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Development of new photosensitizers (PSs) with high singlet oxygen quantum yield and minimal side effects is of great interest in photodynamic therapy (PDT). Herein, a facile strategy to significan...

Purpose: To investigate the protective effect of cimiracemate A on Freund’s adjuvant-induced rheumatoid arthritis (RA) in neonatal rats, and the underlying mechanism. Methods: Rheumatoid arthritis was induced in rat pups using Complete Freund’s adjuvant (100 µg/100 µL/body weight) which was intra-dermally injected at the tail region. After 21 days of establishment of RA, the rats were randomly assigned to four groups of ten rats each: control group, RA group, 5 mg/kg cimiracemate A group, and 10 mg/kg cimiracemate A group. Cimiracemate A was orally administered for 45 days. The effect of cimiracemate A on oxidative stress biomarkers, superoxide dismutase (SOD), malondialdehyde (MDA) and reduced glutathione (GSH) were determined using standard methods. Plasma levels of the inflammatory cytokines interleukin 1β (IL-1β) and tumor necrosis factor-α (TNF-α), and prostaglandin E2 (PGE-2) and matrix metalloproteinase-3 (MMP-3) were determined using enzyme-linked immunosorbent assay (ELISA). Western blotting was used to determine the levels of protein expressions of iNOS, NF-κB and TLR-4. Results: The level of MDA significantly increased and the level of GSH significantly decreased in RA group relative to control group (p < 0.05) following treatment with cimiracemate A. SOD activity was significantly reduced in RA group, when compared with control group (p < 0.05). However, treatment with cimiracemate A significantly and dose-dependently reversed the altered levels of MDA and GSH and SOD activity, when compared with RA group (p < 0.05). Plasma levels of IL-1β, TNF-α, PGE-2 and MMP-3 were significantly higher in RA group than in control group, but were significantly and dosedependently reduced after treatment with cimiracemate A (p < 0.05). There were significant increases in the levels of expression of iNOS, NF-κB and TLR-4 proteins in the chondrocytes of RA group, relative to control group (p < 0.05). However, treatment with cimiracemate A significantly and dose-dependently down-regulated the expressions of these proteins, when compared with RA group (p < 0.05). Conclusion: The results of this study indicate that cimiracemate A confers some degree of protection on arthritic neonatal rats via a mechanism that involves regulation of iNOS/NF-κB/TLR-4 pathway.

Photodynamic therapy (PDT), a light triggered therapeutic mode, has been recognized as an attractive treatment for oncotherapy. The phototoxicity to normal tissues during treatment limited the development of PDT owing to the always “on” properties of photosensitizers. Activatable photosensitizers are of great importance for improving the selectivity of PDT. Herein, we regarded the overexpressed GGT (γ-Glutamyl transpeptidase) enzyme in tumor cells as a biomarker and developed an activatable photosensitizer Cy-GGT by decorating a specific recognition moiety of GGT, L-glutamic acid, to a hemicyanine dye based on photosensitizer Cy-NH2. Cy-GGT was in the “off” state with negligible fluorescence and suppressed singlet oxygen generation, but it could be specifically hydrolyzed to Cy-NH2 in the presence of GGT, accompanied with significant fluorescence recovery and singlet oxygen generation increase under light irradiation. The in vitro and in vivo studies indicated that Cy-GGT was suitable for precise tumor imaging and could work as an efficient photosensitizer for inhibiting tumor growth.

A total scattering neutron instrument is simulated using a ray-tracing package to evaluate the technique and data reduction algorithms. The neutron guide and chopper system were first optimized to ...

The development of new synthetic methods involving radical intermediates to control the absolute configuration of newly formed stereocenters has seen unprecedented growth in the past few decades. Despite significant advances in this topic, catalytic asymmetric direct construction of stereocenters through addition of radicals to internal alkenes is of special interest due to its potential to simultaneously build (more than) two consecutive stereogenic centers. Methodologies such as chiral Lewis acid catalysis, organocatalysis, and transition metal catalysis have been successfully leveraged to exert enantiocontrol in this challenging domain. This tutorial review highlights the recent significant progress in the realm of rapidly and conveniently building enantioenriched stereocenters via addition of radicals to internal alkenes, with an emphasis on mechanistic scenarios governing the absolute stereochemistry and unmet challenges in this emerging and promising field.

Photodynamic cancer therapy has attracted great attention with the increasing threat of tumors, and improving its therapeutic efficacy is highly desirable. However, due to the highly efficient intersystem crossing potency to generate singlet oxygen (1O2), high-efficiency photosensitizers often suffer from weak fluorescence and excess injury to normal tissue. To overcome these obstacles, here we show a reliable self-reporting strategy for real-time monitoring of therapeutic progression. As a proof of concept, a molecular dyad is designed by connecting benzo[a]phenoselenazinium (NBSe) to rhodamine (Rh), namely Rh-NBSe, where the fluorescence of the Rh unit is initially suppressed by the fluorescence resonance energy transfer mechanism, but enabled to recover as feedback signal once the reaction with photosensitized 1O2 takes place. The observed fluorescence increases by irradiation in vitro and in vivo successfully reflect the real-time 1O2 generation speed in photodynamic therapy. In addition, the favorable therapeutic advantages of Rh-NBSe are also verified, for example, the high ΦΔ (0.8) and the low IC50 (0.2 μM, 6 J cm−2). Based on the therapeutic ability and real-time 1O2 self-reporting ability, Rh-NBSe demonstrates significant potential for self-regulating phototherapy., Photodynamic cancer therapy has attracted great attention with the increasing threat of tumors, and improving its therapeutic efficacy is highly desirable.

A catalytic defluorinative hydroarylation of alkenes with polyfluoroarenes in the presence of dppbz-ligated Cu catalyst and silanes was presented for the first time. This method provides a straightforward and alternative avenue to synthetic important polyfluorinated arenes with readily available and bench-stable alkenes as latent nucleophiles, and therefore avoids conventional reliance on stoichiometric quantities of organometallics. This reaction proceeds under very mild conditions and exhibits good functional group compatibility and high level of regioselectivity. The synthetic potential of this method was further demonstrated by the gram-scale synthesis, and an array of experimental studies were also carried out to elaborate the probable mechanism.

Lactic acid bacteria strain (LAB) NCU116 fermented Asparagus officinalis polysaccharides (FAOP) have been proven to cause substantial changes in physicochemical properties such as monosaccharide composition and molecular weight, accounting for their enhanced immune activity than unprocessed Asparagus officinalis polysaccharides (AOP). In the current study, the hepatoprotective effects of FAOP in mice with cyclophosphamide (CTX)-induced hepatotoxicity were investigated. FAOP were more effective than AOP in alleviating CTX-induced hepatic damage, including inhibition of hepatic biochemical markers (ALT, AST, AKP and LDH) and pro-inflammatory cytokines (TNF-α and IL-1β) as well as reinforcement of antioxidant systems (T-AOC, SOD, CAT, and MDA). In particular, compared with AOP, FAOP showed superior performance by promoting GSH biosynthesis, and normalizing the expression level of bile acid receptors (FXR and SHP) and key enzymes in bile acid synthesis (CYP7A1, CYP8B1 and CYP27A1). Modulation of disordered homeostasis of bile acids by FAOP can be attributed to the upregulation of hepatic short chain fatty acid (SCFA) receptors GPR41 and GPR109A as well as intestinal SCFA production. Furthermore, serum metabolomics study validated the hepatoprotective superiority of FAOP than AOP with evidence from variations in bile acid compositions and the construction of related metabolic pathways. Therefore, LAB NCU116 fermentation of Asparagus officinalis was practical and effective to obtain promising hepatoprotective polysaccharides, which might arise from enhanced SCFA production than unprocessed AOP.

The effect of Lactobacillus plantarum-fermentation on the anti-diabetic functionality of Momordica charantia was examined using a high-fat-diet and low-dose streptozocin-induced type 2 diabetic rat model. Fermented Momordica charantia juice (FMCJ) administration mitigated the hyperglycemia, hyperinsulinemia, hyperlipidemia, and oxidative stress in diabetic rats more favorably than the non-fermented counterpart. Treatments with FMCJ improved ergosterols and lysomonomethyl-phosphatidylethanolamines metabolisms more effectively. Supplement of FMCJ regulated the composition of the gut microbiota, such as increased the abundance of Bacteroides caecigallinarum, Oscillibacter ruminantium, Bacteroides thetaiotaomicron, Prevotella loescheii, Prevotella oralis, and Prevotella melaninogenica, in diabetic rats compared with untreated diabetic rats. Moreover, FMCJ-treated diabetic rats exhibited higher concentrations of acetic acid, propionic acid, butyric acid, total short-chain fatty acids and lower pH values in colonic contents than that in non-fermented juice-treated rats. These results demonstrated that Lactobacillus plantarum-fermentation enhanced the anti-diabetic property of MC juice by favoring the regulation of gut microbiota and the production of SCFAs.

Momordica charantia L. has been consumed as a vegetable for thousands of years, and its fruit has various bioactive compounds. The aim of this study was to investigate the effect of fermentation with Lactobacillus plantarum (L. plantarum) NCU116 on the chemical composition, antioxidant activity, and volatile profile of M. charantia juice. Fermentation and sterilization increased the concentrations of short-chain fatty acids, while the total saponins in the juice was reduced. Fermentation increased lactic acid, total phenolics, and total flavonoids. Fermentation improved the phenolic composition of the juice, such as decreased caffeic and p-coumaric acids, and increased dihydrocaffeic and phloretic acids. Furthermore, the antioxidant properties of the juice and phenolic extracts increased after fermentation. Fermentation altered the aroma profile of the juice to confer a more desirable flavor by reducing aldehydes and ketones, while increasing alcohols and acids. Sterilization decreased lactic acid, total phenolic content, phenolic composition, antioxidant activities, and the aroma profile. These results suggested that L. plantarum fermentation had a beneficial effect on the physico-chemical properties, bioactive compounds, antioxidant property, as well as aroma composition of M. charantia.

Dye-sensitized solar cells (DSSC) are of great scientific significance and application prospect and have attracted wide public concern since they were first reported. The charge recombination in the interface of the DSSC nanocrystalline electrode is thought as a critical issue affecting the DSSC’s performance improvement; however, few systematic studies have been carried out to investigate the effect of the electrolyte additives on the charge recombination suppressing. It is reported that the electrolyte additives can enhance the DSSC short-circuit current. In this work, five typical nitrogen-containing six-element heterocyclic additives used in DSSC were researched theoretically at the B3LYP/6-311G** computational level to elucidate the effects of electrolyte additives on DSSC performance. The five additives were pyridine, pyridazine, pyrimidine, pyrazine and 1,3,5-triazine named as A1–A5, respectively. Their molecular properties, some of which are molecule structures, geometrical configurations, dipole moments, charge distributions, vibrational frequencies and frontier orbitals, were calculated and discussed and their effects on DSSC performance were analyzed theoretically. The results showed an enhanced conjugation effect with the increased number of nitrogen atoms in the conjugated rings of A1–A5 molecules and A1–A5 molecules could bond stably onto the electrode surfaces through the coordination bonding of the N atoms. For the electrolyte additives A1–A5-based DSSC devices, open-circuit voltages and light-to-energy conversion efficiencies increased. This work can be helpful to explain the mechanism of charge recombination suppressing of electrolyte additives for DSSC and offers the potential for future development of high-performance DSSC.

Probiotic-fermented carrot juice (PFCJ) is a functional food, for which colloidal stability during storage is essential. The water-soluble polysaccharides (WSPs) it contains provide this stability as colloidal stabilizers; they are pectinic, mainly containing galacturonic acid, galactose and arabinose as monosaccharide units. The particle-size distribution, ζ potential, centrifugal sediment ratio, soluble solids content, total acid and structural features of these WSPs were evaluated as functions of storage time. The PFCJ displayed pseudoplastic fluid behavior. Molecular weight and solid morphology of WSPs did not change significantly with storage, although the molecular weights of WSPs showed a slight decrease. The storage stability is ascribed to its WSPs acting as electrosteric stabilizers (which are very robust colloidal stabilizers) by adsorbing onto the insoluble plant cell wall polysaccharides which comprise the dispersed phase in the suspension. Viscosity and particle size remained relatively stable when stored at 4 °C and 25 °C, while centrifugal sediment ratio, soluble solids content and total acid all increased significantly; these can also be explained in terms of the structure of the WSPs. This can provide guidance to choosing ingredients which improve storage stability and other properties of importance to consumers by using the precepts of electrosteric colloidal stabilization: e.g. the presence of water-soluble polysaccharides with long hydrophilic moieties.

Paocai as a traditional side dish in Asia gains its popularity owing to the favorable tastes, which are bestowed by microbial metabolisms. The microorganisms involved in fermentation are mainly lactic acid bacteria and Saccharomyces, while low-quality Paocai may contain spoilage and potentially pathogenic microorganisms such as Escherichia coli. To monitor and control food safety for direct vat inoculation of Paocai, this study intended to develop propidium monoazide based quantitative PCR to enumerate fermentation starter Lactobacillus plantarum NCU116, as well as Saccharomyces and potentially present pathogenic bacteria. Universal and specific primers targeting different microorganisms were designed to identify and quantify total lactic acid bacteria, Lactobacillus plantarum, Saccharomyces, and Escherichia coli by establishment of standard curves, respectively. Plate counting was performed and showed comparable results to quantitative PCR analysis, indicating the applicability and efficiency of absolute quantitative PCR in fast detection of microbial composition in Paocai system. Nitrite as a hazardous substance in Paocai was also investigated by spectrophotometry and reverse transcription quantitative PCR. The mechanism of nitrite synthesis and degradation was studied, revealing nitrite reductase in lactic acid bacteria as an effective enzyme in reducing nitrite present in the fermented vegetable.

Background Enterovirus (EV) is a common cause of infection in neonates. Neonates are at high risk of enterovirus infection with serious clinical manifestations and high lethality. This review systematically summarized the clinical characteristics of neonates with severe enteroviral infection to provide evidence for the identification and treatment of severe neonatal EV infection. Methods PubMed, Embase, and Web of Science were searched for original studies on neonates with severe EV infections from January 1, 2000, to November 27, 2020. Two reviewers independently screened the literature, extracted the data, and performed a descriptive analysis. Results In total, 66 articles with 237 cases of severe neonatal enterovirus infection were included. All neonates developed severe complications. Among them, 46.0% neonates had hepatitis or coagulopathy, 37.1% had myocarditis, 11.0% had meningoencephalitis, and 5.9% had other complications such as hemophagocytic lymphohistiocytosis and pulmonary hemorrhage. The lethality rate of neonates with severe infection was 30.4%. The highest lethality rate was 38.6%, which was observed in neonates with myocarditis. In 70.5% neonates, the age at the onset of symptoms was less than 7 days. Coxsackievirus B infection was seen in 52.3% neonates. The most common symptoms included temperature abnormalities (127, 53.6%), rash (88, 37.1%), poor feeding (58, 24.5%), and respiratory symptoms (52, 21.9%). The main treatment included transfusion of empirical antibiotics (127, 53.6%), blood components (100, 42.2%), intravenous immunoglobulin (IVIG; 97, 40.9%), mechanical ventilation (51, 21.5%), and extracorporeal membrane oxygenation (ECMO; 43, 18.1%). Additionally, antiviral medications pleconaril (14, 5.9%) and pocapavir (3, 1.3%) were administered. Conclusions Lethality was high in neonates with severe enterovirus infection, especially in those complicated with myocarditis. The most common symptoms included temperature abnormalities, rash, and poor feeding. The chief supportive treatment consisted of transfusion of blood components, mechanical ventilation, and ECMO. Empirical antibiotics and IVIG were widely used. Antiviral medications included pocapavir and pleconaril; however, more clinical evidence regarding their efficacy is needed.

Probiotics are microbes that promote health when consumed in sufficient amounts. They are present in many fermented foods or can be provided directly as supplements. Probiotics utilize non-digestible prebiotic oligosaccharides for growth in the intestinal tract, contributing to a healthy microbiome. The oligosaccharides favored by probiotics are species-dependent, as shown by the selective utilization of substrates in mixed sugar solutions such as crude fructo-oligosaccharides (FOS). Enzymatically produced crude FOS preparations contain abundant monosaccharide byproducts, residual sucrose, and FOS varying in chain length. Here we investigated the metabolic profiles of four probiotic bacteria during the batch fermentation of crude FOS under controlled conditions. We found that Bacillus subtilis rapidly utilized most of the monosaccharides but little sucrose or FOS. We therefore tested the feasibility of a microbial fed-batch fermentation process for the purification of FOS from crude preparations, which increased the purity of FOS from 59.2 to 82.5% with a final concentration of 140 g·l−1. We also tested cell immobilization in alginate beads as a means to remove monosaccharides from crude FOS. This encapsulation concept establishes the basis for new synbiotic formulations that combine probiotic microbes and prebiotic oligosaccharides.

Photosensitizers (PSs) inevitably release a large amount of energy in the form of fluorescence during photodynamic therapy (PDT). However, under the premise of satisfying fluorescence imaging, a large amount of energy is lost, which limits the efficiency of tumor therapy. Accordingly, in this study, we developed a new strategy (BDP-CR) using the single-molecule Förster resonance energy transfer (smFRET) mechanism to transfer part of the fluorescent energy into heat for combined PDT and photothermal therapy (PTT) featuring the “1 + 1 > 2” amplification effect. Under the 671 nm light irradiation, BDP-CR can produce singlet oxygen (1O2) for PDT based on the BDP moiety and also generate hyperthermia to achieve the PTT effect by exciting CR based on the smFRET effect, which effectively kills cancer cells both in vitro and in vivo. This strategy exhibits a broad absorption peak with strong light-harvesting ability, which improves photon utilization for treatment while realizing fluorescence imaging. Of note, owing to the smFRET effect, we achieve a combination treatment outcome at relatively low concentrations and light doses. Thus, we believe that this design concept will provide a new strategy for single-molecule FRET photosensitizers in combination therapy of cancer with potential clinical application prospects., A new strategy (BDP-CR) using the smFRET mechanism to transfer part of the fluorescent energy into heat for combined PDT and PTT featuring the “1 + 1 > 2” amplification effect is presented.

Herein,we reported an unified Cu-catalyzed asymmetric umpolung hydroamination, which is capable of direct preparation of a series of beta-amino acid, ester, amide and nitrile in a highly regio- and enantioselective manner, without the requirement of traditional pre-installation of stoichiometric quantities of auxiliaries.

Background Since December 2019, the 2019 coronavirus disease (COVID-19) has expanded to cause a worldwide outbreak that more than 600,000 people infected and tens of thousands died. To date, the clinical characteristics of COVID-19 patients in the non-Wuhan areas of Hubei Province in China have not been described. Methods We retrospectively analyzed the clinical characteristics and treatment progress of 91 patients diagnosed with COVID-19 in Jingzhou Central Hospital. Results Of the 91 patients diagnosed with COVID-19, 30 cases (33.0%) were severe and two patients (2.2%) died. The severe disease group tended to be older (50.5 vs. 42.0 years; p = 0.049) and have more chronic disease (40% vs. 14.8%; p = 0.009) relative to mild disease group. Only 73.6% of the patients were quantitative polymerase chain reaction (qPCR)-positive on their first tests, while typical chest computed tomography images were obtained for each patient. The most common complaints were cough (n = 75; 82.4%), fever (n = 59; 64.8%), fatigue (n = 35; 38.5%), and diarrhea (n = 14; 15.4%). Non-respiratory injury was identified by elevated levels of aspartate aminotransferase (n = 18; 19.8%), creatinine (n = 5; 5.5%), and creatine kinase (n = 14; 15.4%) in laboratory tests. Twenty-eight cases (30.8%) suffered non-respiratory injury, including 50% of the critically ill patients and 21.3% of the mild patients. Conclusions Overall, the mortality rate of patients in Jingzhou was lower than that of Wuhan. Importantly, we found liver, kidney, digestive tract, and heart injuries in COVID-19 cases besides respiratory problems. Combining chest computed tomography images with the qPCR analysis of throat swab samples can improve the accuracy of COVID-19 diagnosis.

The catalytic asymmetric creation of silanes with silicon stereocenters is a long-sought but underdeveloped topic, and only a handful of examples have been reported. Moreover, the construction of chiral silanes containing (more than) two stereocenters is a more arduous task and remains unexploited. We herein report an unprecedented copper-catalyzed desymmetrizing protoboration of divinyl-substituted silanes with bis(pinacolato)diboron (B2 pin2 ). This method enables the facile preparation of an array of enantiomerically enriched boronate-substituted organosilanes bearing contiguous silicon and carbon stereocenters with exclusive regioselectivity and generally excellent diastereo- and enantioselectivity.

The aim of this study was to investigate the lactic acid bacteria (LAB) and yeast community from home-made sauerkraut collected from Southwest China through culture-dependent and culture-independent technology. Forty-eight samples of home-made sauerkraut were collected from households at three different locations in Southwest China. The pH, total acidity and salt contents among these fermented vegetables were 3.69 ± 0.42, 0.86 ± 0.43 g/100 ml, and 3.86 ± 2.55 g/100 ml, respectively. The number of lactic acid bacteria (LAB) and yeasts were 7.25 ± 1.05 log10 colony-forming units (CFU)/ml and 3.74 ± 1.01 log CFU/ml, respectively. A total of 182 LAB and 81 yeast isolates were identified. The dominant isolates were Lactobacillus plantarum, L. brevis, Pediococcus ethanolidurans, Pichia membranifaciens, P. fermentans and Kazachstania bulderi. Denaturing gradient gel electrophoresis (DGGE) showed that L. plantarum, uncultured Lactobacillus sp, P. ethanolidurans, and K. exigua were the predominant microflora. Our studies demonstrated that the DGGE technique combined with a culture-dependent method is very effective for studying the LAB and yeast community in Chinese traditional fermentation vegetables. The results will give us an understanding of LAB and yeast community of Chinese sauerkraut and improve the knowledge of LAB and yeast community of Chinese sauerkraut.

The non-directed hydrosilylation of cyclopropenes with earth-abundant and environmentally benign base metal catalysis was described. This protocol is effective for a wide array of 3,3-disubstituted and 1,2-disubstituted cyclopropenes, and hence provides a facile and straightforward route to synthetically valuable polysubstituted and challenging fully substituted cyclopropylsilanes with high efficiency and diastereoselectivity.

Short-chain prebiotic fructo-oligosaccharides (FOS) produced by enzymatic conversion from sucrose often contains high concentration of monosaccharides as byproducts. In addition to conventional physical/chemical purification processes, microbial treatment is an alternative method to remove these byproducts. We used Bacillus coagulans to reduce the abundance of byproducts during the enzymatic production of FOS. It is a promising probiotic because this thermophilic and spore-forming bacterium remains viable and stable during food processing and storage. B. coagulans also produces lactic acid during the carbohydrate metabolism and is used industrially to produce lactic acid for medical and food/feed applications. We aimed to establish an evaluation system to screen different strains of B. coagulans for their performance and selected B. coagulans Thorne for the treatment of crude FOS due to its high growth rate, high sporulation rate, and low nutrient requirements. B. coagulans preferentially utilized monosaccharides over other sugar components of the FOS mixture. Glucose and fructose were completely consumed during the fermentation but 85% (w/w) of the total FOS remained. At the end of the fermentation, the total viable cell count of B. coagulans Thorne was 9.9 &times, 108 cfu&middot, mL&minus, 1 and the maximum endospore count was 2.42 &times, 104 cfu&middot, 1.

Clinically, phototherapy is adapted to tumors in semi-enclosed location, such as cervical, head & neck and gastric cancer, using optical fibers to introduce light. Different with general photodynamic therapy, it has special demands of tumor recognition and lower light dose. However, a merge of primary photosensitizer (ALA et.al) and magnetic resonance (or ultrasound) imaging is commonly used in the therapeutic mode, having low efficacy and complicated operation. To realize a fluorescence-guided phototherapy, here we designed a benzophenoxazine-dyad photosensitizer, namely NBS-NBSe, firstly realize a dyad-caused quenching (DCQ) method to regulate the fluorescence of benzophenoxazine as cancer indicator. The DCQ of NBS-NBSe drastically decrease the fluorescence of benzophenothiazine (NBS), while glutathione in cancer can efficiently release the fluorescence (9.3-fold) to guide the optical source in phototherapy. Meanwhile, the high singlet oxygen generation of benzophenoselenzinium (NBSe) provide an efficient photo ablation ability, and the NBS of anti-hypoxia can assist the therapy of hypoxia deep-seated tumors to reduce tumor recurrence. Under the low light dose of 2.4 J/cm2, NBS-NBSe showed excellent therapeutic efficacy toward tumor cells (24-fold than chlorins e6). The fluorescence recognition ability between tumor/normal cells and the powerful phototoxicity ensure the fluorescence-guided therapeutic mode using for these tumors.

Microbial metabolism is considered to have an important influence on the formation of taste, aroma and flavour compounds during vegetable fermentation. However, the relationship between microbial gene expression and the biosynthetic sources of flavor compounds are still unclear. In this study, genetic and metabolite profiles were used to characterize flavour development during Sichuan paocai (SCP) fermentation. Metatranscriptomic results showed that gene expression and enzyme activity by Enterobacteriaceae and Lactobacillaceae were strongly involved in SCP fermentation. Differential expression of 666 genes involving 27 metabolic pathways – most associated with amino acids– accompanied the accumulation of 17 amino acids (from 31.5 μg/mL to 738.4 μg/mL). In addition, 239 volatile organic compounds (VOCs) were identified and odour activity values showed 10 volatile organic compounds (include 5 sulphur compounds) exert an important influence on the aroma of SCP. Sulphur compounds, Glu, Asp, Lactic acid, acetic acid and maltic acid exert an important influence on the sour, umami and sulphur flavour of SCP. The cysteine and methionine metabolism asparate and glutamate biosynthesis and metabolism and pyruvate metabolism were responsible for the key flavours formation. This study provides significant guidance in the aroma, flavour and tastes regulation in SCP fermentation and new product development.

Lactic acid fermentation represents a novel method to produce bioactive functional ingredients, including polysaccharides. In this work, a selected lactic acid bacteria strain NCU116 was used to ferment Asparagus officinalis (asparagus) pulps. Two polysaccharides were subsequently separated from both unprocessed and fermented asparagus pulps, namely, asparagus polysaccharide (AOP) and fermented-AOP (F-AOP). The physicochemical and bioactive properties of AOP and F-AOP were characterized and investigated. High-performance anion-exchange chromatography showed that fermentation increased the proportions of rhamnose, galacturonic acid, and glucuronic acid in polysaccharides by 46.70, 114.09, and 12.75‰, respectively. High-performance size-exclusion chromatography revealed that fermentation decreased the average molecular weight from 181.3 kDa (AOP) to 152.8 kDa (F-AOP). Moreover, the fermentation reduced the particle size and changed the rheology property. In vitro, F-AOP displayed superior free radical scavenging properties compared to AOP, using 2,2-diphenyl-1-picryhydrazyl, hydroxyl, and superoxide anion radical scavenging assays. In vivo, F-AOP administration dose-dependently promoted a gradual shift from Th17-dominant acute inflammatory response (IL-17 and RORγt) to Th1-dominant defensive immune response (IFN-γ and T-bet). These results indicated that the Lactobacillus plantarum NCU116 fermentation was practical and useful to obtain promising bioactive polysaccharides.

The direct synthesis of N-arylamides via the coupling of aryl diazonium tetrafluoroborates and nitriles under transition-metal-free conditions has been developed. The reported protocol is practical and represents an efficient method to produce functionalized amides in moderate to good yields.

The development of an efficient, straightforward approach for access to a wide range of enantioenriched boron-containing 2,3-disubstituted indolines via highly chemo-, diastereo-, and enantioselective copper-catalyzed intramolecular boraylative cyclization of readily available 2-styrylimines is reported. This reaction proceeds under very mild conditions and displays a high degree of functional group compatibility. The practicability of this approach is demonstrated by a gram-scale reaction and further transformations of the chiral borylated indolines.

A metabolomics method based on ultra-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-QTOF/MS) was used to investigate the effect of Lactobacillus plantarum NCU116 on the metabolites of hyperlipidaemic rat model feed by high-fat diet. Nine potential biomarkers (Pantothenic Acid, 5-Hydroxyindole acetaldehyde, Glycocholic Acid, Biliverdin IX, l -Leucine, 2-Phenylethanol glucuronide, Taurocholic acid, Indoleacrylic acid and 2-Arachidonoylglycerol) were identified and the pathway features were analyzed by Mass Profiler Professional (MPP) software. Meanwhile, clustering of principal components analysis (PCA), partial least squares-discriminant analysis (PLS-DA) and hierarchical clustering analysis (HCA) produces and biological pathways including tryptophan metabolism, bile secretion, fatty acid biosynthesis, glucose homeostasis, protein digestion and absorption were affected by L. plantarum NCU116. This study demonstrated that L. plantarum NCU116 improved hyperlipidaemic rats via metabolism pathways of amino acids, bile, fatty acids and glucose.

With the advantages of superior antibacterial activity and probiotic performance, lactic acid bacteria have been attracting considerable attention in the inhibition of Helicobacter pylori. Here, five Lactiplantibacillus plantarum strains were isolated by a multi-step method and characterized in cell adhesion, β-glucosidase activity, antibiotic susceptibility and hemolytic activity. The five strains supernatants can reduce the viable counts of Helicobacter pylori from 7.4 × 108 CFU/mL to 1.5 × 104–2.0 × 105 CFU/mL after treating for 8 h. The five stains supernatants also showed a better inhibitory effect in the urease activity than the other strains, with the decreased activity of 84.3–90.2% and 73.2–84.0% when treated with the supernatants and the strains for 6 h, respectively. The adhesion of Iso05 to GES-1 cells was up to 9.1%, significantly superior to that of the other four strains, adhesion rate of which ranged from 2.1% to 6.1%. Furthermore, the five strains can decrease the adhesion of Helicobacter pylori by 66.0–89.7%, and the β-glucosidase activity of the five strains reached 0.10–0.14 U/g wet cells. Finally, the five strains were safe with nonhemolytic activity. This study contributes to the isolation of lactic acid bacteria with anti-Helicobacter pylori ability and the development of antibiotics-free anti-Helicobacter pylori foods.

A ligand-controlled regiodivergent and enantioselective copper-catalyzed intermolecular hydroallylation of alkynes with allylic phosphates and hydrosilanes has been achieved for the first time. The chiral bidentate sulfonate-containing N-heterocyclic carbene ligated CuCl complex leads to enantioenriched SN2′-type products, whereas the use of the IMesCuCl catalyst affords SN2-type products. Thus a range of chiral branched and achiral linear 1,4-dienes could be facilely synthesized from readily available alkynes in a regiodivergent manner.

Bacterial viability is a requirement for probiotics in food applications, and retaining a high viability rate is important to ensure its beneficial effects. The study aimed to determine the protective effects of different matrices on microencapsulated Lactobacillus casei LK-1 during spray drying, storage and in vitro digestion. Skim milk, trehalose and maltodextrin were used as protective agents to form different bacterial microcapsules by spray drying. Viability of bacteria in capsules stored at different temperatures (−20, 4, 25 and 37 °C) and in capsules with different water activities were studied. The results showed that both storage temperature and water activity had significant influence on viability of L. casei LK-1 and the glass state was necessary but not absolute factors for storage stability. All matrix showed the highest viability when stored at −20 °C and with water activity of 0.11. It was found that skim milk endowed L. casei LK-1 high viability in either gastric or intestinal juice. In general, skim milk protected L. casei LK-1 better than trehalose and maltodextrin during spray drying, storage and simulated digestion. This study demonstrated that it is important to choose appropriate protective agent to achieve high viability in probiotic application.

Phosphotransferase systems are common and essential in bacteria, which are in charge of sugar transportation and phosphorylation. However, phosphotransferase systems were found in recent years to be associated with environmental stress factors. This study investigated the role of the mannose/fructose/sorbose phosphotransferase systems in Enterococcus faecalis OG1RF in adaption to harsh environments by construction of pts mutants. More than one mannose/fructose/sorbose phosphotransferase system was found in E. faecalis OG1RF, and the elimination of pts gene at different loci generated different after-effects corresponding to different ambiences. An in vitro study showed that the presence of intact phosphotransferase systems in E. faecalis OG1RF promoted resistance to hydrogen peroxide and acid and enhanced susceptibility to pediocin. In vivo study demonstrated that the presence of intact phosphotransferase systems induced more hazardous substances like superoxide dismutase (SOD) in Caenorhabditis elegans and enhanced bacterial infection and survival in macrophages J774A.1 and BMM. In addition, phosphotransferase systems regulated transcription of antioxidant and catabolite genes such as katA, gor, lysR, hypR, rex, hprK and tpx to different extents (-6.3- to 3.5-fold). It is therefore suggested that pts genes are regulatory factors promoting adaption of E. faecalis OG1RF to stressful conditions, thereby enhancing the possibility of bacterial survival and infectivity.

Oncomelania hupensis is the intermediate host of Schistosoma japonicum, one of the Schistosoma species that can cause human schistosomiasis. Molluscicidal treatment remains the primary means to control snail. Niclosamide is the only molluscicide recommended by the World Health Organization, and it has been used throughout schistosomiasis-endemic areas in China for almost 30 years. In our previous studies on transcriptomics, morphology, and enzymology of snails after molluscicidal treatment, two effective molluscicides were used, 50% wettable powder of niclosamide ethanolamine salt (WPN) and a new molluscicide derived from niclosamide, the salt of quinoid-2', 5-dichloro-4'-nitro-salicylanilide (LDS, simplified for Liu Dai Shui Yang An). Genes involved in cell structure mintenance, inhibition of neurohumoral transmission, and energy metabolism showed significant differential expression after molluscicide treatments. Damages in the structure of liver and muscle cells were accompanied by inhibited activities of enzymes related to carbohydrate metabolism and energy supply. This study was designed to clarify the dynamic metabolic process by metabonomics, together with the previous transcriptomic and enzymological profiles, to identify potential metabolite markers and metabolism pathways that related to the toxic mechanism of the molluscicide. In total, 56 metabolites were identified for O. hupensis, and 75% of these metabolites consisted of amino acids and derivatives, organic acids, and nucleic acid components. The concentration of glucose, maltose, succinate, choline, and alanine changed significantly after molluscicide treatments. These changes in metabolites mainly occurred in the process of carbohydrate metabolism, energy metabolism, and amino acid metabolism, primarily related to glycolysis/gluconeogenesis, oxidative phosphorylation, and transamination by KEGG pathway identification. Most of the identified pathways were also related to those differentially expressed unigenes and observed enzymes from our previous studies. Inhibited aerobic respiration and oxidative phosphorylation, and energy deficiency were implied further to be the leading causes of the final death of snails after molluscicide treatments. The hypothesised mathematical model in this study identified the rational hysteresis to explain the inconsistency of responses of unigenes, enzymes, and metabolites to molluscicide treatments. This study contributes to the comprehensive understanding of the molluscicidal mechanism in the metabolic process and this could assist in improving existing molluscicide formulations or development of new molluscicides.

Diamondoids are hydrogen-saturated molecular motifs cut out of diamond, forming a class of materials with tunable optoelectronic properties. In this work, we extend previous work on neutral, closed-shell diamondoids by computing with hybrid density functional theory and time-dependent correlation functions vibrationally broadened absorption spectra of cations and radicals derived from the simplest diamondoid, adamantane, namely, the neutral 1- and 2-adamantyl radicals (C10H15), the 1- and 2-adamantyl cations (C10H15+), and the adamantane radical cation (C10H16+). For selected cases, we also report vibrationally broadened emission, photoelectron, and resonance Raman spectra. Furthermore, the effect of the damping factor on the vibrational fine-structure is studied. The following trends are found: (1) Low-energy absorptions of the adamantyl radicals and cations, and of the adamantane cation, are all strongly red-shifted with respect to adamantane; (2) also, emission spectra are strongly red-shifted, whereas photoelectron spectra are less affected for the cases studied; (3) vibrational fine-structures are reduced compared to those of adamantane; (4) the spectroscopic signals of 1- and 2-adamantyl species are significantly different from each other; and (5) reducing the damping factor has only a limited effect on the vibrational fine-structure in most cases. This suggests that removing hydrogen atoms and/or electrons from adamantane leads to new optoelectronic properties, which should be detectable by vibronic spectroscopy.

Graphical abstract The CPV-2 DNA extracted from dog’s intestine was amplified using RPA and transcribed into an RNA copy. The RNA copy was incubated with Cas13a and crRNA, upon activation collateral cleavage activity of Cas13a cleaves all the target RNA and nonspecific RNA in the vicinity producing fluorescent signals within 30 min., Canine parvovirus type 2 (CPV-2) infection is the most lethal disease of dogs with higher mortality in puppies worldwide. In today’s world, dogs are an integral part of our communities as well as dogs breeding and rearing has become a lucrative business. Therefore, a fast, accurate, portable, and cost-effective CPV-2 detection method with the ability for on-site detection is highly desired. In this study, we for the first time proposed a nanosystem for CPV-2 DNA detection with RNA-guided RNA endonuclease Cas13a, which upon activation results in collateral RNA degradation. We expressed LwCas13a in prokaryotic expression system and purified it through nickel column. Activity of Cas13a was verified by RNA-bound fluorescent group while using a quenched fluorescent probe as signals. Further Cas13a was combined with Recombinase polymerase amplification (RPA) and T7 transcription to establish molecular detection system termed specific high-sensitivity enzymatic reporter un-locking (SHERLOCK) for sensitive detection of CPV-2 DNA. This nanosystem can detect 100 amol/L CPV-2 DNA within 30 min. The proposed nanosystem exhibited high specificity when tested for CPV-2 and other dog viruses. This CRISPR-Cas13a mediated sensitive detection approach can be of formidable advantage during CPV-2 outbreaks because it is time-efficient, less laborious and does not involve the use of sophisticated instruments.

This study aimed to investigate the effect of fermentation with Lactobacillus plantarum NCU137 on the nutritional, sensory and stability properties of Coix (Coix lachryma-jobi L.) seed. The nutritional compounds, including free amino acid, free fatty acid, soluble dietary fiber and organic acids of fermented coix seed were significantly (p

Genetic stability of bacterium as a starter culture is vital for product quality in fermentation industry. The commercial strain Lactobacillus plantarum NCU116 widely used in fruit and vegetable fermentation was induced with various stressors to investigate the stability of potential prophages. PHAge Search Tool (PHAST) identified three potential prophages in bacterial genome. By spectrophotometric analysis, mitomycin C (MMC), lactic acid, and bile salt were found to inhibit the growth of L. plantarum NCU116 while ethanol and hydrogen peroxide had no notable impacts. Transcriptions of four phage-synthesizing genes (phaR, phacap, phaada, phatail) and four phage-resistant genes (cas116, helR, hsd1, hsd2) under stressors were investigated by quantitative reverse transcription PCR. MMC was found to most significantly upregulated transcriptions of phage-synthesizing genes, followed by lactic acid and bile salt. By transmission electron microscopy, no virus particles from the lysates of strain NCU116 treated by MMC were observed, corresponding to the result that no phage nucleic acids could be extracted from the supernatants of strain NCU116 treated by MMC. This study suggested that no prophages could be induced from L. plantarum NCU116 by strong inducer MMC, indicating its genetic stability, which supports the comprehensive application of strain NCU116 in industry without causing fermentation failure.

A catalytic chemo-, regio-, and enantioselective allylation of ketones with 1,3 dienes in the presence of ( R, R)-Ph-BPE ligated Cu catalyst and hydrosilane is presented. This method provides a straightforward and alternative avenue to synthesize chiral homoallylic tertiary alcohols with 1,3-dienes as the latent allylic nucleophiles and avoids the traditional reliance on stoichiometric quantities of allylmetal reagents. This transformation proceeds under very mild conditions and displays good functional group tolerance and could be performed on a gram-scale.

The differences in bacterial communities and physicochemical characteristics between salted and salt-free yancai samples from Nanfeng County were compared in this study. Total acid, salinity and lactic acid content in salted group were significantly higher than those in salt-free group, whereas pH value as well as the contents of acetic acid, sucrose, glucose and fructose showed no significant difference between the two groups. 20 phyla, 339 genera and 203 species were observed in all yancai samples. Firmicutes and Proteobacteria were the major phyla. Lactobacillus was the predominant genus in both the salted and the salt-free samples, whereas Pediococcus, as the second most abundant genus in the salted samples, was in fairly low abundance in the salt-free samples. Culture-dependent and -independent methods showed that the major lactic acid bacteria in the salted samples were Lactobacillus plantarum, L. pentosus, Pediococcus pentosus and L. brevis, while the salt-free samples were predominated by L. fermentum, L. coryniformis and L. sp. The result indicated that salinity had a significant effect on the bacterial communities in Nanfeng yancai, which will improve our understanding of the bacterial ecology of yancai, as well as the relationships between physicochemical characteristics and the microbiota of yancai.

The bio-integrated electronics industry is booming and becoming more integrated with biological tissues. However, it is challenging to obtain high-level self-healing of sensitivity and durability of bifunctional sensor when maintaining their long-term fatigue-resistance and high stretchability. Herein, a high performance self-healable bifunctional sensor was demonstrated through synergistic dynamic interactions between polysiloxane and silver nanoflakes (AgFs) and in-situ formed silver nanoparticles (AgNPs). The bifunctional sensor showed high sensitivity (gauge factor reached 39.5), exceptional electrical self-healability (at ambient temperature), and durability (more than 1000 cycles) by virtue of superflexible siloxane chains in the self-healing polymer, strong dynamic silver-thiolate coordination interactions, and the migration of silver nanoparticles. Finally, multiple human motions and health status were monitored, even after multiple cycles of healing, these “self-healed” sensing signals were still extremely consistent with the pristine ones, indicating the excellent reliabilities and healing stabilities of the bifunctional sensor.

A preparation of niclosamide named 50 % wettable powder of niclosamide ethanolamine salt (WPN), the only chemical molluscicide available in China, has been widely used for Oncomelania hupensis control over the past 20 years, but its molluscicidal mechanism has not been elucidated yet. Recently, a derivative of niclosamide, the salt of quinoid-2',5-dichloro-4'-nitro-salicylanilide (Liu Dai Shui Yang An, LDS), has been proven to have equivalent molluscicidal effects as WPN but with lower cost and significantly lower toxicity to fish than WPN. In our previous study, gene expression profiling of O. hupensis showed significantly effects after these two molluscicides had been applied. This study was designed to use morphological and enzymological analyses to further elucidate the mechanism by which these molluscicides cause snail death. After WPN or LDS treatment, the number of mitochondria of O. hupensis was reduced and their cristae appeared unclear, heterochromatin gathered to be polarized, ribosome numbers of the rough endoplasmic reticulums (rERs) decreased, myofilaments in muscle cells became disordered and loose, and cytoplasm in some liver cells was concentrated. Damage of cell structures and organelles suggested inhibited movement ability and effects on liver and energy metabolism following treatment. In parallel, activities of enzymes related with carbohydrate metabolism were inhibited except lactate dehydrogenase (LDH) increased in muscle tissue, and activities of enzymes related with stress response increased followed by decreasing to lower levels than those of the H2O-treated group. This shift of carbohydrate metabolism patterns led to insufficient energy supply and lactic acid accumulation, and variations of nitric oxide synthase (NOS), alanine aminotransferase (ALT), and superoxide dismutase (SOD) during process of molluscicide treatment suggested a stress response of snail to the molluscicides at early stages and later fatal damage in liver and nervous system. In general, effects of WPN and LDS were similar although LDS-treated snails showed more serious damage in the liver and a stronger inhibition of enzymes related with aerobic respiration and stress response. This was consistent with the transcriptome profile obtained previously. However, considering enzyme activities at post-transcriptional and protein levels, comprehensive identification and annotation of potential enzyme-related genes and regulation pattern would be necessary to provide great benefit for understanding of potential mechanism of these molluscicides and even for future molluscicide development.

BACKGROUND Blueberry products have various health benefits due to their high content of dietary anthocyanins. The aim of this study was to investigate the impact of fermentation and sterilization on total anthocyanin content, composition and some quality attributes of blueberry puree. The blueberry puree used here was fermented for 40 h at 37 °C by Lactobacillus after sterilization. The method of ultra-performance liquid chromatography–mass spectrometry was optimized for the rapid analysis of anthocyanins. Quality attributes including pH, color, total soluble solids and viscosity were measured. RESULTS A total of 21 anthocyanins and five anthocyanidins were quantified by ultra-performance liquid chromatography. Fermented blueberry had reduced total anthocyanin content (29%) and levels of individual anthocyanins compared with fresh blueberry. Total anthocyanin content was decreased 46% by sterilization, and different degradation behavior of individual anthocyanin was appeared between fermented and sterilized–fermented blueberry puree. Fermentation and sterilization decreased the total soluble solids and pH and changed color parameters, while minimally influencing viscosity. CONCLUSIONS The loss of total anthocyanin content by fermentation was related to the unstable structure of blueberry anthocyanins. Anthocyanins are sensitive to temperature (>80 °C), and degradation of anthocyanins by sterilization in blueberry should be considered in the fermentation procedure. © 2016 Society of Chemical Industry

The aim of the study was to determine the effects of salt concentration on traditional sauerkraut fermented spontaneously. Lactic acid bacteria (LAB), fungi and Escherichia coli (E. coli) in the brine were analyzed in the three kinds of sauerkraut. The contents of sugars (sucrose, glucose, fructose) and organic acids (lactic acid, acetic acid) in the brine and inside the cabbage were monitored by high-performance liquid chromatography (HPLC). In addition, the pH value was monitored in the brine. Results demonstrated that sucrose and glucose were consumed and fructose was accumulated gradually during fermentation. The whole fermentation process was dominated by LAB and a considerable accumulation of lactic acid was observed both in cabbage and brine at the end of fermentation. Salt concentration had a significant effect on sauerkraut fermentation at early stage. The LAB population and metabolic rate was reduced and the yield of lactic acid decreased with the increase of salt concentration. Suitable salt concentration can effectively inhibit the reproduction of fungi and E. coli. In comparison, high salt concentration delayed the maturation of sauerkraut and inhibited the metabolism of LAB.

A facile, copper-catalyzed aminoarylation reaction of various aryl/alkyl alkynes was realized by utilizing N-fluoroarylsulfonimides (NFSI) as aminoarylation or amination reagent with hydroxyl as directing group. With this methodology, various α,β-unsaturated carbonyl compounds and indenones were efficiently constructed, and the synthetic application for indole derivatives was also provided. The aminoarylation reactions operate via a regiospecific addition of copper-coordinated nitrogen radical to C–C triple bond/Cvinyl–Caryl bond formation followed by other series of radical processes.

In this study, a novel metabolomics method based on ultra-performance liquid chromatography quadrupole time-of-flight mass spectrometry was developed to investigate the effect of Lactobacillus plantarum NCU116 (NCU116) fermented carrot juice on the metabolites of serum from high fat diet and streptozotocin-induced type 2 diabetic rats. Eight potential biomarkers (adenosine, proline, 5-hydroxyindoleacetaldehyde, glycocholic acid, taurochenodeoxycholic acid, sphingosine, theophylline and taurocholic acid) were identified by unpaired t test analysis, and the pathway features were analyzed by Mass Profiler Professional software. Clustering of partial least squares-discriminant analysis showed that biological pathways and processes, including metabolism of lipids, lipoproteins, purine, tryptophan, bile secretion, fatty acid biosynthesis, glycolysis and gluconeogenesis, were affected by NCU116 fermented carrot juice. These results suggest that metabolomics approach is very useful for studying the mechanisms of action of NCU116 supplement on type 2 diabetes.

Current methods of detecting beer spoilage lactic acid bacteria (LAB) are time-consuming and do not differentiate between viable and non-viable bacteria. In this study, a combination of the conventional polymerase chain reaction (PCR) and propidium monoazide (PMA) pretreatment has been described to circumvent the disadvantages. The horA-specific PMA-PCR described here identifies beer spoilage LAB based not on their identity, but on the presence of a gene that is shown to be highly correlated with the ability of LAB to grow in beer. The results suggest that the use of 20 µg/mL or less of PMA did not inhibit the PCR amplification of DNA derived from viable, but putatively non-culturable (VPNC) Lactobacillus acetotolerans. The minimum amount of PMA to completely inhibit the PCR amplification of DNA derived from dead L. acetotolerans cells was 1.5 µg/mL. The detection limit of established PMA-PCR assays was found to be 100 VPNC cells/reaction for the horA gene. Furthermore, the horA-specific PMA-PCR assays were subjected to 18 reference strains, representing 100% specificity with no false positive amplification observed. In conclusion, the use of horA-specific PMA-PCR allows for a substantial reduction in the time required for the detection of potential beer spoilage LAB and efficiently discriminates between live and dead cells. Copyright © 2015 The Institute of Brewing & Distilling

Polyphenols (flavonoids and anthraquinones) are one of the most important phytochemicals in Fagopyrum tataricum L. Gaertn. (tartary buckwheat). However, the relationship between the polyphenols of tartary buckwheat seeds and their morphological variations is unclear. We developed a liquid chromatography-mass spectrometry-based targeted metabolomics method to study the chemical profiles of 60 flavonoids and 11 anthraquinones in 40 seed cultivars (groats and hulls). Both flavonoids and anthraquinones were related to variations in seed color; the fold change from yellowish-brown to black seeds was 1.24-1.55 in groats and 0.26-0.76 in hulls. Only flavonoids contributed to significant differences in seed shape; the fold change from long to short seeds was 1.29-1.78 in groats and 1.39-1.44 in hulls. Some differential metabolites were identified at higher concentrations in hulls than in groats. This study provides new insights into differences in polyphenols among tartary buckwheat seeds with different color and shape.

Two-photon (TP) have been innovatively researched in bio-imaging and photodynamic therapy (PDT) due to the near-infread (NIR) absorption and excellent spatial accuracy, especially for the subcutaneous and deep-seated tumor. For TP excited photosensitizers (PS), the NIR absorption and enough triplet state energy can be simultaneously realized by semi-excited mode. Thus, we reported a boron dipyrromethene based cationic two-photon photosensitizer (TP-Car-BDP) to promote the tumor targeting and optical physical properties for better imaging and therapeutic effect, using two neutral molecules (PG-Car-BDP, C10-Car-BDP) as comparison. As expected, the cationic group could accelerate oil-water balance and cellular uptake, realize structure-inherent targeting in vivo, and induced early apoptosis in PDT. The imaging and therapeutic property of TP-Car-BDP excited by one/two-photon was also compared to illustrate efficacy of TP. Moreover, the high singlet oxygen quantum yield (0.39) and excellent phototoxicity (IC50 of 25.5 nM, MB was 2960 nM) revealed the potential therapeutic capacity.

Vibrationally resolved absorption and emission (fluorescence) spectra of perylene and its N-derivatives in gas phase and in solution (acetonitrile) were simulated using a time-dependent approach based on correlation functions determined by density functional theory. By systematically varying the number and position of N atoms, it is shown that the presence of nitrogen heteroatoms has a negligible effect on the molecular structure and geometric distortions upon electronic transitions, while spectral properties change: in particular the number of N atoms is important while their position is less decisive. Thus, the N-substitution can be used to fine-tune the optical properties of perylene-based molecules.