Well-defined, reversibly light-responsive amphiphilic diblock copolymer grafted with spiropyran, was prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization. The copolymer self-assembles into polymeric micelles in water and exhibits reversible dissolution and re-aggregation characteristics upon ultraviolet (UV) and visible (Vis)-light irradiation. The fluorescence response of spiropyran immobilized onto the copolymer was light switchable. When nitrobenzoxadiazolyl derivative (NBD) dyes are encapsulated into the core of the micelles, a reversible, light-responsive, dual-color fluorescence resonance energy transfer (FRET) system is constructed and processed, which is well regulated by alternatively UV/vis irradiation. We anticipate these photoswitchable and FRET lighting up nanoparticles will be useful in drug delivery and cell imaging or tracking synchronously.

Pyrazoles and their derivatives are important heterocycles found in nature and present in numerous bioactive compounds. In contrast to 3 or 5-aryl pyrazole, the preparation of 4-aryl pyrazole is fairly rare. Utilizing microwave irradiation, the synthesis of 4-substituted-arylpyrazole via Suzuki cross-coupling has been developed with a wide range of substrates. The remarkable advantages of this method are mild reaction conditions, simple operation, high yield, and short reaction time. Product structures were identified by MS, ¹H NMR, ¹³C NMR, and elemental analysis.

CuO nanoparticles were synthesized at a relatively low temperature (80 ℃) for 2 h using polyethylene glycol-glycerol mixture which acts as a capping agent. A detailed characterization of the synthesized nanomaterials were performed utilizing X-ray diffraction (XRD), infra-red spectroscopy (IR), thermogravimetric analysis (TGA-DTA), transmission electron microscopy (TEM), photoluminescence (PL) by studying its crystalline phase, vibrational mode, thermal analysis, morphology and photoluminescence properties. The effect of annealing on the as-prepared nanoparticles were studied and compared with their corresponding bulk counterpart. The synthesized nanoparticles have been screened for in vitro cytotoxicity (IC₅₀) studies against the human cervical adenocarcinoma cell line (HeLa) using MTT assay methods. The as-prepared nanoparticle inhibits the proliferation of this HeLa cell. The standard disc diffusion method has been used to study the antibacterial activity of the samples against the human pathogenic bacteria Escherichia coli (MTCC 729), Proteus mirabilis (MTCC 425) and Klebsiella pneumoniae subsp. pneumoniae (MTCC 432). The results have been compared with the positive control antibiotic gentamycin. The synthesized nanoparticles would provide a potential alternative to antibiotics for controlling some of the microorganisms causing urolithiasis.

An environmentally benign processing approach for furfural production from xylose and xylan under verymild conditions (353-373 K) was developed with the addition of metal chlorides in ChCl-oxalic acid (a deep eutectic solvent (DES)) synthesized from cheap and renewable starting materials). ChCl-oxalic acid acted as both a Brønsted acid catalyst and a reaction medium in this catalytic route. In addition, a biphasic system with methyl isobutyl ketone as an extracting reagent (DES/MIBK) to further increase furfural yield was also proposed. This processing approach for producing furfural eliminated the large energy consumption for high pressure saturated steam and the generation of acidic effluent, which was very difficult to handle. The whole catalytic system was more environmentally friendly compared with the commercial process for furfural production.

The continuous dehydration of D-glucose into 5-hydroxymethylfurfural (HMF) was carried out under mild conditions, using SO₃H-functionalized acidic ionic liquids as catalysts and H₂O-4-methyl-2- pentanone (MIBK) biphasic system as solvent. High glucose conversion of 97.4% with HMF yield of 75.1% was obtained at 120 ℃ for 360 min, also, small amounts of levulinic acid (LA) and formic acid were generated. Generally, the dosage of catalyst and the initial content of glucose influenced the reaction significantly; the HMF selectivity decreased with the excessive elevation of temperature and prolonging of time; and water content in the system had a negative effect on the reaction. The ionic liquid catalyst could be recycled and exhibited constant activity for five successful runs. This paper provided a new strategy for HMF production from glucose.

A new application ofmetal organic framework (MOF) as a pseudo-capacitive material for supercapacitors is investigated. To this end, a simple nickel-based MOF, formulated Ni₃(btc)₂•12H₂O, is synthesized via a hydrothermal reaction. As an electro-active material, such nickel-based MOF exhibits superior pseudocapacitive behavior in KOH aqueous electrolyte with a high specific capacitance of 726 F g^-1. Also, it displays good electrochemical stability with 94.6% of the initial capacitance over consecutive 1000 cycles. In addition, a simple asymmetric supercapacitor with a high energy density of 16.5 Wh kg^-1 is successfully built using the nickel-based MOF as positive electrode and commercial activated carbon as negative electrode in KOH electrolyte.

During the laboratory optimization and the late phase manufacturing studies of the cholesterol absorption inhibitor Ezetimibe 1, the formation of several stereoisomers was observed. To study the complete stereoisomer profile of Ezetimibe 1,we have synthesized and completely characterized several key stereoisomers of Ezetimibe 1 for the first time. This study will provide an access to the reference standard of these stereoisomers andmay have some implications in the development of new medicines.

This work provided the first example of incorporating the oxindole moiety into the Betti bases. The new type of Betti bases were conveniently synthesized in good yields from the three-component reaction of β-naphthol, isatins and cyclic amines, such as piperidine ormorpholine, in methylene dichloride without any other catalyst.

Ionic liquid gel polymers have widely been used as the electrolytes in all-solid-state supercapacitors, but they suffer from low ionic conductivity and poor electrochemical performance. Arc discharge is a fast, low-cost and scalable method to prepare multi-layered graphene nanosheets, and as-made graphene nanosheets (denoted as ad-GNSs) with few defects, high electrical conductivity and high thermal stability should be favorable conductive additive materials. Here, a novel ionic liquid gel polymer electrolyte based on an ionic liquid (EMIMNTF₂) and an copolymer (P(VDF-HFP)) was modified by the addition of ad-GNSs as an ionic conducting promoter. This modified gel electrolyte shows excellent thermal stability up to 400℃ and a wide electrochemical window of 3 V. An all-solid-state supercapacitor based on commercial activated carbon was fabricated using this modified ionic liquid gel polymer electrolyte, which shows obviously improved electrochemical behaviors compared with those of the corresponding all-solid-state supercapacitor using pure ionic liquid gel polymer electrolyte. Specially, smaller internal resistance, higher specific capacitance, better rate performance and cycling stability are achieved. These results indicate that the ionic liquid gel polymers modified by ad-GNSs would be promising and suitable gel electrolytes for high performance all-solid-state electrochemical devices.

Pentylpyridinium tribromide and aqueous ammonium acetate was used for the rapid oxidative conversion of benzyl alcohols, benzaldehydes and benzyl amines to the corresponding benzonitriles in good to excellent yields. This simple, mild and one-pot system provides easy workup and separation of the products.

A convenient, efficient and practical metal-free method for the synthesis of substituted phenols from arylboronic acids has been developed. The protocol uses hydrogen peroxide as a hydroxylating agent, ammonium bicarbonate as an additive, and the reactions were conveniently performed in water at room temperature. Themethod shows an excellent tolerance of functional groups, so it will find a wide variety of applications in academic and industrial research.

A substitution reaction of amines with alcohols for N-alkylated amines has been developed using inexpensive AlC_l3 without any ligand or additive. Either aromatic or aliphatic amines and primary or secondary alcohols perform the AlC_l3-mediated reaction smoothly to afford various N-alkylated amines in satisfactory yields.

A series of SBA-15 supported bimetallic Rh-Ni catalysts with different weight ratio of Rh/Ni in the range of 0-0.04 were prepared for carbon dioxide reforming of methane. The doping effect of Rh on catalytic activity as well as carbon accumulation and removal over the catalysts was studied. The characterization results indicated that the addition of a small amount of Rh promoted the reducibility of Ni particles and decreased the Ni particle size. During the dry reforming reaction, the carbon deposition was originated from CH₄ decomposition and CO disproportionation. The Rh-Ni catalyst with smallmetallic particle size inhibited the carbon formation and exhibited high efficiency in the removal of coke. In comparison with bare Ni-based catalyst, the Rh-Ni bimetallic catalysts showed high activity and stability in the dry reforming of methane.

Dipeptidyl peptidase IV (DPP4) inhibitors are proven in the treatment of type 2 diabetes. We designed and synthesized a series of novel indole compounds that selectively inhibit the activity of DPP4 over dipeptidyl peptidase 9 (DPP9) (>200 fold). We further co-crystallized DPP4 with indole sulfonamide (compound 1) to confirm a proposed binding mode. Good metabolic stability of the indole compounds represents another positive attribute for further development.

In this paper, an efficient synthesis of 5-alkynyl-1,2,3-triazoles through a one-pot aerobic oxidative coupling reaction of various alkynes and azides has been developed. Further derivatization of 5-alkynyl-1,2,3-triazoles readily yielded 5-carbonyl-1,2,3-triazoles, 5-carboxylic-1,2,3-triazole, 5-hydroxyalkyl-1,2,3-triazoles and 5-quinoxaline-1,2,3-triazole, which provided an entry into structurally diverse 5-functionalized-1,2,3-triazoles.

This study aimed to establish a rapid analytical method to determine antioxidants in essence. A simple, efficient and practical, vortex-assisted, cloud-point extraction (VACPE) procedure is proposed for extracting and pre-concentrating four different of synthetic phenolic antioxidants (SPAs), propyl gallate (PG), tert-butylhydroquinone (TBHQ), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) in essence prior to high performance liquid chromatography (HPLC) analysis. The non-ionic surfactant, fatty alcohol polyoxyethylene ether-9 (AEO-9), was used as extractant and vortex-mixing was utilized to reduce extraction time and improve extraction efficiency. The effective parameters of the extraction process, such as volume of extraction solvent, pH, vortex-mixing time, equilibration temperature and time, were optimized. Under the optimum conditions, the linear range of PG, TBHQ, BHA and BHT was 8.0-800 ng/mL. All correlation coefficients of the calibration curves were higher than 0.996 and relative standard deviations (RSD, n=5) were 2.36%-5.46%. The proposed method was successfully applied to the extraction and determination of antioxidants in essence samples with satisfactory relative recoveries of 89.4%-103.5%. The results confirmed the SPAs of essence could be effectively monitored by this method and also established good reference criteria for essence.

3-(Diphenylphosphino)propanoic acid (L2) has proved to be an efficient ligand for the copper-catalyzed C-N coupling reactions. N-arylation of imidazoles with aryl iodides catalyzed by CuCl/L2 was smoothly carried out in DMSO at 100 ℃ with a yield up to 98%. N-arylation of 1H-pyrazole with aryl iodides and bromides catalyzed by Cu(OAc)₂/L2 in 1,4-dioxane also gave the corresponding products with yields of 40%-98%.

A facile, one-pot synthesis of N-aryl propargylamine from aromatic boronic acid, aqueous ammonia, and propargyl bromide has been achieved under microwave-assisted conditions. The reactions can be smoothly completed within a total 10 min through a two-step procedure, including copper-catalyzed coupling of aromatic boronic acids with aqueous ammonia and following propargylation by propargyl bromide.

meso-Tetrakis(4-aminophenyl)porphyrin (TAPP) can self-assemble into nanostructures with different morphologies by a phase-transfer method. The morphologies (nanospheres, nanorods and nanothorns) of porphyrin nanoaggregates could be easily tuned just by changing the concentration of porphyrin in a proper solvent at room temperature. HRTEM images revealed the formation of highly ordered supramolecular arrays of TAPP, i.e., superlattice of TAPP molecules in nanoaggregates, which agreed well with the size of one molecule of TAPP. UV-vis absorption spectra showed an obvious red shift of the Soret band of TAPP, indicating the formation of J-aggregates of TAPP in nanoaggregates.

Metabolomics is an emerging field dealing with the measurement and interpretation of small molecular byproducts of biochemical processes, or metabolites, which can be used to generate profiles from biological samples. Promising for use in pathophysiology, metabolomic profiles give the immediate biological state of a sample. These profiles are altered in diseases and are detectable in biological samples, such as tissue, blood, urine, saliva, and others. Most remarkably, metabolic profiles usually are altered before symptoms appear in a patient. For this reason, metabolomics has potential as a reliable method for an early diagnosis of diseases through disease biomarker identification. This application is most prevalent in cancer, such as head and neck cancer (HNC). Metabolomic studies offer avenues to improve on current medical techniques through the application of mass spectrometry (MS), nuclear magnetic resonance spectroscopy (NMR), and statistical analysis to determine better biomarkers than those currently known. In this review, we discuss the use of MS and NMR tools for detecting biomarkers in tissue and fluid samples, and the appropriateness of metabolomics in analyzing cancer. Advantages, disadvantages, and recent studies on metabolomic profiling techniques in HNC analysis are also discussed herein.

We describe a novel method for the synthesis a new magnetic bromochromate hybrid nanomaterial, Fe₃O₄@SiO₂@TEA@[CrO₃Br], as a catalyst.Thephysical properties,morphology andmagnetic investigations of magnetic bromochromate hybrid nanomaterials are identified by transmission electron microscopy (TEM), scanning electronmicroscopy (SEM)and vibrating samplemagnetometer (VSM)techniques. Fourier transform infrared (FT-IR), elemental analysis, X-ray fluorescence (XRF), X-ray diffraction (XRD) were also used for structural identification. The quantity of chromiumis approximately 0.38%, which confirms to the immobilization amount of [CrO₃Br] and is equal to 0.007 mol/100 g.

The objective of this study was to investigate the potential of methoxy polyethylene glycol (mPEG) grafted chitosan (mPEG-g-CS) to be used as a drug carrier. mPEG-g-CS was successfully synthesized by one-step method with formaldehyde. The substitution degree of mPEG on chitosan was calculated by elemental analysis and was found to be (3.23±0.25)%. mPEG-g-CS self-assembled micelles were prepared by ultrasonic method with the controlled size of 178.5-195.1 nm and spherical morphology. Stable dispersion of the micelles was formed with the zeta potential of 2.3-30.2 mV. 5-Fluorouracil (5-FU), an anticancer chemotherapy drug, was used as a model drug to evaluate the efficiency of the new drug delivery carrier. The loading efficiency of 5-FU was (4.01±0.03)%, and the drug-loaded mPEG-g-CS self-assembled micelle showed a controlled-release effect. In summary, the mPEG-g-CS self-assembled micelle is proved to be a promising carrier with controlled particle size and controlled-release effect. Therefore, it has great potential for the application as 5-FU carriers for effective anti-tumor activity.

10 mol% CuI combined with the DMEDA ligand can efficiently catalyze the N-arylation of 2-arylindoles with aryl iodides and aryl bromides in good to excellent yields. The aryl halides bearing electron-rich or electron-deficient functional groups can be well tolerated under this mild reaction conditions.

A polyvinylpolypyrrolidone supported triflic acid was shown to be useful as a recyclable heterogeneous catalyst for the rapid and efficient synthesis of quinoxaline derivatives in good-to-excellent yields. The catalyst is easily prepared, air-stable, reusable, and easily removed from the reaction mixtures.

Isoquinoline reacts with dialkyl acetylenedicarboxylates in the presence of kojic acid or 8-hydroxyquinoline to generate 1,2-dihydroisoquinoline derivatives. The simplicity, mild reaction conditions and high yields of products make it an interesting process compared to other approaches. The compounds have been analyzed for antibacterial activity against Gram negative and Gram positive bacteria. The results indicated that 1,2-dihydroisoquinolines derived from kojic acid are effective against all of the studied bacteria especially against Bacillus subtilis, while the products obtained from 8-hydroxyquinoline are active only against Gram positive bacteria.

In this work, solid-phase microextraction coupled with gas chromatography-mass spectrometry was developed to determine trace levels of nitrobenzene compounds in water and soil samples. Graphene was chosen as the extractionmaterial and its composite was coated on a stainless steel wire through sol- gel technique for the solid phase microextraction. The key parameters influencing the extraction efficiency were optimized. Under the optimal conditions, the linearity for the compounds was observed in the range of 0.02-15.0 μg/L for water samples, and 0.2-60.0 μg/kg for soil samples, with the correlation coefficients (r) of 0.9966-0.9987. The limits of detection of the method were 0.0025-0.005 μg/L for water samples, and 0.02-0.04 μg/kg for soil samples. The recoveries for the spiked samples were in the range of 72.0%-113.2%, and the precision, expressed as the relative standard deviations, was less than 12.1%.

A simple and practical method for the synthesis of N-substituted-2-aminobenzothiazoles via a crosscoupling reaction of 2-iodo anilines with isothiocyanates is envisaged using nano copper oxide as a recyclable catalyst and Cs₂CO₃ as a base in PEG-400, as a bio-degradable, reusable, inexpensive and nontoxic reaction medium, under ligand-free conditions. The present tandem process underlines environmental acceptability to access a wide range of N-substituted-2-aminobenzothiazoles in good to excellent yields.

A simple and efficient Knoevenagel condensation between α,β-unsaturated aldehydes and active methylene compounds is reported. Notably, this condensation can be catalyzed by PPL (lipase from porcine pancreas) with satisfied yields (49%-92%). Moreover, PPL induces moderate Z/E selectivity in the Knoevenagel condensation.

Reaction temperature is one of the key parameters in the synthesis ofmetal-organic frameworks (MOFs). Though there is no convergence with regard to the various experimental parameters, reaction temperature has been found to have remarkable influence on the formation and structure of MOFs, especially toward the control of topology and dimensionality of the MOF structures. Theoretically, the reaction temperature affects directly the reaction energy barrier in reaction thermodynamics and the reaction rate in the reaction kinetics. This review aims to show the influence of reaction temperature on crystal growth/assembly, structural modulation and transformation of MOFs, and to provide primary information and insights into the design and assembly of desired MOFs.

A simple synthetic protocol has been developed involving the three-component reaction between 1,2-diamines, ethyl pyruvate and α-bromo ketones in the presence of FeCl₃ as a catalyst. A number of pyrrolo[1,2-a]quinoxaline and pyrrolo[1,2-a]pyrazine derivatives were synthesized in excellent yields using this protocol.

Nanopore technique plays an important role in single molecule detection, which illuminates the properties of an individual molecule by analyzing the blockage durations and currents. However, the traditional exponential function is lack of efficiency to describe the distributions of blockage durations in nanopore experiments. Herein, we introduced an exponentially modified Gaussian (EMG) function to fit the duration histograms of both simulated events and experimental events. In comparison with the traditional exponential function, our results demonstrated that the EMG provides a better fit while covers the entire range of the distributions. In particular, the fitted parameters of EMG could be directly used to discriminate the sequence length of the oligonucleotides at single molecule level.

The novel coordination structures of europium and terbium chloride-picolinamide complexes (EuCl₃•(C₆H₆N₂O)₂•5H₂O, Eu-pa and TbCl₃•(C₆H₆N₂O)₂•5H₂O, Tb-pa) are reported. The crystal structures in the solid state are characterized by X-ray single crystal diffraction, FTIR, Raman, FIR, THz and luminescence spectroscopy. In the crystal structures, the pyridyl nitrogen and carbonyl oxygen atoms in picolinamide are coordinated to the metal ions to form a five-membered ring structure. The experimental results indicate the similar coordination structures of Eu and Tb-pa complexes and the changes of hydrogen bonds and conformation of the ligands induced by complexation. The results provide models for the coordination structures of lanthanide ions with ligands having amide groups.

An EPDDMAC-GE polymer (hydrophilic molecule) has been synthesized based on epoxypropyl dodecyl dimethyl ammonium chloride (EPDDMAC) and gelatin. A DEEPSAC-GE polymer (hydrophobicmolecule) has been synthesized based on diethyl-2,3-epoxypropyl-[3-methyldimethoxyl] silpropyl ammonium chloride (DEEPSAC) and gelatin. Compared with initial gelatin, the gelatin modified with quaternary ammonium salts containing epoxide groups exhibits stronger antibacterial activity.

This work aimed at effectively utilizing the chemically depolymerized waste poly(ethylene terephthalate) (PET) fibers into useful products for the textile industry. PET fibers were glycolytically degraded by excess ethylene glycol as depolymerizing agent and zinc acetate dihydrate as catalyst. The glycolysis product, bis(2-hydroxyethyl) terephthalate (BHET), was purified through repeated crystallization to get an average yield above 80%. Then, BHET was nitrated, reduced, and azotized to get diazonium salt. Finally, the produced diazonium salt was coupled with 1-(4-sulfophenyl)-3-methyl-5-pyrazolone to get azo dyestuff. The structures of BHET and azo dyestuff were identified by FTIR and 1H NMR spectra and elemental analysis. Nylon filaments dyed by the synthesized azo dyestuff with the dye bath pH from 4.14 to 5.88 showed bright yellow color. The performances of the dyestuff were described with dye uptake, color fastness, K/S, L^*, a^*, b^*, and ΔE^* values.

To study the synthesis of 3,4-dihydro-2H-3-phenyl-1,3-benzoxazine (benzoxazine), the reaction paths of phenol, aniline and formaldehyde were investigated by analyzing the synthesis crude products. With the aid of high-performance liquid chromatography (HPLC), chromatographic column and preparative HPLC, seven compounds originated from the crude products were obtained and their chemical structures were elucidated. Possible reaction paths are proposed based on these compounds. Results show that Nhydroxymethyl aniline (HMA) derived from the reaction of formaldehyde and aniline is probably the key intermediate during the reaction. HMA can react with itself or other reactants to form other intermediates, such as 1,3,5-triphenyl-1,3,5-triazinane and 2-((phenylamino)methyl)phenol, and further form benzoxazine and byproducts.

Reusable acidic nickel oxide nanoparticles have been synthesized, characterized and applied as a catalyst to convert 2-aminoaryl ketones and β-ketoesters/ketones into the corresponding quinolines in good yields with high selectivity. This could serve as a simple and convenient procedure for the Friedlander annulations.