Three-Component Cycloaddition To Synthesize Aziridines and 1,2,3-Triazolines.

An efficient three-component cycloaddition of oxa(aza)bicyclic alkenes/norbornene in the presence of NaN3 and arylsulfonyl chlorides was developed, affording the corresponding aziridine products in good yields (up to 82%) with moderate to good endo/exo selectivities (up to >99:1 endo/exo). Further studies showed that the cycloaddition of oxa(aza)bicyclic alkenes in the presence of NaN3 and chloroalkanes could afford the exo-cycloadduct 1,2,3-triazolines in good to excellent yields (up to 95%). Compared with the existing methodologies, the current protocol demands very simple and mild reaction conditions and is a metal-free catalyzed reaction. In addition, a plausible mechanism for the cycloaddition reaction was also proposed.

Palladium-Catalyzed syn-Stereocontrolled Ring Opening of Oxabicyclic Alkenes with Arylsulfonyl Hydrazides.

A novel palladium-catalyzed ring-opening reaction of oxabicyclic alkenes with arylsulfonyl hydrazides was first developed. In this work, we provide an efficient one-pot reaction to afford the corresponding cis-2-aryl-1,2-dihydronaphthalen-1-ols and 2-aryl-naphthalenes in moderate to excellent yields (up to 95%) under an open-air condition. Various types of functional groups attached to the substrates were tolerated well in this method. Among them, the cis-1,2-configuration of product 3ag was confirmed by X-ray crystallographic analysis. In addition, a plausible mechanism for ring opening was also proposed.

Spatial-temporal distribution of phthalate esters from riverine outlets of Pearl River Delta in China.

The aquatic environments of the Pearl River Delta (PRD) in China have been contaminated by various industrial chemicals from local industries. In this study, the spatial-temporal distribution of six priority phthalate esters (PAEs) in surface water and sediments from the PRD was investigated. The PAEs were detected with total concentrations (Σ6PAEs) ranging from 0.35 to 20.70 µg L⁻¹ in surface water and dry weight ranging from 0.88 to 5.69 µg g⁻¹ in sediments. The Σ6PAEs concentrations in surface water were higher in the wet season than those in the dry season, while the opposite pattern was observed in sediments. Di(2-ethylhexyl) phthalate (DEHP) was the most abundant congener, which was higher than those reported in the literature. Risk quotients for relevant aquatic organisms were obtained and showed that most of these PAEs, in particular, butyl benzyl phthalate, DEHP and di-n-octyl phthalate, have significant potential health and ecological risks for the aquatic environment studied.

Plant-Based Bimetallic Silver-Zinc Oxide Nanoparticles: A Comprehensive Perspective of Synthesis, Biomedical Applications, and Future Trends.

The universal emphasis on the study of green nanotechnology has led to biologically harmless uses of wide-ranged nanomaterials. Nanotechnology deals with the production of nanosized particles with regular morphology and properties. Various researches have been directed on nanomaterial synthesis by physical, chemical, and biological means. Understanding the safety of both environment and in vivo, a biogenic approach particularly plant-derived synthesis is the best strategy. Silver-zinc oxide nanoparticles are most effective. Moreover, these engineered nanomaterials via morphological modifications attain improved performance in antimicrobial, biomedical, environmental, and therapeutic applications. This article evaluates manufacturing strategies for silver-zinc oxide nanoparticles via plant-derived means along with highlighting their broad range of uses in bionanotechnology.

Construction of two 3D homochiral frameworks with 1D chiral pores via chiral recognition.

The reactions of a pair of enantiomers of macrocyclic nickel(II) complexes with racemic penicillamine generated two 3D hydrogen-bonded homochiral frameworks of {[Ni(f-(SS)-L)](2)(l-pends)(ClO(4))(2)}(n) (Λ-1) and {[Ni(f-(RR)-L)](2)(d-pends) (ClO(4))(2)}(n) (Δ-1). The frameworks possess 1D tubular pores and opposite right/left-handed helical porous surfaces (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane; pends(2-) = penicillaminedisulfide anion).

Comprehensive transcriptome and metabolome profiling reveal metabolic mechanisms of Nitraria sibirica Pall. to salt stress.

Nitraria sibirica Pall., a typical halophyte that can survive under extreme drought conditions and in saline-alkali environments, exhibits strong salt tolerance and environmental adaptability. Understanding the mechanism of molecular and physiological metabolic response to salt stress of plant will better promote the cultivation and use of halophytes. To explore the mechanism of molecular and physiological metabolic of N. sibirica response to salt stress, two-month-old seedlings were treated with 0, 100, and 400 mM NaCl. The results showed that the differentially expressed genes between 100 and 400 mmol L-1 NaCl and unsalted treatment showed significant enrichment in GO terms such as binding, cell wall, extemal encapsulating structure, extracellular region and nucleotide binding. KEGG enrichment analysis found that NaCl treatment had a significant effect on the metabolic pathways in N. sibirica leaves, which mainly including plant-pathogen interaction, amino acid metabolism of the beta alanine, arginine, proline and glycine metabolism, carbon metabolism of glycolysis, gluconeogenesis, galactose, starch and sucrose metabolism, plant hormone signal transduction and spliceosome. Metabolomics analysis found that the differential metabolites between the unsalted treatment and the NaCl treatment are mainly amino acids (proline, aspartic acid, methionine, etc.), organic acids (oxaloacetic acid, fumaric acid, nicotinic acid, etc.) and polyhydric alcohols (inositol, ribitol, etc.), etc. KEGG annotation and enrichment analysis showed that 100 mmol L-1 NaCl treatment had a greater effect on the sulfur metabolism, cysteine and methionine metabolism in N. sibirica leaves, while various amino acid metabolism, TCA cycle, photosynthetic carbon fixation and sulfur metabolism and other metabolic pathways have been significantly affected by 400 mmol L-1 NaCl treatment. Correlation analysis of differential genes in transcriptome and differential metabolites in metabolome have found that the genes of AMY2, BAM1, GPAT3, ASP1, CML38 and RPL4 and the metabolites of L-cysteine, proline, 4-aminobutyric acid and oxaloacetate played an important role in N. sibirica salt tolerance control. This is a further improvement of the salt tolerance mechanism of N. sibirica, and it will provide a theoretical basis and technical support for treatment of saline-alkali soil and the cultivation of halophytes.

Tissue tolerance mechanisms conferring salinity tolerance in a halophytic perennial species Nitraria sibirica Pall.

Plant salt tolerance relies on a coordinated functioning of different tissues and organs. Salinity tissue tolerance is one of the key traits that confer plant adaptation to saline environment. This trait implies maintenance low cytosolic Na+/K+ ratio in metabolically active cellular compartments. In this study, we used Nitraria sibirica Pall., a perennial woody halophyte species, to understand the mechanistic basis of its salinity tissue tolerance. The results showed that the growth of seedlings was stimulated by 100-200 mM NaCl treatment. The ions distribution analysis showed that the leaves act as an Na+ sink, while the plant roots possess superior K+ retention. The excessive Na+ absorbed from the soil was mainly transported to the shoot and was eventuallysequestrated into mesophyll vacuoles in the leaves. As a result, N. sibirica could keep the optimal balance of K+/Na+ at a tissue- and cell-specific level under saline condition. To enable this, N. sibirica increased both vacuolar H+-ATPase and H+-PPase enzymes activities and up-regulated the expressions of NsVHA, NsVP1 and NsNHX1 genes. Vacuolar Na+ sequestration in the leaf mesophyll, mediated by NsVHA, NsVP1 and NsNHX1, reduced the Na+ concentration in cytosol and inhibited further K+ loss. Meanwhile, N. sibirica enhanced the Two Pore K+ expression at the transcriptional level to promote K+ efflux from vacuole into cytoplasm, assisting in maintaining cytosolic K+ homeostasis. It is concluded that the tissue tolerance traits such as vacuolar Na+ sequestration and intracellular K+ homeostasis are critical to confer adaptation of N. sibirica to soil salinity.

A dual-response ratiometric fluorescent probe for hypochlorite and hydrazine detection and its imaging in living cells.

In this work, a dual-response ratiometric fluorescent probe (E)-3-(5-(2-nitrovinyl)thiophen-2-yl)-9-phenyl-9H-carbazole (NTPC) for high selectivity and sensitivity detection of ClO- and N2H4 was successfully developed. This probe NTPC showed ratiometric fluorescent response to ClO- and N2H4, which induces obvious naked-eye color changes, respectively. In addition, the NTPC for ClO- and N2H4 detection displayed low detection limits of 71.4 nM and 0.6 µM, respectively. And the sensing mechanism of NTPC with ClO- and N2H4 was well confirmed by 1H NMR and HR-MS spectra. Moreover, this novel probe was applied to monitoring and differentiating ClO- and N2H4 in living cells, and exhibits good biocompatibility and low cytotoxicity.

Degradation mechanism, intermediates and toxicology assessment of tris-(2-chloroisopropyl) phosphate using ultraviolet activated hydrogen peroxide.

Organophosphate flame retardants (OPFRs), one kind of emerging flame retardants, have received prevalent attention owing to their ubiquity in aquatic matrices and their characteristics of being refractory to biodegradation. In current research, the degradation mechanism of tris-(2-chloroisopropyl) phosphate (TCPP), one of OPFRs, and its toxicological evaluation using UV-driven hydroxyl radical oxidation were investigated. A pseudo-first order reaction was fitted with an apparent rate constant (Kobs) of 0.1328 min-1 on transformation of TCPP in the case of CH2O2 0.1 mM, pH 6.6-7.1 and 4.7 mW cm-2 UV irradiation. High resolution mass spectroscopy analyses identified nine degradation products (eg., C6H13Cl2O4P (m/z 251.0002), C9H17Cl2O5P (m/z 307.0266), C9H17Cl2O6P (m/z 323.0217), C9H18Cl3O5P (m/z 343.0033)) during transformation of TCPP. The removal efficiency dropped by inhibitory effect of natural organic matters and anions, implying that the complete mineralization of TCPP may be difficult in actual water treatment process. The toxicity assessment has shown an decrease in reactive oxygen species (ROS) and apoptosis, membrane potential (MP) elevation of Escherichia coli, and biological molecular function revision (eg., metabolism and DNA biosynthesis), indicating that toxicity of degradation products were conspicuously decreased in comparison with intact TCPP. To sum up, effective detoxification of TCPP can be realized by a UV driving radical-based oxidation, which will provide an alternative safe treatment method to control TCPP in water matrix.

Tailoring the Vertical Morphology of Organic Films for Efficient Planar-Si/Organic Hybrid Solar Cells by Facile Nonpolar Solvent Treatment.

The optical and electrical properties of the blending organic film poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (PEDOT:PSS) are strongly affected by its morphology, resulting in the performance variation in Si/organic hybrid solar cells. Here, a facile postsolvent treatment is used to tailor the vertical morphology of PEDOT:PSS by introducing a nonpolar solvent. X-ray photoelectron spectroscopy depth-profiling measurements show that the distribution of PEDOT and PSS on the surface of n-type Si can be changed by nonpolar solvent n-hexane (NHX) treatment, where more PSS aggregate at the bottom of the blend film and more PEDOT float up to the top, as compared with the reference sample. As a result, after NHX treatment, the average lifetime of the Si/organic films is increased from 152 µs for untreated samples to 248 µs for NHX-treated ones because of the better passivation effect of PSS on Si. Moreover, the transmission line model measurements indicate that the contact resistance (RC) of PEDOT:PSS film and the Ag electrode is decreased for better charge collection after NHX treatment. Eventually, the best power conversion efficiency (PCE) of 13.78% for NHX-treated planar solar cells is obtained, much higher than the PCE (with best of 12.78%) of reference devices without nonpolar solvent treatment. Our results provide a facile method to tailor the vertical morphology of the PEDOT:PSS in Si/organic hybrid solar cells.

Two novel polysaccharides from Solanum nigrum L. exert potential prebiotic effects in an in vitro fermentation model.

In this research, two novel polysaccharides (S1 and S2) from Solanum nigrum L were extracted and purified. Then homogeneity, molecular weights, major chemical contents and monosaccharide compositions of S1 and S2 were determined. Then, the effects of S1 and S2 on human faecal microbial community and short-chain fatty acid production were investigated using an in vitro fermentation model. Results showed that S1 and S2 have different impacts on human gut microbiota in vitro. S1 selectively promoted the abundance of 9 genera and the production of propionic acid, butyric acid, isobutyric acid, valeric acid and isovaleric acid; while S2 selectively promoted the abundance of 8 genera and the production of acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid and succinic acid. Also, S1 group had higher abundance of genera Butyricimonas and Megamonas and higher levels of lactic acid than S2; while S2 group had higher abundance of Megaphaera and higher levels of butyric acid, valeric acid, isobutyric acid, isovaleric acid and succinic acid comparably. We concluded that S1 and S2 may have potential prebiotic functions.

Controllable Cs xFA1- xPbI3 Single-Crystal Morphology via Rationally Regulating the Diffusion and Collision of Micelles toward High-Performance Photon Detectors.

Cs xFA1- xPbI3 single crystals are expected to provide more excitement in optoelectronic applications, including photodetector, laser, light-emitting diode, etc. Herein, we aim to gain an in-depth understanding of the growth mechanisms of perovskite single crystal with various morphologies in view of microscopic dynamics by the combination of component, structure, and solvent engineering. A sequence of Cs xFA1- xPbI3 (0 ≤ x ≤ 0.14) perovskite single crystals with a dodecahedron morphology and tunable aspect ratio can be obtained by means of a solution-processed uniform-cooling approach. The optimized Cs0.1FA0.9PbI3 single crystals prepared in γ-butyrolactone mixed with dimethyl sulfoxide are theoretically and experimentally demonstrated to have superior performances, e.g., extremely higher long-term stability, lower trap density, and higher mobility. The broadband absorption, i.e., 300-910 nm, enables its application in near-infrared detection (880 nm), and the corresponding detector demonstrates higher responsivity at different light intensities and a fast photocurrent response (τ1 = 11 µs, τ2 = 10 µs). Equally important, we also explore the application of optimized Cs0.1FA0.9PbI3 single crystals with a tunable aspect ratio in an X-ray detector and the extremely high sensitivity (2772.1 µC Gyair-1 cm-2 under a bias of 150 V) demonstrates their good potential for radiation detection.

[FTIR studies of L-threonic acid and its metal compounds].

Highly pure solid compounds, such as L-threonic acid, calcium L-threonate, magnesium L-threonate, manganese L-threonate, cobalt L-threonate, nickel L-theronate, and zinc L-threonate, were prepared, wherein, L-threonic acid was obtained from calcium L-threonate by strong acid type ion exchange process, calcium L-threonate or zinc L-threonate was prepared by alcohol extracting the concentrated filter liquor of the reaction of Vc, H2O2 and CaCO3 or ZnCO3, the reminder of the compounds were synthesized using alcohol extracting the concentrated solution derived from the reaction of L-threonic acid solution, prepared by double decomposition reaction of calcium L-threonate with oxalic acid, and superfluous MgO, MnCO3, Co2(OH)2CO3 and Ni2(OH)2CO3. The compositions of the compounds were determined by chemical and elemental analysis, and these compounds have the formula M(C4H7O5)2.nH2O (M = Ca, Zn, n = 0; M = Mg, Mn, Co, n = 1; M = Ni, n = 2). The purity of the compounds was 99.60% by HPLC. The IR spectra of the complexes were similar with each other but different from that of L-threonic acid. The characteristic absorption peaks of water were not observed in those of calcium L-threonate or zinc L-threonate, which showed that the molecule of water was not involved in the complexes. Further analyses indicate that M2+ in the compounds coordinated to oxygen atom of the carboxy group, while the proton of the carboxyl group was dissociated and the proton belonging to hydroxyl was not M2+ coordinated to L-threonic acid through the sp3 hybrizated fashion. It was assumed that the coordination number of M2+ was 4.

Novel mixed-valent Co(II)2Co(III)4Ln(III)4 aggregates with ligands derived from tris-(hydroxymethyl)aminomethane (Tris).

Isostructural Co(II)2Co(III)4Ln(III)4 (Ln = Y (1), Gd (2) and Dy (3)) coordination clusters formed using the ligand Tris are the first examples of 3d-4f complexes involving this ligand and show weak ferromagnetic coupling between the Co(II) ions and slow relaxation (SMM) behaviour for 3.