One-Pot Synthesis of 1,3,5-Trisubstitued Pyrazoles via Immobilized Thermomyces lanuginosus Lipase (TLL) on a Metal-Organic Framework.

A regioselective enzyme-catalyzed system is selected for the synthesis of 1,3,5-trisubstituted pyrazole derivatives by adding phenyl hydrazines, nitroolefins, and benzaldehydes. The reaction is performed in a one-pot vessel with a yield ranging from 49 to 90%. TLL@MMI, immobilized Thermomyces lanuginosus lipase (TLL) on a multivariate of MOF-5/IRMOF-3 (MMI), showed good performance for the catalysis of this reaction. The prepared biocatalyst was characterized by FTIR, XRD, SEM, and EDX. The thermal and solvent stability of TLL@MMI was investigated in MeOH and EtOH after 24 h incubation. In the presence of 100% concentrations of EtOH, TLL@MMI has 80% activity.

Novel Gold Nanoparticles: Green Synthesis with Eryngium thyrsoideum Boiss Extract, Characterization, and In Vivo Investigations on Inflammatory Gene Expression and Biochemical Parameters in Type 2 Diabetic Rats.

In this work, we synthesized and reported gold nanoparticles (Au NPs) with Eryngium thyrsoideum Boiss plant extract for first time. The plant extract has important effect as reducing and stabilizing agent for preparation of Au nanoparticles. The synthesized gold nanoparticles were characterized with FT-IR, UV-vis, XRD, SEM, and TEM analyses. All analyses confirmed successful synthesis of gold nanoparticles with high purity. The antidiabetic activity of synthesized Au NPs was investigated on type 2 diabetic rats by studying their influences on serum biochemical parameters and inflammatory markers. Obtained results revealed that hepatic enzymes, TNF-α, and interleukin-6 of diabetic rats receiving gold nanoparticles decreased in compare with healthy control rats. As inflammatory markers are main reasons for hyperglycemic-induced insulin resistance in diabetes, Au NPs have a possible option for management of the diabetes-related complication via their potent anti-inflammatory and hypoglycemic effects.

Carboxymethyl cellulose/tetracycline@UiO-66 nanocomposite hydrogel films as a potential antibacterial wound dressing.

Designing an antibacterial agent with a suitable water vapor permeability, good mechanical properties, and controlled antibiotic release is a promising method for stopping bacterial infection in wound tissue. In this respect, this work aims to prepare novel flexible polymeric hydrogel films via integrating UiO-66 into the polymeric carboxymethyl cellulose (CMC) hydrogel for improving the mechanical and antibiotic release performances. First, we performed a green hydrothermal synthetic method to synthesis UiO-66 and followed by encapsulating Tetracycline (TC) through immersion in its aqueous solution. Also, the casting technique was utilized to integrate different concentrations of the TC-encapsulated UiO-66 (TC@UiO-66, 5% to 15%) in the polymeric CMC matrix (CMC/TC@UiO-66) cross-linked by citric acid and plasticized by glycerol. The release performance showed a low initial burst release with a controlled release over 72 h in the artificial sweat and simulated wound exudate (PBS, pH 7.4) media. The in vitro cytotoxicity and antibacterial activity results revealed a good cytocompatibility toward Human skin fibroblast (HFF-1) cells and a significant activity against both E. coli and S. aureus with 1.3 and 1.7 cm inhibition zone, respectively. The obtained results recommend CMC/TC@UiO-66 films as a potential antibacterial wound dressing.

Biosynthesis of Novel Silver Nanoparticles Using Eryngium thyrsoideum Boiss Extract and Comparison of their Antidiabetic Activity with Chemical Synthesized Silver Nanoparticles in Diabetic Rats.

In the present study, silver nanoparticles (1) were synthesized by green method using Eryngium campestre Boiss aqueous extract and silver nanoparticles (2) were synthesized with chemical method. The silver nanoparticles (1) and (2) were characterized with FT-IR, UV-Vis, XRD, EDX, SEM, and TEM analyses. The effects of silver nanoparticles (1) and (2) were investigated on glucose, hematology, and blood biochemical parameters in alloxan- induced diabetes type 1 model rats. Diabetic or intact rats received intraperitoneal injection of saline or 2.5 mg/kg of silver nanoparticles (1) and (2) for 14 consecutive days. Hematological parameters and serum concentration of FBS, HbA1C, ALT, AST, GGT, ALP, albumin, creatinine, and urea were determined. Interestingly, silver NPs (1) or (2) did not exert toxic influences on hematological parameters and liver and kidney function in intact rats. Both silver nanoparticles (1) and (2) exert hypoglycemic effects in diabetic rats. They did not alter urea, creatinine, and hematological parameters except white blood cell (WBC) count in diabetic rats. Silver nanoparticles (1) decreased significantly liver enzyme levels including ALT and AST of diabetic rats. However silver nanoparticles (2) could not suppress the increased levels of liver enzymes in diabetic rats. In comparison with silver nanoparticles (2), the silver nanoparticles (1) are more protective than the same dose of silver nanoparticles (2) in the regulation and improving the liver function in diabetic rats. Also, silver nanoparticles (1) may exert protective effects on liver damage of diabetic rats rather than kidney damage.

Introducing Bluish-Green Light-Emitting Diodes (OLEDs) and Tuning Their Color Intensity by Uranium Complexes: Synthesis, Characterization, and Photoluminescence Studies of 8-Hydroxyquinoline Complexes of Uranium.

To improve our understanding of the chemistry of actinide complexes and to spur their development in the field of actinide markers, two new uranium complexes were synthesized using 8-hydroxyquinoline and 5,7-dichloro-8-hydroxyquinoline. The prepared complexes were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, ultraviolet-visible spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The impact of the electron-withdrawing group of the ligand on the photoluminescence spectra of the complexes in solution and in the solid state was scrutinized. The bandgap of the complexes was calculated using the density functional theory (DFT) method to investigate the effects of the electron-withdrawing groups on energy levels. The synthesized uranium complexes demonstrated appropriate levels of the lowest unoccupied molecular orbital energy, leading to favorable dye stability. The prepared uranium complexes showed blue fluorescent emission, and the sample with the most intense fluorescence was used to construct bluish-green organic light-emitting diodes using simple solution processing fabrication methods. Absorbance spectra, emission spectra, DFT-calculated energy levels, and comparisons of the fabricated organic light-emitting diodes indicated that the electron-withdrawing group was a key factor in photoluminescence behavior.

Direct conversion of inorganic complexes to platinum/thin oxide nanoparticles decorated on MOF-derived chromium oxide/nanoporous carbon composite as an efficient electrocatalyst for ethanol oxidation reaction.

In this work, we present the design and fabrication of a novel nanocomposite based on noble metal and metal oxide nanoparticles dispersed on highly porous carbon obtained via the pyrolysis of an inorganic complex and metal-organic frameworks. This nanocomposite is prepared by a two-step procedure: first, the composite support of nanoporous carbon (NPC) is obtained by the direct carbonization of the Cr-benzene dicarboxylic ligand (BDC) MOF in an Argon atmosphere at 500 °C (Cr2O3-NPC). A mixture containing Cr2O3-NPC and [PtCl(SnCl3)(SMe2)2] is then prepared, and underflow of Argon is heated to 380 °C. Finally, Pt-SnO2 nanoparticles are loaded on the Cr2O3-NPC support, and the obtained nanocomposite was denoted as Pt-SnO2/Cr2O3-NPC. The morphology and crystalline structure of the prepared nanocomposites were characterized using XRD, SEM, EDX, FT-IR, and XPS. In addition, the prepared nanocomposite was examined as a novel electrocatalyst for the ethanol electro-oxidation reaction (EOR). The obtained results demonstrated that, compared with Pt/Cr2O3-NPC, Pt-SnO2/Cr2O3-NPC showed higher electrocatalytic activity, lower onset potential, and a higher level of poisoning tolerance toward of ethanol oxidation in acidic media. The overall results corroborate the predominant role of SnO2 as an excellent catalytic-enhancing agent thorough facilitating the charge transfer process and increasing the CO poisoning oxidation by the spillover of OHads to the Pt surface. Thus, the prepared Pt-SnO2/Cr2O3-NPC catalyst could be considered a promising anode catalyst for direct ethanol fuel cells.

Fabrication of blue organic light-emitting diodes from novel uranium complexes: synthesis, characterization, and electroluminescence studies of uranium anthracene-9-carboxylate complexes.

In this study, three uranium(vi) complexes, [UO2(C15H9O2)2(CH3CH2OH)2]·2CH3CH2OH (1), [U2O4(C15H9O2)2(CH3O)2(CH3OH)2]·2CH3OH (2), and [U2O4(C15H9O2)4(CH3OH)2]·2H2O (3), were prepared by reacting anthracene-9-carboxylic acid with uranyl acetate dihydrate using various ligand to uranyl acetate ratios in different solvents. The infrared and UV-Vis spectra along with elemental and thermal analyses showed the formation of mono- and dinuclear anthracene-9-carboxylate complexes of uranium. A 1 to 3 molar ratio of uranyl acetate to anthracene-9-carboxylic acid in ethanol resulted in the formation of the mononuclear complex 1, whereas a 1 to 2 and 1 to 3 molar ratio of uranyl acetate to anthracene-9-carboxylic acid in methanol produced the dinuclear complexes 2 and 3, respectively. Single-crystal structure determinations of 1, 2 and 3 revealed hexagonal bipyramidal geometries for the mononuclear uranium complex of 1 and a pentagonal geometry for the dinuclear uranium complexes of 2 and 3. The single-crystal structures of complexes 2 and 3 showed π-π interactions in contrast to complex 1. The strong π-π interactions in complex 2 and 3 lead to an enhanced photoluminescence intensity in comparison with 1 without π-π interaction. The optical properties of the prepared complexes are associated with the ligand-induced resonant system. The fluorescent uranium complex 1 that showed a blue emission upon excitation at 270 nm was used for the fabrication of a blue organic light-emitting diode (BOLED), an industrially important OLED, using a simple solution-process fabrication method.

Dispersive magnetic solid-phase extraction of phthalate esters from water samples and human plasma based on a nanosorbent composed of MIL-101(Cr) metal-organic framework and magnetite nanoparticles before their determination by GC-MS.

In this study, a magnetic metal-organic framework was synthesized simply and utilized in the dispersive magnetic solid-phase extraction of five phthalate esters followed by their determination by gas chromatography with mass spectrometry. First, MIL-101(Cr) was prepared hydrothermally in water medium without using highly corrosive hydrofluoric acid, utilizing an autoclave oven heat supply. Afterward, Fe3 O4 nanoparticles were decorated into the matrix of MIL-101(Cr) to fabricate magnetic MIL-101 nanocomposite. The nanocomposite was characterized by various techniques. The parameters affecting dispersive magnetic solid-phase extraction efficiency were optimized and obtained as: a sorbent amount of 15 mg; a sorption time of 20 min; an elution time of 5 min; NaCl concentration, 10% w/v; type and volume of the eluent 1 mL n-hexane/acetone (1:1 v/v). Under the optimum conditions detection limits and linear dynamic ranges were achieved in the range of 0.08-0.15 and 0.5-200 µg/L, respectively. The intra- and interday RSD% values were obtained in the range of 2.5-9.5 and 4.6-10.4, respectively. Ultimately, the applicability of the method was successfully confirmed by the extraction and determination of the model analytes in water samples, and human plasma in the range of microgram per liter and satisfactory results were obtained.

Synthesis and characterization of a series of novel perovskite-type LaMnO3/Keggin-type polyoxometalate hybrid nanomaterials for fast and selective removal of cationic dyes from aqueous solutions.

In this paper, Keggin-type heteropoly acids H3PMo12O40 (PMo12), H3PW12O40 (PW12) and H4SiW12O40 (SiW12) were successfully supported on silica-coated perovskite type LaMnO3 nanoparticles by a simple acid-base reaction. These novel hybrid nanomaterials (denoted as LaMnO3@SiO2/PMo12 (1), LaMnO3@SiO2/PW12 (2), and LaMnO3@SiO2/SiW12 (3)) were characterized by means of FT-IR, PXRD, inductively coupled plasma (ICP) spectrometry, SEM, EDX, TEM and BET surface area analysis. Furthermore, the adsorption abilities of 1-3 were tested towards cationic methylene blue (MB) and anionic methyl orange (MO) dyes. The results revealed that the MB dye can be removed almost completely (≥98%) by adsorbents 1-3 in 1, 30 and 0.5 minutes, respectively. For the most efficient adsorbent 3, the effects of the initial concentration and the initial pH values of MB solution on its adsorption ability were examined. Furthermore, the selective adsorption of the hybrid materials towards mixed MB & MO solution was investigated. The nanomaterials 1-3 could be easily separated from the aqueous solution and reused several times without any impact on their adsorption abilities and structures.

Preparation and characterization of the pH and thermosensitive magnetic molecular imprinted nanoparticle polymer for the cancer drug delivery.

A novel pH and thermosensitive magnetic nanoparticle polymer composite [poly(NIPAAM@Fe3O4 MNPs/TMSPMC/DOX)] was synthesized by radical polymerization of N-isopropylacrylamide (NIPAAM) and the methacrylate functionalized Fe3O4 nanoparticles/DOX complex using AIBN and EGDMA, and used as a drug carrier for the DOX drug delivery. Formation of poly(NIPAAM@Fe3O4 MNPs/TMSPMC/DOX) was confirmed by FTIR, XRD, UV-Vis, VSM, TGA-DTA and SEM. The results showed the high DOX loading controls release. Moreover, it showed the lower critical solution temperature of 40°C which can be beneficial in cancer drug delivery, since the temperature of cancer cells is higher than normal ones, and DOX can be released selectively in cancer cells.

Structural and spectroscopic characterizations of aluminum phenoxide.

A synthetic route to obtain crystalline aluminum phenoxide was established. Its molecular structure in solid-state and solution is unambiguously determined by single-crystal X-ray diffraction and (1)H, (13)C and (27)Al NMR spectroscopy. The single-crystal X-ray analysis revealed the presence of the dimeric THF adduct [Al(OPh)3·THF]2 with a disordered trigonal bipyramidal geometry at the aluminum atom which is bonded to a THF ligand, two terminal and two bridging phenoxy groups (OPh). The solution behavior of the title compound was investigated by (27)Al NMR in non-coordinating (CDCl3) as well as coordinating (THF) solvents at different temperatures. The obtained results indicate the presence of four- and five-coordinate species in solution.

Occurrence of non-steroidal anti-inflammatory drugs in Tehran source water, municipal and hospital wastewaters, and their ecotoxicological risk assessment.

Pharmaceuticals are becoming widely distributed in waters and wastewaters and pose a serious threat to public health. The present study aimed to analyze non-steroidal anti-inflammatory drugs (NSAIDs) in surface waters, drinking water, and wastewater in Tehran, Iran. Thirty-six samples were collected from surface waters, tap water, and influent and effluent of municipal and hospital wastewater treatment plants (WWTP). A solid-phase extraction (SPE) followed by liquid chromatography-tandem mass spectrometry method was used for the determination of pharmaceuticals, namely ibuprofen (IBP), naproxen (NPX), diclofenac (DIC), and indomethacin (IDM). IBP was found in most of the samples and had the highest concentration. The highest concentrations of NSAIDs were found in the municipal WWTP influents and hospital WWTP effluents. In the municipal WWTP influent samples, the concentrations of IBP, NPX, DIC, and IDM were 1.05, 0.43, 0.23, and 0.11 µg/L, respectively. DIC was found only in one river sample. All NSAIDs were detected in tap water samples. However, their concentration was very low and the maximum values for IBP, NPX, DIC, and IDM were 47, 39, 24, and 37 ng/L, respectively, in tap water samples. Results showed that the measured pharmaceuticals were detected in all rivers with low concentrations in nanograms per liter range, except DIC which was found only in one river. Furthermore, this study showed that the aforementioned pharmaceuticals are not completely removed during their passage through WWTPs. A potential environmental risk of selected NSAIDs for the urban wastewater has been discussed. However, given their low measured concentrations, no ecotoxicological effect is suspected to occur.

Dithizone-modified graphene oxide nano-sheet as a sorbent for pre-concentration and determination of cadmium and lead ions in food.

Graphene oxide nano-sheet was modified with dithizone as a novel sorbent for selective pre-concentration and determination of Cd(II) and Pb(II) in food. The sorbent was characterised by various analytical methods and the effective parameters for Cd(II) and Pb(II) adsorption were optimised during this work. The high adsorption capacity and selectivity of this sorbent makes the method capable of fast determinations of the Cd(II) and Pb(II) content in complicated matrices even at µg l(-1) levels using commonly available instrumentation. The precision of this method was < 1.9% from 10 duplicate determinations and its accuracy verified using standard reference materials. Finally, this method was applied to the determination of Cd(II) and Pb(II) ions in common food samples and satisfactory results were obtained.

Application of solvent-assisted dispersive solid phase extraction as a new, fast, simple and reliable preconcentration and trace detection of lead and cadmium ions in fruit and water samples.

In this research, a new sample treatment technique termed solvent-assisted dispersive solid phase extraction (SA-DSPE) was developed. The new method was based on the dispersion of the sorbent into the sample to maximize the contact surface. In this approach, the dispersion of the sorbent at a very low milligram level was achieved by injecting a mixture solution of the sorbent and disperser solvent into the aqueous sample. Thereby, a cloudy solution formed. The cloudy solution resulted from the dispersion of the fine particles of the sorbent in the bulk aqueous sample. After extraction, the cloudy solution was centrifuged and the enriched analytes in the sediment phase dissolved in ethanol and determined by flame atomic absorption spectrophotometer. Under the optimized conditions, the detection limit for lead and cadmium ions was 1.2 µg L(-1) and 0.2 µg L(-1), respectively. Furthermore, the preconcentration factor was 299.3 and 137.1 for cadmium and lead ions, respectively. SA-DSPE was successfully applied for trace determination of lead and cadmium in fruit (Citrus limetta, Kiwi and pomegranate) and water samples. Finally, the introduced sample preparation method can be used as a simple, rapid, reliable, selective and sensitive method for flame atomic absorption spectrophotometric determination of trace levels of lead and cadmium ions in fruit and water samples.

N-Functionalized L-proline anchored MCM-41: a novel organic-inorganic hybrid material for solvent-free aminolysis of styrene oxide under microwave irradiation.

A novel organic-inorganic hybrid material, namely L-prol-N-pMCM-41, was synthesized via two steps by covalently anchoring N-functionalized proline derivative (L-prol-N-pTMS) into the pore channels of MCM-41 silica. The prepared material was characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), nitrogen adsorption-desorption isotherm, Brunauer-Emmett-Teller (BET) surface area analysis, and Fourier Transform Infrared spectroscopy (FTIR). The immobilized catalyst demonstrated moderate to high catalytic activity and excellent regioselectivity for the ring opening of styrene oxide with aniline derivatives under microwave irradiation and solvent-free conditions. The catalyst could be rapidly separated from the reaction mixture and reused up to five runs with good conversion and high regioselectivity.

Structural and spectroscopic characterizations of tetra-nuclear niobium(V) complexes of quinolinol derivatives.

Reactions between niobium ethoxide and 8-hydroxy-2-methylquinoline or 5-chloro-8-hydroxyquinoline have been explored. Two new tetranuclear heteroleptic niobium complexes containing oxo, ethoxo, and quinolinate chelate rings have been synthesized and characterized by (1)H, (13)C and (93)Nb NMR, UV-Vis, and FT-IR spectroscopies, and single-crystal X-ray diffraction. The molecular structures of the niobium complexes, [Nb4(µ-O)4(µ-OEt)2(ONC10H8)2(OEt)8] (I) and [Nb4(µ-O)4(µ-OEt)2(ONC9H5Cl)2(OEt)8] (II), are composed of a pair of edge-sharing bioctahedral moieties in which connected via two almost linear oxo-bridges, with a large difference in the NbO distances. Single-crystal structures showed both complexes are centrosymmetric and contain two distinct Nb centers, and results confirmed by observation of two niobium signals in the (93)Nb NMR spectra of complexes.

Porous-membrane-protected polyaniline-coated SBA-15 nanocomposite micro-solid-phase extraction followed by high-performance liquid chromatography for the determination of parabens in cosmetic products and wastewater.

A SBA-15/polyaniline para-toluenesulfonic acid nanocomposite supported micro-solid-phase extraction procedure has been developed for the extraction of parabens (methylparaben, ethylparaben, and propylparaben) from wastewater and cosmetic products. The variables of interest in the extraction process were pH of sample, sample and eluent volumes, sorbent amount, salting-out effect, extraction and desorption time, and stirring rate. A Plackett-Burman design was performed for the screening of variables in order to determine the significant variables affecting the extraction efficiency. Then, the significant factors were optimized by using a central composite design. The optimum experimental conditions found at 50 mL sample solution, extraction and desorption times of 40 and 20 min, respectively, 500 µL of 3% v/v acetic acid in methanol as eluent, 0.01 M salt addition, and 10 mg of the sorbent. Under the optimum conditions, the developed method provided detection limits in the range of 0.08-0.4 ng/mL with good repeatability (RSD% < 7) and linearity (r(2) = 0.997-0.999) for the three parabens. Finally, this fast and efficient method was employed for the determination of target analytes in cosmetic products and wastewater, and satisfactory results were obtained.

Application of mercapto ordered carbohydrate-derived porous carbons for trace detection of cadmium and copper ions in agricultural products.

In this paper, we have introduced nanoporous carbon modified with mercapto groups as a new solid-phase method for extraction of cadmium(II) and copper(II) ions. The modified nanoporous carbon sorbent was characterised by thermogravimetric analysis, differential thermal analysis, transmission electron microscopy, Fourier transform infrared spectrometry, X-ray diffraction, and nitrogen adsorption surface area (BET) measurements. Effects of pH value, flow rates, type, concentration and volume of the eluent, breakthrough volume, and effect of other ions were studied. The experimental results show that simultaneous trace cadmium(II) and copper(II) ions can be quantitatively preconcentrated at pH 6.0 with recoveries >97%. Under optimised conditions, limits of detection are 0.04 and 0.09 ng mL(-1) for the ions of cadmium and copper respectively, and the precision of the method for analysis of cadmium and copper ions (5.0 µg of each target ions, N=8) are 2.4% and 2.1%, respectively. The obtained capacities of mercapto-nanoporous carbon were found to be 145 and 95 mg g(-1) for cadmium and copper ions, respectively. The accuracy of the proposed procedure was verified by analysing standard reference material. Finally, the introduced sorbent was successfully applied for trace determination of cadmium and copper ions in food samples.

Sonoelectrochemical synthesis of a new nano lead(II) complex with quinoline-2-carboxylic acid ligand: a precursor to produce pure phase nano-sized lead(II) oxide.

A new lead complex, [Pb(Q)2] (1) (Q=quinoline-2-carboxylic acid), was prepared via conventional electrochemical method in a fast and facile process and fully characterized by (1)H and (13)C NMR, IR, UV spectroscopies and elemental analysis. The nano-structures of same compound were successfully prepared at 25, 48 and 60°C by a facile and environment-friendly sonoelectrochemical route. The new nano-structure particles were characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analysis. Thermal stability of single-crystal and nano-size samples of the prepared compound was studied by thermogravimetric and differential thermal analysis. The effect of sonoelectrochemical temperature on particle size has been investigated, and possible explanations offered. The photoluminescence properties of the nano-structured and crystalline bulk of the prepared complex at room temperature in the solid state have been investigated in detail. The results indicate that the size of the complex particles has an important effect on the optical properties of it. The prepared complexes, as bulk and as nano-particles, were utilized as a precursor for preparation of PbO nanoparticles by direct thermal decomposition at 600°C in air. The nano-structures of PbO were characterized by scanning electron microscopy, X-ray powder diffraction and IR spectroscopy.