Cross-Layer Contrastive Learning of Latent Semantics for Facial Expression Recognition.

Convolutional neural networks (CNNs) have achieved significant improvement for the task of facial expression recognition. However, current training still suffers from the inconsistent learning intensities among different layers, i.e., the feature representations in the shallow layers are not sufficiently learned compared with those in deep layers. To this end, this work proposes a contrastive learning framework to align the feature semantics of shallow and deep layers, followed by an attention module for representing the multi-scale features in the weight-adaptive manner. The proposed algorithm has three main merits. First, the learning intensity, defined as the magnitude of the backpropagation gradient, of the features on the shallow layer is enhanced by cross-layer contrastive learning. Second, the latent semantics in the shallow-layer and deep-layer features are explored and aligned in the contrastive learning, and thus the fine-grained characteristics of expressions can be taken into account for the feature representation learning. Third, by integrating the multi-scale features from multiple layers with an attention module, our algorithm achieved the state-of-the-art performances, i.e. 92.21%, 89.50%, 62.82%, on three in-the-wild expression databases, i.e. RAF-DB, FERPlus, SFEW, and the second best performance, i.e. 65.29% on AffectNet dataset. Our codes will be made publicly available.

Review on chitosan-based antibacterial hydrogels: Preparation, mechanisms, and applications.

Chitosan (CS) is known for its remarkable properties, such as good biocompatibility, biodegradability, and renewability, in addition to its antibacterial and biological activities. However, as CS is insoluble in water, it displays limited antibacterial performance under neutral and physiological conditions. A viable solution to this problem is grafting chemically modified groups onto the CS framework, thereby increasing its solubility and enhancing its antibacterial effect. Herein, the antibacterial action mechanism of CS and its derivatives is reviewed, confirming the prevalent use of composite materials comprising CS and its derivatives as an antibacterial agent. Generally, the antimicrobial ability of CS-based biomaterials can be enhanced by incorporating supplementary polymers and antimicrobial agents. Research on CS-based composite biomaterials is ongoing and numerous types of biomaterials have been reported, including inorganic nanoparticles, antibacterial agents, and CS derivatives. The development of these composite materials has considerably expanded the application of CS-based antibacterial materials. This study reviews the latest progress in research regarding CS-based composite hydrogels for wound repair, tissue engineering, drug release, water purification, and three-dimensional printing applications. Finally, the summary and future outlook of CS-based antibacterial hydrogels are presented in anticipation of a broader range of applications of CS-based antibacterial hydrogels.

Mechanism of dioscin ameliorating renal fibrosis through NF­κB signaling pathway­mediated inflammatory response.

Dioscin (DIS) is a natural compound derived from Chinese herbal medicine. In recent years, multiple studies have reported that DIS has immunoregulation, anti­fibrosis, anti­inflammation, anti­viral and anti­tumor effects. However, the mechanism by which DIS ameliorates renal fibrosis and inflammation remains to be elucidated. The aim of the present study was to investigate the role of DIS in renal fibrosis and inflammation and to explore its underlying mechanism. It used network pharmacology to predict the targets of DIS for the treatment of renal interstitial fibrosis. The present study was performed using unilateral ureteral obstruction mice and HK­2 cells in vivo and in vitro. The mice were treated with different doses of DIS. Kidney tissues were collected for histopathology staining, western blotting, immunohistochemistry staining and reverse transcription­quantitative (RT­q) PCR. TGF­ß1 (2 ng/ml) was used to induce renal fibrosis in the cells. Then, cells were respectively treated with DIS (3.125, 6.25, 12.5 µM) and Bay11­7082 (an inhibitor of NF­κB p65 nuclear transcription, 1 µM) for another 24 h. The expressions of inflammatory factors and NF­κB pathway proteins were detected by immunofluorescence, ELISA, western blotting and RT­qPCR. DIS alleviated renal injury in the UUO mice. Mechanistically, DIS not only decreased the expressions of inflammatory factors including IL­1ß, NOD­like receptor thermal protein domain associated protein 3, monocyte chemotactic protein 1, IL­6, TNF­α and IL­18 but also reduced the level of phosphorylation of NF­κB p65 in vivo and in vitro, which was similar to the impact of Bay11­7082. DIS ameliorated renal fibrosis by inhibiting the NF­κB signaling pathway­mediated inflammatory response, which may be a therapeutic pathway for delaying chronic kidney disease.

A Highly Enantioselective Homoenolate Michael Addition/Esterification Sequence of Cyclohexadienone-Tethered Enals via NHC Catalysis.

Reported here is a highly enantioselective homoenolate Michael addition/esterification sequence of cyclohexadienone-tethered enals via N-heterocyclic carbene (NHC) catalysis, affording the enantiopure cis-hydrobenzofurans, cis-hydroindoles, and cis-hydroindenes. The NHC catalyst bearing a nitro group greatly enhances the stereocontrol, and a bulky N-aryl substituent of the triazolium salt in the catalyst is helpful for inhibiting the further aldol condensation after homoenolate Michael addition. The utility of this protocol is highlighted by a gram-scale experiment and versatile downstream transformations.

CuI-Catalyzed Decarboxylative Thiolation of Propargylic Cyclic Carbonates/Carbamates to Access Allenyl Thioethers.

The first CuI-catalyzed decarboxylative thiolation of terminal alkyne-substituted cyclic carbonates/carbamates to access allenes has been developed. A wide range of hydroxymethyl- and aminomethyl-containing allenyl thioethers were smoothly obtained in good to excellent yields under mild conditions. The copper-allenylidene intermediate among the process is crucial to the decarboxylative thiolation reaction. This method opens up a new channel to access allenyl thioether compounds.

Benzylidene succinimides as 3C synthons for the asymmetric tandem Mannich reaction/transamidation of cyclic trifluoromethyl ketimines to obtain F3C-containing polycyclic dihydroquinazolinones.

By taking advantage of benzylidene succinimides as a new class of 3C synthons, a highly diastereo- and enantioselective tandem Mannich reaction/transamidation has been established by reacting them with cyclic trifluoromethyl N-acyl ketimines. Using a Cinchona alkaloid-derived squaramide as the catalyst, the tandem reaction proceeded smoothly under mild conditions and afforded a range of F3C-containing chiral polycyclic dihydroquinazolinones with excellent results (up to 99% yield, all cases >20 : 1 dr, up to 99% ee).

Copper-Catalyzed Decarboxylative [3 + 2] Annulation of Ethynylethylene Carbonates with Azlactones: Access to γ-Butyrolactones Bearing Two Vicinal Quaternary Carbon Centers.

An efficient decarboxylative [3 + 2] annulation reaction of ethynylethylene carbonates and azlactones has been developed with a copper salt as catalyst. This practical methodology gives access to a diverse library of γ-butyrolactones bearing α,ß-two vicinal quaternary carbon centers in good to high yields with good levels of diastereoselectivities (up to 98% yield, >95:5 dr). Preliminary trials on enantioselective variant with a chiral PyBox ligand provided chiral products in up to 71% ee. This synthetic method features mild reaction conditions, broad functional group tolerance, large-scale synthesis, and versatile products transformation. A plausible catalytic cycle for the protocol is proposed based on previous related studies and our experimental observations.

Nanoengineering 2D Dendritic PdAgPt Nanoalloys with Edge-Enriched Active Sites for Enhanced Alcohol Electroxidation and Electrocatalytic Hydrogen Evolution.

Lots of research studies reveal that the surface atoms on the top/bottom facets of the nanosheets are the key features in enhancing electrocatalytic activity while the edge and corner sites of electrocatalysts often possess superior activity. Herein, we report 2D dendritic PdAgPt ternary nanoalloys with abundant crystal defects such as steps, twin boundary, and atomic holes, which can effectively work as catalytic active-sites. The morphology of PdAgPt nanoalloys can be regulated readily from dendritic nanosheets to nanowheels. Compared with binary Pd68Ag32 nanodendrites, Pd62Pt38 nanospheres, and Pt/C catalyst, the composition- and morphology-optimized Pd43Ag21Pt36 nanowheels exhibit the best mass/specific activity and stability for methanol/ethanol oxidation reaction (MOR/EOR). The mass peak current density for EOR/MOR of Pd43Ag21Pt36 is 7.08/3.50 times of the Pt/C catalyst. Simultaneously, the hydrogen evolution reaction performance of the Pd43Ag21Pt36 nanowheels in terms of the lowest overpotential of 9 mv at a current density of 10 mA/cm2 and high electrochemical stability is much better than that of binary Pd68Ag32 nanodendrites, Pd62Pt38 nanospheres, and Pt/C.

Enantioselective synthesis of isoquinoline-1,3(2H,4H)-dione derivatives via a chiral phosphoric acid catalyzed aza-Friedel-Crafts reaction.

A highly enantioselective aza-Friedel-Crafts reaction of structurally new ketimines with indoles and pyrrole is developed by using a chiral phosphoric acid as the catalyst. This protocol enables the first enantioselective synthesis of isoquinoline-1,3(2H,4H)-dione derivatives in good to excellent yields (up to 99% yield) and excellent enantioselectivities (up to >99% ee).

Organocatalytic Asymmetric [3 + 2] Cycloaddition of N-2,2,2-Trifluoroethylisatin Ketimines with ß-Trifluoromethyl Electron-Deficient Alkenes: Access to Vicinally Bis(trifluoromethyl)-Substituted 3,2'-Pyrrolidinyl Spirooxindoles.

N-2,2,2-Trifluoroethylisatin ketimines with ß-trifluoromethyl enones, 3-trifluoroethylidene oxindole, and 3-trifluoroethylidene benzofuranone can undergo asymmetric [3 + 2] cycloaddition, catalyzed by chiral bifunctional squaramide-tertiary amine catalysts, affording a wide spectrum of 3,2'-pyrrolidinyl spirooxindoles. The significance of this protocol is highlighted by its extremely high efficiency in the construction of the structurally diverse spirocyclic oxindoles, bearing a vicinally bis(trifluoromethyl)-substituted pyrrolidine moiety, including four contiguous stereocenters, in high yields with excellent stereocontrol.

Photochemical Cleavage of Benzylic C-N Bond To Release Amines.

The 3-(diethylamino)benzyl (DEABn) group has been studied for releasing primary, secondary, and tertiary amines by direct photochemical breaking of the benzylic C-N bond. While photochemical release of primary and secondary amines provides high yields in methanol, release of tertiary amines in MeCN/water can improve yields and reduce the undesired dealkylation side reaction.

Structurally simple benzyl-type photolabile protecting groups for direct release of alcohols and carboxylic acids.

Structurally simple benzyl-type photolabile protecting groups (PPGs) have been developed to release alcohols and carboxylic acids. Release of two substrates from one PPG chromophore has also been accomplished.

Photochemical formation and cleavage of C-N bond.

A new photochemical method of C-N bond formation has been developed. A properly substituted trityl alcohol can cleave the benzylic C-O bond and replace it with a C-N bond which is stable under the irradiation conditions. The C-N bond can then be photochemically cleaved with the same light source when the nitrogen is protonated.

Unleash metformin: reconsideration of the contraindication in patients with renal impairment.

OBJECTIVE: To evaluate the expanded use of metformin in renal impairment. DATA SOURCES: The MEDLINE database via PubMed, Web of Science, and Cumulative Index to Nursing and Allied Health were searched in August 2013 and included studies from 1950 onward. STUDY SELECTION AND DATA EXTRACTION: The search included comparative trials, observational cohort studies, and meta-analyses using the terms diabetes mellitus, metformin, renal insufficiency, and acidosis, lactic. DATA SYNTHESIS: One randomized controlled trial, 1 meta-analysis, 1 case-control, and 3 prospective-cohort studies, representing about 150 000 patients, revealed that metformin is safe in patients with stable mild-moderate renal impairment. The incidence of lactic acidosis is low and similar to sulfonylureas. In addition, reduced risks of cardiovascular disease, all-cause mortality, or any acidosis/serious infection were seen with metformin use in mild-to-moderate renal impairment. CONCLUSIONS: Data over the past decade refute the historical contraindication in patients with renal impairment and suggest that the risk of metformin-associated lactic acidosis is low in stable mild-to-moderate renal impairment and similar to the risk with other type 2 diabetes mellitus (DM2) medications with no renal impairment restrictions. Because of its unique impact on microvascular and macrovascular complications, it is advantageous to utilize metformin as the cornerstone in DM2 treatment for as long as possible, including in those patients with mild to moderate stages of renal impairment with no additional contraindications. A dosage reduction is recommended if estimated glomerular filtration rate (eGFR) is between 30 and 45 mL/min/1.73 m(2) and discontinuation if eGFR is <30 mL/min/1.73 m(2).

Application of new photolabile protecting groups as photocleavable joints of block copolymers.

New photoresponsive block copolymers (BCPs) have been developed by incorporating photocleavable units. These photocleavable units are derived from robust photolabile protecting groups (PPGs); UV irradiation cleaves the BCPs and releases a well-defined chemically active functional group at the cleaved end of a PS polymer.

Discovery and utilization of biocatalysts for chiral synthesis: an overview of Chinese scientists' research and development.

The importance of chiral issues in active pharmaceutical ingredients has been widely recognized not only by pharmacologists, but also by chemists, chemical engineers and administrators. In fact, the worldwide sales of single-enantiomer drugs have exceeded US $150 billion. Among them the contribution rate of biocatalysis technology is ever increasing (up to 15-20%). This chapter will focus on the biocatalytic synthesis of chiral compounds useful for pharmaceutical industry. Diverse enzymes, such as oxidoreductases, epoxide hydrolases, nitrilases/nitrile hydratases and hydroxy nitrile lyases which were isolated from various sources including microorganisms and plants, and the methodology for utilizing these enzymes in enantioselective or asymmetric synthesis will be discussed briefly.

Adzuki bean: a new resource of biocatalyst for asymmetric reduction of aromatic ketones with high stereoselectivity and substrate tolerance.

A new resource of biocatalyst for asymmetric reduction of aromatic ketones has been discovered for the first time from a common plant seed, adzuki bean, i.e. Phaseolus angularis (Willd.) W.F. Wight. The study investigated the best methods to prepare the biocatalyst and its ability to reduce ketones. Our results indicated that the biocatalyst from adzuki bean could reduce various aromatic ketones at relatively high concentrations (e.g. 100mM), exhibiting excellent stereoselectivity (>98% e.e.). In addition, it was found that NADPH acts as the reducing cofactor, which can be regenerated by the crude enzyme system itself using glucose as an auxiliary substrate.

Isolation of Rhodococcus sp. strain ECU0066, a new sulfide monooxygenase-producing strain for asymmetric sulfoxidation.

A new and efficient sulfide monooxygenase-producing strain, ECU0066, was isolated and identified as a Rhodococcus sp. that could transform phenylmethyl sulfide (PMS) to (S)-sulfoxide with 99% enantiomeric excess via two steps of enantioselective oxidations. Its enzyme activity could be effectively induced by adding PMS or phenylmethyl sulfoxide (PMSO) directly to a rich medium at the early log phase (6 h) of fermentation, resulting in over 10-times-higher production of the enzyme. This bacterial strain also displayed fairly good activity and enantioselectivity toward seven other sulfides, indicating a good potential for practical application in asymmetric synthesis of chiral sulfoxides.

Synthesis of novel salidroside esters by lipase-mediated acylation with various functional acyl groups.

Salidroside, a natural glycoside, was enzymatically derived for the first time into novel esters using lipase as biocatalyst. The reaction system of glycoside acylation was optimized, and the effect of solvent nature, concentrations of substrate and biocatalyst, and acyl donors' structure on the acylation was studied. In the optimal system, various structures of acyl donors, either natural or unnatural, including short alkyl acyl groups, long chain acyl groups and acyl donors with aryl group were connected to molecular backbone of the glycoside, forming various structures of novel glycoside esters.

Environmentally benign synthesis of natural glycosides using apple seed meal as green and robust biocatalyst.

Salidroside is a natural glycoside with pharmacological activities of resisting anoxia, microwave radiation and fatigue, improving oxygen lack, and postponing ageing. In this work, salidroside and other natural glucosides such as cinnamyl O-beta-d-glucopyranoside and 4-methoxybenzyl O-beta-d-glucopyranoside were efficiently synthesized via an environmentally benign and energy economic process. In the synthetic process, apple seed, easily available from discards of fruit processing factories, was employed as a natural and green catalyst. Moreover, all of the catalyst, solvent and excessive substrate was reused or recycled. The biocatalytic reaction was carried out in a clean and less toxic medium of aqueous tert-butanol and the glucoside produced was selectively removed from reaction mixture by alumina column adsorption, making excessive substrate (aglycon) recyclable for a repeated use in the next batch of reaction. For improvement of the biocatalyst stability, apple seed meal was further cross-linked by glutaraldehyde, yielding a net-like porous structure within which the dissociating proteins were immobilized, resulting in improved permeability of the biocatalyst. After the simple cross-linking treatment, the half-life of apple seed catalyst was significantly improved from 29 days to 51 days. The productivity of the bioreactor in the case of salidroside can reach ca. 1.9 gl(-1)d(-1), affording the product in up to 99.3% purity after refinement.