Selective hydrodeoxygenation of lignin-derived phenolic monomers to cyclohexanol over tungstated zirconia supported ruthenium catalysts.

The selective hydrodeoxygenation (HDO) of lignin-derived methoxyphenols to cyclohexanol is one of the most significant transformation in biomass conversion since cyclohexanol is an important industrial raw material. This study has disclosed a series of tungstated zirconia with different Zr/W ratio supported Ru catalysts (Ru/xZrW, x means the molar ration of Zr/W) for the hydrodeoxygenation (HDO) of guaiacol to cyclohexanol. Among these catalysts, Ru/16ZrW has the best catalytic activity, which can achieve 92% yield of cyclohexanol under the conditions of 180 oC and 1 MPa H2 pressure for 2 h (TOF 231 h-1). Compared with Ru/ZrO2, Ru/16ZrW has smaller particles, more dispersed and electron-rich Ru species, significant hydrogen spillover and more acid sites, which are the main reason for its excellent performance on this reaction. Apart from guaiacol, other methoxy substitution phenols and organosolv lignin can also be converted into cyclohexanol via hydrodeoxygenation reactions over this catalyst.

Exploring the Correlation between Azido-Tetrazolo Tautomerizations and Isomer Structures: Electron Density of Bonding N Atoms and N-N Bond Polarity.

Azido-tetrazolo tautomerizations between azido N-heteroaromatic compounds and tetrazole-fused energetic materials can produce a new generation of high-energy density compounds. Density functional theory (DFT) computations are performed to explore the relationship between reaction barriers and electron densities of bonding N atoms, i.e., the terminal N1 and heterocyclic N2 atoms, for six reported tautomerizations. The results reveal four linear correlations between reverse reaction barriers (Gr) and the electron densities of N1 and N2 atoms in the product. N1 electron density (ρN1) and N-N bond polarity, as measured by the difference between the electron densities on the two N atoms (ΔρN = ρN1 - ρN2) in products, are inversely proportional to the reverse reaction barriers. They are also proportional to the energy barrier differences between the forward and reverse reactions (ΔG = Gf - Gr). Polar solvents, including DMSO, water, and acetone, can effectively increase the reverse reaction barriers (Gr) by improving the stability of products. This regularity is further confirmed by its application to four additional tautomerizations and can be used to screen out unfavorable azido-tetrazolo tautomerization reactions and increase the success rate of such synthesis.

S-Doping Regulated Iron Spin States in Fe-N-C Single-Atom Material for Enhanced Peroxidase-Mimicking Activity at Neutral pH.

Designing biomimetic nanomaterials with peroxidase (POD)-like activity at neutral pH remains a significant challenge. An S-doping strategy is developed to afford an iron single-atom nanomaterial (Fe1@CN-S) with high POD-like activity under neutral conditions. To the best of knowledge, there is the first example on the achievement of excellent POD-like activity under neutral conditions by regulating the active site structure. S-doping not only promotes the dissociation of the N─H bond in 3,3″,5,5″-tetramethylbenzidine (TMB), but also facilitates the desorption of OH* by the transformation of iron species' spin states from middle-spin (MS FeII) to low-spin (LS FeII). Meanwhile, LS FeII sites typically have more unfilled d orbitals, thereby exhibiting stronger interactions with H2O2 than MS FeII, which can enhance POD-like activity. Finally, a one-pot visual detection of glucose at pH 7 is performed, demonstrating the best selectivity and sensitivity than previous reports.

Nanozyme sensor array based on Fe, Se co-doped carbon material for the discrimination of Sulfur-containing compounds.

Developing methods for the accurate identification and analysis of sulfur-containing compounds (SCCs) is of great significance because of their essential roles in living organisms and the diagnosis of diseases. Herein, Se-doping improved oxidase-like activity of iron-based carbon material (Fe-Se/NC) was prepared and applied to construct a four-channel colorimetric sensor array for the detection and identification of SCCs (including biothiols and sulfur-containing metal salts). Fe-Se/NC can realize the chromogenic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by activating O2 without relying on H2O2, which can be inhibited by different SCCs to diverse degrees to produce different colorimetric response changes as "fingerprints" on the sensor array. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) revealed that nine kinds of SCCs could be well discriminated. The sensor array was also applied for the detection of SCCs with a linear range of 1-50 µM and a limit of detection of 0.07-0.2 µM. Moreover, colorimetric sensor array inspired by the different levels of SCCs in real samples were used to discriminate cancer cells and food samples, demonstrating its potential application in the field of disease diagnosis and food monitoring. ENVIRONMENTAL IMPLICATIONS: In this work, a four-channel colorimetric sensor array for accurate SCCs identification and detection was successfully constructed. The colorimetric sensor array inspired by the different levels of SCCs in real samples were also used to discriminate cancer cells and food samples. Therefore, this Fe-Se/NC based sensor array is expected to be applied in the field of environmental monitoring and environment related disease diagnosis.

Study on the Interactions Between Cisplatin and Cadherin by Fluorescence Spectrometry and Atomic Force Microscopy.

Cisplatin is an important platinum drug in cancer chemotherapy in clinical practice. It is well established that the main target of cisplatin is nuclear DNA. However, recent studies have demonstrated that platinum drugs may act on some important functional proteins in the human body. E-cadherin is a newly discovered glycoprotein that has been regarded as an important sign of the occurrence and development of some tumors. This study examines the interactions between cisplatin and E-cadherin by fluorescence spectrometry and atomic force microscopy (AFM). The fluorescence spectrometry results indicated that cisplatin can efficiently quench the fluorescence of E-cadherin. The calculated binding constant Kb was 3.20 × 106 (25 ℃), 1.36 × 106(31 ℃), and 8.22 × 105 L mol-1 (37 ℃). These results reveal that the fluorescence quenching effect of cisplatin on E-cadherin is static quenching. The obtained thermodynamic parameters ΔH < 0, ΔS < 0, and ΔG < 0, indicate that the binding of cisplatin on E-cadherin is a spontaneous process dominated by hydrogen bonds and Van der Waals forces. The AFM results revealed that E-cadherins are interlaced with each other to form a spherical-chain structure. The addition of cisplatin can significantly disrupt the interlaced structure of the E-cadherin molecules.

Green Synthesis and Antimicrobial Study on Functionalized Chestnut-Shell-Extract Ag Nanoparticles.

The chestnut shell is usually discarded as agricultural waste and the random deposition of it can cause environmental problems. In this study, monodisperse crystalline Ag nanoparticles (AgNPs) were synthesized by a hydrothermal approach, in which the chestnut shell extract served as both reducing agent and stabilizer. The synthesized Ag nanoparticles were characterized by ultraviolet-visible (UV) spectrophotometry, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) measurements. The TEM, XRD and XPS results revealed that the synthesized product was spherical Ag nanoparticles with a face-centered cubic crystal structure. The antimicrobial activity test indicated that the Ag nanoparticles modified by the chestnut shell extract had an obvious inhibitory effect on Escherichia coli, Staphylococcus aureus and Candida albicans. The measured MIC and MBC of functionalized chestnut-shell-extract AgNPs against E. coli, S. aureus and C. albicans is relatively low, which indicated that the present functionalized chestnut-shell-extract AgNPs are an efficient antimicrobial agent.

N, S Co-Coordinated Zinc Single-Atom Catalysts for N-Alkylation of Aromatic Amines with Alcohols: The Role of S-Doping in the Reaction.

S-doping emerged as a promising approach to further improve the catalytic performance of carbon-based materials for organic synthesis. Herein, a facile and gram-scale strategy was developed using zeolitic imidazole frameworks (ZIFs) as a precursor for the fabrication of the ZIF-derived N, S co-doped carbon-supported zinc single-atom catalyst (CNS@Zn1-AA) via the pyrolysis of S-doped ZIF-8, which was modified by aniline, ammonia and thiourea and prepared by one-pot ball milling at room temperature. This catalyst, in which Zn is dispersed as the single atom, displays superior activity in N-alkylation via the hydrogen-borrowing strategy (120 °C, turnover frequency (TOF) up to 8.4 h-1). S-doping significantly enhanced the catalytic activity of CNS@Zn1-AA, as it increased the specific surface area and defects of this material and simultaneously increased the electron density of Zn sites in this catalyst. Furthermore, this catalyst had excellent stability and recyclability, and no obvious loss in activity after eight runs.

Recent Advances in Carbon-Based Iron Catalysts for Organic Synthesis.

Carbon-based iron catalysts combining the advantages of iron and carbon material are efficient and sustainable catalysts for green organic synthesis. The present review summarizes the recent examples of carbon-based iron catalysts for organic reactions, including reduction, oxidation, tandem and other reactions. In addition, the introduction strategies of iron into carbon materials and the structure and activity relationship (SAR) between these catalysts and organic reactions are also highlighted. Moreover, the challenges and opportunities of organic synthesis over carbon-based iron catalysts have also been addressed. This review will stimulate more systematic and in-depth investigations on carbon-based iron catalysts for exploring sustainable organic chemistry.

Iron single-atom anchored N-doped carbon as a 'laccase-like' nanozyme for the degradation and detection of phenolic pollutants and adrenaline.

To solve the inherent defects of laccase, the first iron single-atom anchored N-doped carbon material (Fe1@CN-20) as a laccase mimic was disclosed. The FeN4 structure of this material can well mimic the catalytic activity of laccase. Although Fe1@CN-20 has a lower metal content (2.9 wt%) than any previously reported laccase mimics, it exhibits kinetic constants comparable to those of laccase, as its Km (Michaelis constant) and Vmax (maximum rate) are 0.070 mM and 2.25 µM/min respectively, which are similar to those of laccase (0.078 mM, 2.49 µM/min). This catalyst displays excellent stability even under extreme pH (2-9), high temperature (100 °C), strong ionic strength (500 mM of NaCl), high ethanol concentration (volume ratio 40%) and long storage time (2 months). Additionally, it can be reused for at least 7 times with only a slight loss in activity. Therefore, this material has a much lower price and better stability and recyclability than laccase, which has been applied in the detection and degradation of a series of phenolic compounds. In the detection of adrenaline, Fe1@CN-20 achieved a detection limit of 1.3 µM, indicating it is more sensitive than laccase (3.9 µM).

The interaction of proanthocyanidins with DNA molecules studied by atomic force microscopy and spectroscopic method.

The interactions of the naturally available botanicals with DNA molecules have received considerable attention owing to the potential to develop for medicinal agents. In this study, the interaction of proanthocyanidins with DNA molecules was studied by atomic force microscopy (AFM) and spectroscopic method. The AFM observation indicated that proanthocyanidins induced DNA molecules from double helix chains to the thick rope and toroids. The heights of the formed DNA structures are more than eight times than that of DNA double helix. Spectroscopic measurement results revealed that proanthocyanidins intercalated between the base pairs of DNA in the intercalative binding mode, which resulted in unwinding the DNA helix, twisting the DNA strands and finally transforming into the supercoiled DNA structures. All these results implied that DNA molecule is an important interaction target of proanthocyanidins, and the formed compact DNA structures have biological significance on the gene expression and regulation.

Catalytic Diastereo- and Enantioconvergent Synthesis of Vicinal Diamines from Diols through Borrowing Hydrogen.

We present herein an unprecedented diastereoconvergent synthesis of vicinal diamines from diols through an economical, redox-neutral process. Under cooperative ruthenium and Lewis acid catalysis, readily available anilines and 1,2-diols (as a mixture of diastereomers) couple to forge two C-N bonds in an efficient and diastereoselective fashion. By identifying an effective chiral iridium/phosphoric acid co-catalyzed procedure, the first enantioconvergent double amination of racemic 1,2-diols has also been achieved, resulting in a practical access to highly valuable enantioenriched vicinal diamines.

Clinical impact of recreational drug use among people living with HIV in southern Taiwan.

BACKGROUND: It is unclear about the impact of recreational drug use on the adherence, drug-drug interaction and the occurrence of sexual transmitted diseases (STDs) among people living with HIV. MATERIAL AND METHODS: A retrospective study was conducted between Dec 2016, and July 2018 to assess the clinical impact of recreational drug consumption in people living with HIV with antiretroviral therapy. We collected data of the demographics, recreational drug use, laboratory results and STDs diagnoses. Potential drug-drug interactions were checked with reference databases. The association between recreational drug use and STDs, HIV viral load suppression and drug interactions were evaluated. RESULTS: A total of 462 participants were enrolled, included 384 recreational drug users and 78 non-recreational drug users. Younger age (adjusted odds ratio [aOR], 0.94; 95% CI: 0.91-0.98; p = 0.001), longer HIV infection period (aOR, 1.11; 95% CI: 1.03-1.20; p = 0.009) and poor antiretroviral drug adherence (1-2 pills missing per month: aOR, 6.82; 95% CI: 3.50-13.27; p < 0.001; >2 pills missing per month: aOR, 3.50; 95% CI: 1.28-9.61; p = 0.015) were factors associated with recreational drug use. Methamphetamine and nitrites were two most common recreational drugs. Recreational drug use was significantly associated with STDs in one-year follow-up period (aOR, 2.43; 95% CI: 1.11-5.32; p = 0.027) but was not significantly associated with unsuppressed viral load, though a trend was observed (OR, 2.23; 95% CI: 0.92-5.37; p = 0.074). Potential interactions with recreational drugs included 33.1% antiretroviral drugs and 31.3% medications for comorbidities. CONCLUSION: Recreational drug was associated with STDs. A great proportion of the patients consuming recreational drugs had potential interactions with antiretroviral drugs and medications for comorbidities. The association of recreational drug use and unsuppressed viral load warrants further investigation.

Stereoselective Synthesis of Alkenyl Silanes, Sulfones, Phosphine Oxides, and Nitroolefins by Radical C-S Bond Cleavage of Arylalkenyl Sulfides.

A radical-mediated approach has been introduced for the C-S bond activation of arylalkenyl sulfides. The protocol provides an efficient approach for the generation of various alkenes including alkenyl silanes, sulfones, phosphine oxides, and nitroolefins. In most cases, these radical substitutions are performed under metal-free conditions with stereospecificity.

Acid/Phosphide-Induced Radical Route to Alkyl and Alkenyl Sulfides and Phosphonothioates from Sodium Arylsulfinates in Water.

A newly developed aqueous system with acid and phosphide was introduced in which odorless and stable sodium arylsulfinates can in situ generate arylsulfenyl radicals. These radicals have high reactivity to react with alkynes, alkenes, and H-phosphine oxides for the synthesis of alkyl and alkenyl sulfides and phosphonothioates. The control experiments and quantum calculations are also performed to gain insights into the generation mechanism of arylsulfenyl radicals. Notably, the chemistry is free of thiol odors, organic solvents, and metals.

Radical Route to 1,4-Benzothiazine Derivatives from 2-Aminobenzenethiols and Ketones under Transition-Metal-Free Conditions.

Transition-metal-free radical access to 1,4-benzothiazine derivatives from o-aminobenzenethiols is disclosed. This procedure is available for various ketones including α,ß-unsaturated, cyclic, linear, and fluoroalkyl ketones to generate a number of 1,4-benzothiazines, which exist in numerous bioactive and natural molecules, rendering this protocol attractive to both synthetic and medicinal chemistry.

A Route to α-Fluoroalkyl Sulfides from α-Fluorodiaroylmethanes.

α,α-Difluorodiaroylmethane can be used as a nucleophilic difluoromethylation reagent for generating α-thioaryl-α,α-difluoroacetophenones (Ar(1)COCF2SAr) and difluoromethylthiolated arenes (ArSCF2H) under transition-metal-free conditions. The reaction selectivity is mainly dependent on temperature. The method has also been extended to the synthesis of α-thioaryl-α-monofluoroacetophenones using α-monofluorodibenzoylmethane. Moreover, the benzoyl cation derived from α,α-difluorodibenzoylmethane can react with nucleophiles to afford the desired products in a one-pot process.

Odorless, One-Pot Regio- and Stereoselective Iodothiolation of Alkynes with Sodium Arenesulfinates under Metal-Free Conditions in Water.

A newly developed regio- and stereoselective radical addition of alkyne under metal-free conidtions has been disclosed. This chemistry, in which odorless sodium arenesulfinates in place of thiols are used as the sulfur reagent, provides an efficient, one-pot approach for the generation of ß-iodoalkenyl sulfides, which can be easily further functionalized to derive various alkenes and alkynyl sulfides rendering this methodology attractive to both synthetic and medicinal chemistry.

Serum MMP-9 is elevated in children with asthma.

This study explored the association of matrix metalloproteinase-9 (MMP-9) serum concentration and gene polymorphism with childhood asthma. Serum levels of MMP-9 were determined by sandwich enzyme-linked immunosorbent assay (ELISA) in 65 children with asthma (cases) and 68 healthy children (controls), and the -1562C/T polymorphism in MMP-9 was detected by polymerase chain reaction and restriction fragment-length polymorphism (PCR-RFLP) analysis. The results showed that the mean serum levels of MMP-9 in the children with asthma (136.53 ± 29.96 ng/ml) were significantly higher than that in the healthy controls (45.08 ± 12.53 ng/ml; P<0.05). At MMP-9 base position -1562, the frequencies of the genotypes CC, CT and TT in cases were 67.7, 29.2 and 3.1% and in controls were 73.5, 25.0 and 1.5%. The allele frequencies of C and T in cases vs. controls were 82.3 and 17.7% vs. 86.0 and 14.0%, respectively. No statistically significant difference was detected in genotype or allele frequency between these groups. In addition, no significant difference in serum levels of MMP-9 was observed within groups among children with different genotypes (P>0.05). Therefore, whereas serum levels of MMP-9 are associated with the occurrence of childhood asthma, the MMP-9 -1562C/T gene polymorphism has no correlation with the pathogenesis of childhood asthma.