Increasing electrochemical carbon dioxide reduction to methane via a novel copper-based conductive metal organic framework.

The development of a new system for the electrochemical carbon dioxide reduction reaction (ECO2RR) to methane (CH4) is challenging, and novel conductive metal organic frameworks (c-MOFs) for efficient ECO2RR to CH4 are critical to this system. Here, we report a novel c-MOF, copper-pyromellitic dianhydride-2-methylbenzimidazole (Cu-PD-2-MBI), in which the introduction of electron-withdrawing 2-methylbenzimidazole (2-MBI) into the copper-pyromellitic dianhydride (Cu-PD) interlayer elevated the valence of copper (Cu) ions, which improved the ECO2RR performance of Cu-PD-2-MBI. Cu-PD-2-MBI was tested in a flow cell, and the Faradaic efficiency of CH4 reached 73.7 %, with a corresponding partial current density of -428.3 mA·cm-2 at -1.3 V, which was higher than those of most reported Cu-based catalysts. Further exploration via theoretical calculations indicated that the intercalated 2-MBI in Cu-PD-2-MBI induced a shift in the d-band center in the Cu sites from -2.63 to -1.86 eV and reduced the formation energy of the *COOH and *CHO intermediates in the process of generating CH4 compared with those of the reference Cu-PD catalyst.

Promotion of Fast and Efficient Singlet Fission Process of PDI Dimers by Selenium Substitution.

Singlet fission (SF) is a triplet generation mechanism capable of turning a singlet exciton into two triplet excitons. It has the potential to enhance the power conversion efficiency of single-junction solar cells. Perylene diimides (PDIs) are a class of dye molecules with photovoltaic properties and are beginning to receive more and more attention due to their potential for SF. Here, we report a selenium-substituted PDI dimer, Se-PDI-II, and we studied its SF mechanism by using steady-state, transient absorption, and time-resolved photoluminescence spectroscopy. Compared with the unsubstituted dimer PDI-II, we found that the introduction of selenium atoms can suppress excimer emission during the SF process, showing much higher SF efficiency and triplet yield.

Photocatalytic CO2 Reduction by Near-Infrared-Light (1200†nm) Irradiation and a Ruthenium-Intercalated NiAl-Layered Double Hydroxide.

Near-infrared light-driven photocatalytic CO2 reduction (NIR-CO2PR) holds tremendous promise for the production of valuable commodity chemicals and fuels. However, designing photocatalysts capable of reducing CO2 with low energy NIR photons remains challenging. Herein, a novel NIR-driven photocatalyst comprising an anionic Ru complex intercalated between NiAl-layered double hydroxide nanosheets (NiAl-Ru-LDH) is shown to deliver efficient CO2 photoreduction (0.887 µmol h-1) with CO selectivity of 84.81 % under 1200 nm illumination and excellent stability over 50 testing cycles. This remarkable performance results from the intercalated Ru complex lowering the LDH band gap (0.98 eV) via a compression-related charge redistribution phenomenon. Furthermore, transient absorption spectroscopy data verified light-induced electron transfer from the Ru complex towards the LDH sheets, increasing the availability of electrons to drive CO2PR. The presence of hydroxyl defects in the LDH sheets promotes the adsorption of CO2 molecules and lowers the energy barriers for NIR-CO2PR to CO. To our knowledge, this is one of the first reports of NIR-CO2PR at wavelengths up to 1200 nm in LDH-based photocatalyst systems.

Open Active Sites in Ni-Based MOF with High Oxidation States for Electrooxidation of Benzyl Alcohol.

The kinetics of electrocatalytic reactions are closely related to the number and intrinsic activity of the active sites. Open active sites offer easy access to the substrate and allow for efficient desorption and diffusion of reaction products without significant hindrance. Metal-organic frameworks (MOFs) with open active sites show great potential in this context. To increase the density of active sites, trimesic acid was utilized as a ligand to anchor more Ni sites and in situ construct the nickel foam-loaded Ni-based trimesic MOF electrocatalyst (Ni-TMA-MOF/NF). When tested as an electrocatalyst for benzyl alcohol oxidation, Ni-TMA-MOF/NF exhibited lower overpotential and superior durability compared to Ni foam-loaded Ni-based terephthalic MOF electrocatalyst (Ni-PTA-MOF/NF) and Ni(OH)2 nanosheet array (Ni(OH)2/NF). Ni-TMA-MOF/NF required only a low potential of 1.65 V to achieve a high current density of 400 mA cm-2. Even after 40000 s of electrocatalytic oxidation at 1.5 V, Ni-TMA-MOF/NF maintained a current density of 175 mA cm-2 with ∼68% retention, showing its potential for benzyl alcohol oxidation. Through a combination of experimental and theoretical investigations, it was found that Ni-TMA-MOF/NF displayed superior electrocatalytic activity due to an optimized electron structure with high-valence Ni species and a high density of active sites, enabling long-term stable operation at high current densities. This study provides a new perspective on the design of electrocatalysts for benzyl alcohol oxidation.

Genome-wide identification and examination of the wheat glycosyltransferase family 43 regulation during Fusarium graminearum infection.

In Arabidopsis and rice, the glycosyltransferase (GT) 43 family is involved in xylan synthesis. However, there have been limited reports on the study of the TaGT43 family in wheat. In this study, 28 TaGT43 family members were identified in wheat (Triticum aestivum L.) and clustered into three major groups based on the similarity of amino acid sequences. The results of the TaGT43 family's conserved motif and gene structure analyses agree with this result. Collinearity analysis revealed segmental duplications mainly promoted TaGT43 family expansion. cis-Acting element analysis revealed that the TaGT43 genes were involved in the light response, phytohormone response, abiotic/biotic stress response, and growth and development. The TaGT43 family showed a tissue-specific expression pattern, primarily expressed in roots and stems. Besides, the transcriptional and expression levels of multiple TaGT43 genes were upregulated during the infection of F. graminearum. According to metabolomics studies, F. graminearum infection affected the phenylpropanoid biosynthesis pathway in wheat, a critical factor in cell wall construction. Furthermore, GO enrichment analysis indicated that the TaGT43 genes play a significant role in cell wall organization. Based on these results, it may be concluded that the TaGT43 family mediates cell wall organization in response to F. graminearum infection.

In situ topotactic formation of an inorganic intergrowth bulk NiS/FeS@MgFe-LDH heterojunction to simulate CODH for the photocatalytic reduction of CO2.

Enzyme-mimetic photocatalysis has been attracting much attention in bionic research, in which carbon monoxide dehydrogenase (CODH) is a suitable prototype for simulation to meet environmental and energy needs. In this study, we utilized the structural memory effect of layered double hydroxides (LDHs) to build inorganic intergrowth bulk heterojunctions (IIBHs) NiS/FeS@MgFe-LDHs via a pyrolytic topological vulcanization (PTV) method that imitated active C-clusters [Ni-4Fe-4S] in CODH. Enzyme mimicry was evaluated in terms of the microstructure and catalytic reaction site. The similarity between the microstructure of NiS/FeS@MgFe-LDHs and the CODH active group was demonstrated through XRD, XAFS and other characterisations. Subsequently, the obtained in situ irradiated X-ray photoelectron spectra and transient absorption spectra indicated the photogenerated electron transfer of the IIBH, wherein electrons finally accumulated in the conduction band of the NiS domain for the photocatalytic CO2 reduction reaction, which was similar to that of C-clusters [Ni-4Fe-4S] in which the Ni2+ ion was the reactive site. As a result, NiS/FeS@MgFe-LDHs achieved a high yield of CO at a rate of 2151.974 µmol g-1 h-1, which was 39.8 and 9.7 times more than that of NiMgFe-LDHs and NiMgFe-MMO, respectively. The study offers an innovative design route for developing IIBHs, providing novel opportunities for enzyme-mimetic photocatalysis.

Nonfullerene Acceptor Featuring Unique Self-Regulation Effect for Organic Solar Cells with 19 % Efficiency.

The blend nanomorphology of electron-donor (D) and -acceptor (A) materials is of vital importance to achieving highly efficient organic solar cells. Exogenous additives especially aromatic additives are always needed to further optimize the nanomorphology of blend films, which is hardly compatible with industrial manufacture. Herein, we proposed a unique approach to meticulously modulate the aggregation behavior of NFAs in both crystal and thin film nanomorphology via self-regulation effect. Nonfullerene acceptor Z9 was designed and synthesized by tethering phenyl groups on the inner side chains of the Y6 backbone. Compared with Y6, the tethered phenyl groups participated in the molecular aggregation via the π-π stacking of phenyl-phenyl and phenyl-2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (IC-2F) groups, which induced 3D charge transport with phenyl-mediated super-exchange electron coupling. Moreover, ordered molecular packing with suitable phase separation was observed in Z9-based blend films. High power conversion efficiencies (PCEs) of 19.0 % (certified PCE of 18.6 %) for Z9-based devices were achieved without additives, indicating the great potential of the self-regulation strategy in NFA design.

Microplastic fragmentation by rotifers in aquatic ecosystems contributes to global nanoplastic pollution.

The role of aquatic organisms in the biological fragmentation of microplastics and their contribution to global nanoplastic pollution are poorly understood. Here we present a biological fragmentation pathway that generates nanoplastics during the ingestion of microplastics by rotifers, a commonly found and globally distributed surface water zooplankton relevant for nutrient recycling. Both marine and freshwater rotifers could rapidly grind polystyrene, polyethylene and photo-aged microplastics, thus releasing smaller particulates during ingestion. Nanoindentation studies of the trophi of the rotifer chitinous mastax revealed a Young's modulus of 1.46 GPa, which was higher than the 0.79 GPa for polystyrene microparticles, suggesting a fragmentation mechanism through grinding the edges of microplastics. Marine and freshwater rotifers generated over 3.48 × 105 and 3.66 × 105 submicrometre particles per rotifer in a day, respectively, from photo-aged microplastics. Our data suggest the ubiquitous occurrence of microplastic fragmentation by different rotifer species in natural aquatic environments of both primary and secondary microplastics of various polymer compositions and provide previously unidentified insights into the fate of microplastics and the source of nanoplastics in global surface waters.

Suppressing electron-phonon coupling in organic photovoltaics for high-efficiency power conversion.

The nonradiative energy loss (∆Enr) is a critical factor to limit the efficiency of organic solar cells. Generally, strong electron-phonon coupling induced by molecular motion generates fast nonradiative decay and causes high ∆Enr. How to restrict molecular motion and achieve a low ∆Enr is a sticking point. Herein, the free volume ratio (FVR) is proposed as an indicator to evaluate molecular motion, providing new molecular design rationale to suppress nonradiative decay. Theoretical and experimental results indicate proper proliferation of alkyl side-chain can decrease FVR and restrict molecular motion, leading to reduced electron-phonon coupling while maintaining ideal nanomorphology. The reduced FVR and favorable morphology are simultaneously obtained in AQx-6 with pinpoint alkyl chain proliferation, achieving a high PCE of 18.6% with optimized VOC, JSC and FF. Our study discovered aggregation-state regulation is of great importance to the reduction of electron-phonon coupling, which paves the way to high-efficiency OSCs.

Mechanistic Understanding toward the Maternal Transfer of Nanoplastics in Daphnia magna.

Nanoplastics induce transgenerational toxicity to aquatic organisms, but the specific pathways for the maternal transfer of nanoplastics remain unclear. Herein, laser scanning confocal microscopy (LSCM) observations identified the specific pathways on the maternal transfer of polystyrene (PS) nanoplastics (25 nm) in Daphnia magna. In vivo and in vitro experiments showed that PS nanoplastics could enter the brood chamber through its opening and then be internalized to eggs and embryos using LSCM imaging (pathway I). In addition, PS nanoplastics were observed in the oocytes of the ovary, demonstrating gut-ovary-oocyte transfer (pathway II). Furthermore, label-free hyperspectral imaging was used to detect the distribution of nanoplastics in the embryos and ovary of Daphnia, again confirming the maternal transfer of nanoplastics through the two pathways mentioned above. The contribution from pathway I (88%) was much higher than pathway II (12%) based on nanoflow cytometry quantification. In addition, maternal transfer in Daphnia depended on the particle size of PS nanoplastics, as demonstrated by using LSCM and hyperspectral imaging. Unlike 25 nm nanoplastics, 50 nm PS nanoplastics could enter the brood chamber and the eggs/embryos (pathway I), but were not detected in the ovary (pathway II); 100 nm PS nanoplastics were difficult to be internalized by eggs/embryos and could not enter the ovary either. These findings provide insight into the maternal transfer mechanisms of nanoplastics in Daphnia, and are critical for better understanding the transgenerational toxicity of aquatic organisms.

Prevalence and associated factors of mortality after percutaneous coronary intervention for adult patients with ST-elevation myocardial infarction: A systematic review and meta-analysis.

Background: There is a paucity of systematic reviews on the associated factors of mortality among ST-elevation myocardial infarction (STEMI) patients after percutaneous coronary intervention (PCI). This meta-analysis was designed to synthesize available evidence on the prevalence and associated factors of mortality after PCI for adult patients with STEMI. Materials and Methods: Databases including the Cochrane Library, PubMed, Web of Science, Embase, Ovid, Scopus, ProQuest, MEDLINE, and CINAHL Complete were searched systematically to identify relevant articles published from January 2008 to March 2020 on factors affecting mortality after PCI in STEMI patients. Meta-analysis was conducted using Stata 12.0 software package. Results: Our search yielded 91 cohort studies involving a total of 199, 339 participants. The pooled mortality rate for STEMI patients after PCI was 10%. After controlling for grouping criteria or follow-up time, the following 17 risk factors were significantly associated with mortality for STEMI patients after PCI: advanced age (odds ratio [OR] = 3.89), female (OR = 2.01), out-of-hospital cardiac arrest (OR = 5.55), cardiogenic shock (OR = 4.83), renal dysfunction (OR = 3.50), admission anemia (OR = 3.28), hyperuricemia (OR = 2.71), elevated blood glucose level (OR = 2.00), diabetes mellitus (OR = 1.8), chronic total occlusion (OR = 2.56), Q wave (OR = 2.18), without prodromal angina (OR = 2.12), delay in door-to-balloon time (OR = 1.72), delay in symptom onset-to-balloon time (OR = 1.43), anterior infarction (OR = 1.66), ST-segment resolution (OR = 1.40), and delay in symptom onset-to-door time (OR = 1.29). Conclusion: The pooled prevalence of mortality after PCI for STEMI patients was 10%, and 17 risk factors were significantly associated with mortality for STEMI patients after PCI.

Transfer of CeO2 nanoparticles between freshwater omnivorous organisms: Effect of feces and necrophagy.

Transfer of CeO2 engineered nanoparticles (NPs) through feces was investigated between two omnivorous organisms, red crucian carp (Carassius auratus red var.) and crayfish (Procambarus clarkii). Upon water exposure (5 mg/L, 7 days), the highest bioaccumulation was observed in carp gills (5.95 µg Ce/g D.W.) and crayfish hepatopancreas (648 µg Ce/g D.W.), with the bioconcentration factors (BCFs) at 0.45 and 3.61, respectively. In addition, 97.4% and 73.0% of ingested Ce were excreted by carp and crayfish, respectively. The feces of carp and crayfish were collected and fed to crayfish and carp, respectively. After feces exposure, bioconcentration was observed in both carp (BCF, 3.00) and crayfish (BCF, 4.56). After feeding crayfish with carp bodies (1.85 µg Ce/g D.W.), CeO2 NPs were not biomagnified (biomagnification factor, 0.28). Upon water exposure, CeO2 NPs were transformed into Ce(III) in the feces of both carp (24.6%) and crayfish (13.6%), and the transformation was stronger after subsequent feces exposure (100% and 73.7%, respectively). Feces exposure lowered histopathological damage, oxidative stress, and nutritional quality (e.g., crude proteins, microelements, amino acids) to carp and crayfish in comparison with water exposure. This research highlights the importance of feces exposure on the transfer and fate of NPs in aquatic ecosystems.

Intrachain and Interchain Excited-State Dynamics of Temperature-Dependent Aggregation Copolymer in Solution.

Poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene)-co-(1,3-di(5-thiophene-2-yl)-5,7-bis (2-ethylhexyl)benzo[1,2-c:4,5-c']dithiophene-4,8-dione)] (PBDB-T) is a donor-acceptor copolymer widely used as a donor material in high-efficiency organic solar cells. In this work, we studied the temperature-dependent aggregation properties of PBDB-T in solution. Through the characterization of UV-vis absorption and the photoluminescence spectrum, we found that PBDB-T formed strong interchain interactions that facilitate aggregation at room temperature. In contrast, warmer temperatures cause PBDB-T to coil and increase intrachain interactions, thus reducing aggregation. We further use transient absorption spectroscopy to explore the effect of temperature-dependent aggregation behavior on excited-state dynamics. The results show that the intrachain interaction is beneficial to increase the production of polaron pairs, and the interchain interaction is beneficial to accelerate the production of free polarons. Finally, we investigated the corresponding films and demonstrated that regulating the solution aggregation is an effective way to control the crystallinity, and morphology of the corresponding films.

The relationship between body mass index and stroke: a systemic review and meta-analysis.

BACKGROUND: Stroke is an acute cerebrovascular event closely related to brain tissue damage, and is one of the major causes of death and disability in worldwide. Various studies have reported the effects of body mass index (BMI) on the risk of stroke, but the results remain varied and these results have not been synthesized. Therefore, a meta-analysis was performed to evaluate the relationship between BMI and the risk of stroke. OBJECTIVES: This systematic review was conducted to explore the relationship between BMI and the risk of stroke. METHODS: PubMed, EMBASE, Web of Science and Cochrane Library, China Knowledge Resource Integrated Database (CNKI), WanFang Database, Chinese Biomedical Database (CBM), and CQVIP were comprehensively searched for studies exploring the relationship between BMI and stroke from inception to December 1, 2021. RESULTS: This review included 24 studies involving 5,798,826 subjects. The results of meta-analysis showed that the pooled RR of stroke risk was 0.93 (95% confidence interval [CI] 0.82-1.06, I2 = 88.8%, P = 0.29) for the underweight group. Higher BMI (overweight or obese group) was associated with an increased overall risk of stroke, with pooled RR values of 1.25 (95% CI 1.16-1.34, I2 = 84.8%, P = 0.00) and 1.47 (95% CI: 1.02-2.11, I2 = 99.4%, P = 0.04). CONCLUSION: The risk of stroke was positively correlated with BMI, and the association was stronger in male and ischemic stroke. Lowering BMI can be used as a way to prevent stroke, and for people who are overweight or obese, lowering body weight can reduce the risk of stroke.

Prediction Models for Conversion From Mild Cognitive Impairment to Alzheimer's Disease: A Systematic Review and Meta-Analysis.

Background and Purpose: Alzheimer's disease (AD) is a devastating neurodegenerative disorder with no cure, and available treatments are only able to postpone the progression of the disease. Mild cognitive impairment (MCI) is considered to be a transitional stage preceding AD. Therefore, prediction models for conversion from MCI to AD are desperately required. These will allow early treatment of patients with MCI before they develop AD. This study performed a systematic review and meta-analysis to summarize the reported risk prediction models and identify the most prevalent factors for conversion from MCI to AD. Methods: We systematically reviewed the studies from the databases of PubMed, CINAHL Plus, Web of Science, Embase, and Cochrane Library, which were searched through September 2021. Two reviewers independently identified eligible articles and extracted the data. We used the Critical Appraisal and Data Extraction for Systematic Reviews of Prediction Modeling Studies (CHARMS) checklist for the risk of bias assessment. Results: In total, 18 articles describing the prediction models for conversion from MCI to AD were identified. The dementia conversion rate of elderly patients with MCI ranged from 14.49 to 87%. Models in 12 studies were developed using the data from the Alzheimer's Disease Neuroimaging Initiative (ADNI). C-index/area under the receiver operating characteristic curve (AUC) of development models were 0.67-0.98, and the validation models were 0.62-0.96. MRI, apolipoprotein E genotype 4 (APOE4), older age, Mini-Mental State Examination (MMSE) score, and Alzheimer's Disease Assessment Scale cognitive (ADAS-cog) score were the most common and strongest predictors included in the models. Conclusion: In this systematic review, many prediction models have been developed and have good predictive performance, but the lack of external validation of models limited the extensive application in the general population. In clinical practice, it is recommended that medical professionals adopt a comprehensive forecasting method rather than a single predictive factor to screen patients with a high risk of MCI. Future research should pay attention to the improvement, calibration, and validation of existing models while considering new variables, new methods, and differences in risk profiles across populations.

Ultrathin Two-Dimensional Bimetal-Organic Framework Nanosheets as High-Performance Electrocatalysts for Benzyl Alcohol Oxidation.

Ultrathin two-dimensional metal-organic frameworks (2D MOFs) have the potential to improve the oxidation of benzyl alcohol (BA) with a large surface area and open catalytic active sites. To achieve high-efficiency electrocatalysts for the oxidation of benzyl alcohol, a moderate solvothermal method was evolved to synthesize a series of 2D MOFs on nickel foam (Ni-MOF/NF, NiCo-61-MOF/NF, NiCo-21-MOF/NF). As the electrocatalyst used for the oxidation of benzyl alcohol, NiCo-61-MOF/NF presented a lower overpotential and superior chemical durability than other electrocatalysts; it only required a potential of ∼1.52 V (vs RHE) to reach 338.16 mA cm-2, with an oxidation efficiency of more than 86%. Besides, after continuous electrocatalysis for 20 000 s at 1.42 V (vs RHE), the current density of NiCo-61-MOF/NF nanosheets was still 38.67 mA cm-2 with 77.34% retention. This demonstrated that NiCo-61-MOF/NF nanosheet electrocatalysts had great potential for benzyl alcohol oxidation. From both the experimental and theoretical studies, it was discovered that NiCo-61-MOF/NF nanosheets have the highest electrocatalytic activity due to their distinctive ultrathin 2D structure, optimized electron structure, and more accessible active sites. This finding would pave a brand-new thought for the design of electrocatalysts with electrocatalytic activity for benzyl alcohol oxidation (EBO).

Factors influencing the social participation ability of rural older adults in China: A cross-sectional study.

Objective: To investigate the epidemiology and influencing factors of social participation ability of rural older adults in China. Methods: From March to April 2021, 3450 older adults in poverty aged 60 and above registered in Jishishan County (J County) were selected by cluster sampling for a cross-sectional questionnaire survey and their social participation ability was assessed using the Ability Assessment of older adults (MZ/T039-2013). The results were statistically analyzed and an ordered multi-category logistic regression analysis was used to analyze the effect of influencing factors on the social participation ability of rural older adults. Results: 3,346 questionnaires were collected, with an effective recovery rate of 96.99%. Out of all the participants, 1,355 (40.5%) of the 3,346 cases had intact social participation ability, while 1,991 (59.5%) had different degrees of loss of social participation ability, of which 1,393 (41.14%) were mildly impaired, 419 (12.5%) were moderately impaired and 179 (5.3%) were severely impaired. Age, educational level, religious belief, living status, whether suffering from dementia and the occurrence of accidents in recent 30 days were influencing factors on the social participation ability (p < 0.05). Conclusion: The rate of impaired social participation ability among older adults was >50% and age, educational level, religious beliefs, living status, whether suffering from dementia, and the occurrence of accidents in recent 30 days (such as falls, choking, loss) were significant factors influencing the ability of social participation of rural older adults.

Accurate Quantum Wave Packet Study of the Deep Well D+ + HD Reaction: Product Ro-vibrational State-Resolved Integral and Differential Cross Sections.

The H+ + H2 reaction and its isotopic variants as the simplest triatomic ion-molecule reactive system have been attracting much interests, however there are few studies on the titled reaction at state-to-state level until recent years. In this work, accurate state-to-state quantum dynamics studies of the titled reaction have been carried out by a reactant Jacobi coordinate-based time-dependent wave packet approach on diabatic potential energy surfaces constructed by Kamisaka et al. Product ro-vibrational state-resolved information has been calculated for collision energies up to 0.2 eV with maximal total angular momentum J = 40. The necessity of including all K-component for accounting the Coriolis coupling for the reaction has been illuminated. Competitions between the two product channels, (D+ + HD' → D'+ + HD and D+ + HD' → H+ + DD') were investigated. Total integral cross sections suggest that resonances enhance the reactivity of channel D+ + HD'→ H+ + DD', however, resonances depress the reactivity of the another channel D+ + HD' → D'+ + HD. The structures of the differential cross sections are complicated and depend strongly on collision energies of the two channels and also on the product rotational states. All of the product ro-vibrational state-resolved differential cross sections for this reaction do not exhibit rigorous backward-forward symmetry which may indicate that the lifetimes of the intermediate resonance complexes should not be that long. The dynamical observables of this deuterated isotopic reaction are quite different from the reaction of H+ + H2 → H2 + H+ reported previously.

Molecular characterization and analysis of high-level multidrug-resistance of Shigella flexneri serotype 4s strains from China.

To conduct the first comprehensive analysis of Shigella flexneri serotype 4s, a novel serotype found in 2010, we identified 24 serotype 4s isolates from 1973 shigellosis cases in China (2002-2014). The isolates were characterized by single nucleotide polymorphism (SNP) phylogenetic analysis, pulsed-field gel electrophoresis (PFGE) and multilocus sequence typing (MLST) to determine their genetic relatedness, and analysed further for their antimicrobial susceptibilities and antimicrobial resistance determinants. The PFGE and SNP phylogenetic analyses suggest that S. flexneri serotype 4s strains are derived from multiple serotypes, including two predominant serotypes in China: serotype X variant and serotype II. Three new sequence types were identified by MLST. All isolates were resistant to ticarcillin, ampicillin and tetracycline, with high-level resistance to third-generation cephalosporins. Notably, all the isolates were multidrug resistant (MDR), with the highest levels of resistance observed for eight antimicrobials classes. Most isolates contain various antimicrobial resistance determinants. In conclusion, we found that serotype 4s isolates have multiple evolutionary sources, diverse biochemical characteristics and genomes, and highly prevalent multidrug resistance and antimicrobial-resistant determinants. With few clinical treatment options, continuous monitoring and timely intervention against this emerging MDR serotype is essential. The possibility that serotype 4s will become the next predominant serotype exists.

Rational Design and Optimization of Trypsin Inhibitory Peptides with Antibacterial Activity.

Small natural or synthetic peptides have been reported to exhibit potent inhibitory capability against trypsin, some of which were also found to have antibacterial potency. Here, we described a successful application of in silico-in vitro integrated approach to rationally design and optimize bifunctional peptides with both trypsin inhibitory and antimicrobial activities. In the procedure, computer-aided methods including protein docking, peptide redocking, molecular dynamics simulations and binding free energy calculations were employed to model and analyze the intermolecular interaction between human trypsin (hT) and natural trypsin inhibitors (TIs). Based on the modeled hT-TI complex structures a number of promising peptide fragments were derived from the trypsin inhibitory loop of TIs, which were then tested experimentally to determine their inhibitory potency on recombinant hT protein as well as their antibacterial potency against three clinical strains. Consequently, few peptides were found to possess a good profile of trypsin inhibitory and antibacterial bi-functionality. Structural visualization and noncovalent examination of hT complex with a potent peptide revealed that the hydrophobic forces and van der Waals contacts between the peptide nonpolar residues and the hydrophobic pocket around hT active site confer significant stability to the complex architecture, while few specific hydrogen bonds and cation-π interactions at the complex interface contribute to peptide selectivity for hT.