pump is a key driver of the ocean's long‐term carbon sink. Mass‐balance modeling shows deep‐ocean DOC not captured by SPE is enriched in 13C, highlighting the need for continued research on non‐retained DOC to predict mechanisms that drive ocean carbon storage. Plain Language Summary: The global oceans play an important role in Earth's climate, and dissolved organic carbon (DOC) (produced by surface ocean photosynthesis) has been recognized as a potential long‐term carbon sink in the deep ocean. However, the mechanisms behind the long‐term sink remain unknown. Recent research has shown that a phenomenon called the microbial carbon pump (MCP) may be a driving force in the production of long‐lasting "recalcitrant" DOC via heterotrophic consumption of nitrogen and phosphorus rich biomolecules and subsequent production of recalcitrant DOC as by‐product. The work presented here shows that this phenomenon, previously recognized on regional scales, may be systematic across the global oceans, indicated by our measurements in the Pacific, Indian, and Southern Oceans. Key Points: Solid‐phase extracted dissolved organic carbon has low isotope signatures relative to bulk dissolved organic carbon in three ocean basinsThis research supports the hypothesis that bacteria drive the storage of recalcitrant organic matter through successive reworkingIsotope measurements show hydrothermal vent influence likely captured in deep‐ocean solid‐phase extracted dissolved organic carbon [ABSTRACT FROM AUTHOR]

Giant molecular acceptors (GMAs) are typically designed through the conjugated linking of individual small molecule acceptors (SMAs). This design imparts an extended molecular size, elevating the glass transition temperature (Tg) relative to their SMA counterparts. Consequently, it effectively suppresses the thermodynamic relaxation of the acceptor component when blended with polymer donors to construct stable polymer solar cells (PSCs). Despite their merits, the optimization of their chemical structure for further enhancing of device performance remains challenge. Different from previous reports utilizing p‐type linkers, here, we explore an n‐type linker, specifically the benzothiadiazole unit, to dimerize the SMA units via a click‐like Knoevenagel condensation, affording BT‐DL. In comparison with B‐DL with a benzene linkage, BT‐DL exhibits significantly stronger intramolecular super‐exchange coupling, a desirable property for the acceptor component. Furthermore, BT‐DL demonstrates a higher film absorption coefficient, redshifted absorption, larger crystalline coherence, and higher electron mobility. These inherent advantages of BT‐DL translate into a higher power conversion efficiency of 18.49 % in PSCs, a substantial improvement over the 9.17 % efficiency observed in corresponding devices with B‐DL as the acceptor. Notably, the BT‐DL based device exhibits exceptional stability, retaining over 90 % of its initial efficiency even after enduring 1000 hours of thermal stress at 90 °C. This work provides a cost‐effective approach to the synthesis of n‐type linker‐dimerized GMAs, and highlight their potential advantage in enhancing intramolecular coupling for more efficient and durable photovoltaic technologies. [ABSTRACT FROM AUTHOR]

π–π interactions are among the most important intermolecular interactions in supramolecular systems. Here we determine experimentally a universal parameter for their strength that is simply based on the size of the interacting contact surfaces. Toward this goal we designed a new cyclophane based on terrylene bisimide (TBI) π‐walls connected by para‐xylylene spacer units. With its extended π‐surface this cyclophane proved to be an excellent and universal host for the complexation of π‐conjugated guests, including small and large polycyclic aromatic hydrocarbons (PAHs) as well as dye molecules. The observed binding constants range up to 108 M−1 and show a linear dependence on the 2D area size of the guest molecules. This correlation can be used for the prediction of binding constants and for the design of new host–guest systems based on the herewith derived universal Gibbs interaction energy parameter of 0.31 kJ/molÅ2 in chloroform. [ABSTRACT FROM AUTHOR]

BACKGROUND: Several different factors underlie the molecular mechanisms of phenolic compound‐protein interactions. They include the environmental conditions. In the case of γ‐conglutin, pH conditions translate directly into the adoption of two distinct oligomeric assemblies, i.e. hexameric (pH 7.5) or monomeric (pH 4.5). This paper reports research on the pH‐dependent oligomerization of γ‐conglutin in terms of its ability to form complexes with a model flavonoid (vitexin). RESULTS: Fluorescence‐quenching thermodynamic measurements indicate that hydrogen bonds, electrostatic forces, and van der Waals interactions are the main driving forces involved in the complex formation. The interaction turned out to be a spontaneous and exothermic process. Assessment of structural composition (secondary structure changes and arrangement/dynamics of aromatic amino acids), molecular size, and the thermal stability of the different oligomeric forms showed that γ‐conglutin in a monomeric state was less affected by vitexin during the interaction. CONCLUSION: The data show precisely how environmental conditions might influence phenolic compound‐protein complex formation directly. This knowledge is essential for the preparation of food products containing γ‐conglutin. The results can contribute to a better understanding of the detailed fate of this unique health‐promoting lupin seed protein after its intake. © 2023 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

BACKGROUND: Zanthoxylum seed, as a low‐cost and easily accessible plant protein resource, has good potential in the food industry. But protein and its hydrolysates from Zanthoxylum seed are underutilized due to the dearth of studies on them. This study aimed to investigate the structure and physicochemical and biological activities of Zanthoxylum seed protein (ZSP) hydrolysates prepared using Protamex®, Alcalase®, Neutrase®, trypsin, or pepsin. RESULTS: Hydrolysis using each of the five enzymes diminished average particle size and molecular weight of ZSP but increased random coil content. ZSP hydrolysate prepared using pepsin had the highest degree of hydrolysis (24.07%) and the smallest molecular weight (<13 kDa) and average particle size (129.80 nm) with the highest solubility (98.9%). In contrast, ZSP hydrolysate prepared using Alcalase had the highest surface hydrophobicity and foaming capacity (88.89%), as well as the lowest foam stability (45.00%). Moreover, ZSP hydrolysate prepared using Alcalase exhibited the best hydroxyl‐radical scavenging (half maximal inhibitory concentration (IC50) 1.94 mg mL−1) and ferrous‐ion chelating (IC50 0.61 mg mL−1) activities. Additionally, ZSP hydrolysate prepared using pepsin displayed the highest angiotensin‐converting enzyme inhibition activity (IC50 0.54 mg mL−1). CONCLUSION: These data showed that enzyme hydrolysis improved the physicochemical properties of ZSP, and enzymatic hydrolysates of ZSP exhibited significant biological activity. These results provided validation for application of ZSP enzymatic hydrolysates as antioxidants and antihypertensive agents in the food or medicinal industries. © 2023 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

Collagen is widely used in the development of new functional materials due to its high structural stability, good biocompatibility, and excellent hydrophilicity, but the collagen protein denatures easily, which makes its thermal stability and mechanical strength difficult to reach some of the parameters required in the application. To solve this, protein crosslinking is an effective way to better use collagen. In this paper, we compared the thermal stability and morphological stability of three kinds of sulfonated calixarenes crosslinked collagen before and after the treatment. The results showed that sulfonated calixarenes could significantly improve the thermal stability and morphological stability of dermal collagen. The reinforcing and toughening mechanism of the sulfonated calixarenes was revealed by scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), ultraviolet--visible--near-infrared (UV--vis--NIR) spectrometer, X-ray diffraction detection (XRD), atomic force microscopy (AFM), and circular dichroism (CD) detection. The results showed that sulfonated calixarenes were evenly distributed in collagen fibers and formed hydrogen bonds or electrovalent bonds with amino groups, peptide groups, or amide groups in collagen to improve the thermal stability of the collagen. Three kinds of sulfonated calixarenes enter collagen fiber to support the collagen, increase the three-dimensional weave angle of collagen, and improve the physical and mechanical properties of collagen, thereby toughening and enhancing the collagen. Based on the above studies, the reinforcing and toughening mechanism of the sulfonated calixarenes crosslinked collagen was established. Confirmed the existence of hydrogen bonds between the three sulfonated calixarenes and collagen, and the nonchemical bond energy of the system was proportional to the molecular size of sulfonated calixarenes. [ABSTRACT FROM AUTHOR]

Surface‐enhanced Raman spectroscopy (SERS) is a powerful analysis technique, and the SERS sensitivity is strongly dependent on metallic nanogaps with a greatly enhanced local electromagnetic field (i.e., hot spots). Once the analytes are located in the hot spot region, their Raman signals are enormously amplified. However, delivering analytes into such tiny hot spots remains a great challenge, particularly for molecules with small Raman scattering cross‐sections and no metal affinity. Here, by employing the isotropic contraction characteristics of polyvinyl chloride (PVC) when heated, a molecule trapping and SERS sensing strategy is demonstrated based on a large‐area ordered gold‐coated polystyrene nanospheres (PS@Au NSs) array with well‐controlled gap size assembled on PVC sheet. Compared with the traditional contraction‐adsorption mode, the developed adsorption‐contraction mode enables efficient delivery of analytes with or without metal affinity into the hot spots between the PS@Au NSs, leading to a significantly improved SERS performance with a large SERS enhancement factor of ≈3.57 × 107. The contractible SERS substrate exhibits a high sensitivity of 10−12 m for rhodamine 6G (R6G), 10−10 m for thiram, and 5 × 10−6 m for 2,3,4‐trichlorobiphenyl, as well as good signal reproducibility with relative standard deviations of 2.81% and 4.25% for R6G and thiram, respectively. [ABSTRACT FROM AUTHOR]

BACKGROUND: Pyranoanthocyanins are stable anthocyanin derivatives. Carboxylpyranoanthocyanin is one of the simplest pyranoanthocyanin, among which the production of carboxylpyranocyanidin‐3‐O‐glucoside (crboxyl‐pycy‐3‐gluc) is most feasible as a result of the abundance of its reactant, cyanidin‐3‐O‐glucoside (Cy‐3‐gluc). RESULTS: In the present study, carboxyl‐pycy‐3‐gluc was synthesized and its stability during processing and after ingestion as well as its bioavailability in vivo were comprehensively evaluated. Our results indicated that the color of carboxyl‐pycy‐3‐gluc remained more stable compared to Cy‐3‐gluc when facing the large‐span pH variation. The high retention of anthocyanin symbolized the superb stability under thermal processing, sulfur dioxide bleaching and ultrasonic treatment of carboxyl‐pycy‐3‐gluc. Because of the stability under the alkaline condition, carboxyl‐pycy‐3‐gluc is more stable after oral‐gastrointestinal digestion. After in vitro gut microbiota fermentation, the retention of carboxyl‐pycy‐3‐gluc was significantly higher than that of Cy‐3‐gluc. The larger molecular size made absorption of carboxyl‐pycy‐3‐gluc into blood more difficult than its precursor. CONCLUSION: The present study demonstrated the promising stability of carboxyl‐pycy‐3‐gluc during food processing and after digestion, confirming the potential of carboxyl‐pycy‐3‐gluc as a colorant. © 2023 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

Summary: High‐intensity ultrasound (HIUS) treatment is a physical method utilised to modify and improve some technologically important compounds (such as protein, fibres) that serves as an environment‐friendly process. In this regard, the effect of HIUS on the composition and emulsifying properties of quinoa okara fractions was analysed. Dispersions (1:10) of ground quinoa grains alkalinised to pH 9.0 were treated by high‐intensity ultrasound. Quinoa okara and sonicated quinoa okara (SQOK) exhibited a similar extraction yield (60%), although SQOK showed a three‐fold increase in protein content. Scanning electron microscopy showed that HIUS reduced the particle size of okara molecular structures. Analysis of O/W emulsions formulated with the okara samples demonstrated that the SQOK had a smaller droplet size and increased the stability of the system against the destabilisation processes of creaming and coalescence. The quinoa okara optimised with the application of the clean ultrasound technology allows adding value to a by‐product with potential applications as a food emulsifier. Quinoa okara could be used as an innovative additive for application in the emerging plant‐based food market. [ABSTRACT FROM AUTHOR]

Polyphenols are well documented against the inhibition of foodborne toxicants in meat, such as heterocyclic amines, Maillard's reaction products, and protein oxidation, by means of their radical scavenging ability, metal chelation, antioxidant properties, and ability to form protein–polyphenol complexes (PPCs). However, their thermal stability, low polarity, degree of dispersion and polymerization, reactivity, solubility, gel forming properties, low bioaccessibility index during digestion, and negative impact on sensory properties are all questionable at oil‐in‐water interface. This paper aims to review the possibility and efficacy of polyphenols against the inhibition of mutagenic and carcinogenic oxidative products in thermally processed meat. The major findings revealed that structure of polyphenols, for example, molecular size, no of substituted carbons, hydroxyl groups and their position, sufficient size to occupy reacting sites, and ability to form quinones, are the main technical points that affect their reactivity in order to form PPCs. Following a discussion of the future of polyphenols in meat‐based products, this paper offers intervention strategies, such as the combined use of food additives and hydrocolloids, processing techniques, precursors, and structure‐binding relationships, which can react synergistically with polyphenols to improve their effectiveness during intensive thermal processing. This comprehensive review serves as a valuable source for food scientists, providing insights and recommendations for the appropriate use of polyphenols in meat‐based products. [ABSTRACT FROM AUTHOR]

The article discusses the use of thorough QT studies (T-QTs) in drug development programs to assess the risk of drug-induced QT prolongation, a potential cardiac side effect. While T-QTs have been successful in identifying drugs with QT prolongation risk, they are expensive to conduct. New guidelines have been introduced to provide alternative, cheaper pathways for evaluating proarrhythmic risk. However, T-QTs are still being performed in approximately 50% of drug development programs. The article also explores the need for clinical QT assessment for large targeted proteins and novel biological modalities, suggesting that the risk of QT prolongation for these drugs is low and minimal clinical evaluation may be sufficient. [Extracted from the article]

High power conversion efficiency (PCE), long‐term stability, and mechanical robustness are prerequisites for the commercial applications of organic solar cells (OSCs). In this study, a new star‐shaped trimer acceptor (TYT‐S) is developed and high‐performance OSCs with a PCE of 19.0%, high photo‐stability (t80% lifetime = 2600 h under 1‐sun illumination), and mechanical robustness with a crack‐onset strain (COS) of 21.6% are achieved. The isotropic molecular structure of TYT‐S affords efficient multi‐directional charge transport and high electron mobility. Furthermore, its amorphous structure prevents the formation of brittle crystal‐to‐crystal interfaces, significantly enhancing the mechanical properties of the OSC. As a result, the TYT‐S‐based OSCs demonstrate a significantly higher PCE (19.0%) and stretchability (COS = 21.6%) than the linear‐shaped trimer acceptor (TYT‐L)‐based OSCs (PCE = 17.5% and COS = 6.4%) and the small‐molecule acceptor (MYT)‐based OSCs (PCE = 16.5% and COS = 1.3%). In addition, the increased molecular size of TYT‐S, relative to that of MYT and dimer (DYT), suppresses the diffusion kinetics of the acceptor molecules, substantially improving the photostability of the OSCs. Finally, to effectively demonstrate the potential of TYT‐S, intrinsically stretchable (IS)‐OSCs are constructed. The TYT‐S‐based IS‐OSCs exhibit high device stretchability (strain at PCE80% = 31%) and PCE of 14.4%. [ABSTRACT FROM AUTHOR]

Reliable structure elucidation of covalent organic cage compounds remains challenging as routine analysis might leave ambiguities. Diffusion‐ordered NMR spectroscopy (DOSY) allows insight into the molecular size and mass of the species present in solution, but a systematic evaluation of the diffusion behavior for cage assemblies is rarely considered. Here we report the synthesis of four series of covalent organic cages based on tribenzotriquinacenes and diboronic acids with varying geometry and exohedral substituents. We provide a guideline for the consistent measurement of diffusion coefficients from 1H‐DOSY NMR spectroscopy, which was utilized to study the diffusion behavior for the whole set of cages and selected examples from the literature. For structurally similar cages, a linear correlation between the solvodynamic volume and the molecular mass allows precise size determination. For more complex systems, multiple parameters, such as window size or rigid exohedral functionalization. further modulate cage diffusion in solution. [ABSTRACT FROM AUTHOR]

The pursuit of synthetic receptors with high binding affinities has long been a central focus in supramolecular chemistry, driven by their significant practical relevance in various fields. Despite the numerous synthetic receptors that have been developed, most exhibit binding affinities in the micromolar range or lower. Only a few exceptional receptors achieve binding affinities exceeding 109 M−1, and their substrate scopes remain rather limited. In this context, we introduce SC[5]A, a conjugated corral‐shaped macrocycle functionalized with ten sulfate groups. Owing to its deep one‐dimensional confined hydrophobic cavity and multiple sulfate groups, SC[5]A displays an extraordinarily high binding strength of up to 1011 M−1 towards several size‐matched, rod‐shaped organic dications in water. Besides, its conformation exhibits good adaptability, allowing it to encapsulate a wide range of other guests with diverse molecular sizes, shapes, and functionalities, exhibiting relatively strong affinities (Ka=106–108 M−1). Additionally, we've explored the preliminary application of SC[5]A in alleviating blood coagulation induced by hexadimethrine bromide in vitro and in vivo. Therefore, the combination of ultrahigh binding affinities (towards complementary guests) and adaptive recognition capability (towards a wide range of functional guests) of SC[5]A positions it as exceptionally valuable for numerous practical applications. [ABSTRACT FROM AUTHOR]

Nitrous oxide (N2O), as the third largest greenhouse gas in the world, also has great applications in daily life and industrial production, like anesthetic, foaming agent, combustion supporting agent, N or O atomic donor. The capture of N2O in adipic acid tail gas is of great significance but remains challenging due to the similarity with CO2 in molecular size and physical properties. Herein, the influence of cation types on CO2−N2O separation in zeolite was studied comprehensively. In particular, the inverse adsorption of CO2−N2O was achieved by AgZK‐5, which preferentially adsorbs N2O over CO2, making it capable of trapping N2O from an N2O/CO2 mixture. AgZK‐5 shows a recorded N2O/CO2 selectivity of 2.2, and the breakthrough experiment indicates excellent performance for N2O/CO2 separation. The density functional theory (DFT) calculation shows that Ag+ has stronger adsorption energy with N2O, and the kinetics of N2O is slightly faster than that of CO2 on AgZK‐5. [ABSTRACT FROM AUTHOR]

The tandem reactions of 2,5‐bis(trifluoromethyl)‐1,3,4‐oxadiazole with conjugated, unconjugated, acyclic, and cyclic dienes have been studied at the M06‐2X/6‐311++G(d,p) level of theory. The rate‐determining step is the initial [4+2] cycloaddition in the tandem reaction of 2,5‐bis(trifluoromethyl)‐1,3,4‐oxadiazole with acyclic, cyclic, conjugated, and unconjugated dienes, whereas the stereochemistry of the tandem adduct is determined by the [3+2] step. The exo‐coupling is kinetically favored over the endo‐coupling in the initial [4+2] reaction of 2,5‐(bis‐trifluoromethyl)‐1,3,4‐oxadiazole with all the considered dienes. In the retro [3+2] step (N2 extrusion), higher activation energy is required to furnish the carbonyl ylide in the reaction of 2,5‐(bis‐trifluoromethyl)‐1,3,4‐oxadiazole with conjugated and unconjugated cyclic dienes as compared with the reaction with unconjugated acyclic dienes. At the stereochemistry [3+2] step, the intermolecular addition is kinetically favored over the intramolecular addition in the [3+2] reaction of 2,5‐(bis‐trifluoromethyl)‐1,3,4‐oxadiazole with both conjugated or unconjugated cyclic dienes and unconjugated acyclic dienes. The reaction proceeds with low activation energies when conjugated and unconjugated cyclic dienes are participating, compared with those of unconjugated acyclic dienes. Overall, the tandem process proceeds via an asynchronous one‐step mechanism [4+2] coupling in an exo‐ or endo‐cycloaddition fashion, followed by a retro [3+2], which extrudes the N2, and then the stereo‐determining intermolecular or intramolecular [3+2] cycloaddition step, which leads to the tandem products. The polarity of both inter‐ and intra‐molecular cycloaddition steps can be influenced by two factors: the nature of the heteroatom present on the diene molecule and the size of the cyclic diene. These factors play a role in determining the reactivity and electron distribution within the diene, thereby impacting the overall polarity of the cycloaddition reactions. [ABSTRACT FROM AUTHOR]

Soft porous coordination polymers (PCPs) have the remarkable ability to recognize similar molecules as a result of their structural dynamics. However, their guest‐induced gate‐opening behaviors often lead to issues with selectivity and separation efficiency, as co‐adsorption is nearly unavoidable. Herein, we report a strategy of a confined‐rotational shutter, in which the rotation of pyridyl rings within the confined nanospace of a halogen‐bonded coordination framework (NTU‐88) creates a maximum aperture of 4.4 Å, which is very close to the molecular size of propyne (C3H4: 4.4 Å), but smaller than that of propylene (C3H6: 5.4 Å). This has been evidenced by crystallographic analyses and modelling calculations. The NTU‐88o (open phase of activated NTU‐88) demonstrates dedicated C3H4 adsorption, and thereby leads to a sieving separation of C3H4/C3H6 under ambient conditions. The integrated nature of high uptake ratio, considerable capacity, scalable synthesis, and good stability make NTU‐88 a promising candidate for the feasible removal of C3H4 from C3H4/C3H6 mixtures. In principle, this strategy holds high potential for extension to soft families, making it a powerful tool for optimizing materials that can tackle challenging separations with no co‐adsorption, while retaining the crucial aspect of high capacity. [ABSTRACT FROM AUTHOR]

By combining the unique characteristics of molecular bottlebrushes (MBBs) and the properties of stimuli‐responsive polymers, we show that MBBs with randomly grafted poly(n‐butyl acrylate) and pH‐responsive poly(2‐(N,N‐diethylamino)ethyl methacrylate) (PDEAEMA) side chains are efficient and robust pH‐responsive emulsifiers. Water‐in‐toluene emulsions were formed at pH 4.0 and disrupted by increasing the pH to 10.0. The emulsion generation and disruption was reversible over the ten cycles investigated, and the bottlebrushes remained intact. The exceptional emulsion stability stemmed from the high interfacial binding energy of MBBs, imparted by their large molecular size and Janus architecture at the interface, as evidenced by the interfacial jamming and wrinkling of the assemblies upon reducing the interfacial area. At pH 10.0, PDEAEMA became water‐insoluble, and the MBBs desorbed from the interface, causing de‐emulsification. Consequently, we have shown that the judicious design of MBBs can generate properties of particle emulsifiers from their large size, while the responsiveness of the MBBs enables more potential applications. [ABSTRACT FROM AUTHOR]