Effect of ring coordination of pyridine-3,5-dicarboxylate and metatungstate to Ln ions on metatungstate structure: Synthesis, structure and optical property of four new compounds

Four novel compounds based on α-metatungstate [H₂W₁₂O₄₀]⁶⁻ (W₁₂) and Ln-organic complexes, (NH₄)₄[Ln₂(L)₂(H₂O)₉(H₂W₁₂O₄₀)]·nH₂O (Ln=Eu^III (1), Gd^III (2), Dy^III (4), n=11; Tb^III (3), n=12; L=pyridine-3,5-dicarboxylate dianion) have been synthesized in aqueous solution and characterized by element analysis, IR spectrometry and thermogravimetric analysis. Single-crystal X-ray diffraction analyses reveal these compounds are isostructural with a P21/n space group. The W₁₂ cluster acting as a tridentate ligand connects three Ln³⁺ ions, in turn, each Ln2 ion links two W₁₂ clusters, as a result, a W₁₂-Ln polymeric chain is formed. Coordination of pyridine-3,5-dicarboxylate ligands to the Ln³⁺ ions leads to a Ln-L polymeric chain. The two chains, W₁₂-Ln and Ln-L, share Ln2 ions, resulting in a 2-D layer. Ring coordination of pyridine-3,5-dicarboxylate and W₁₂ to the Ln ions changes some bond angles of W₁₂ that leads to a slight distortion of W₁₂ and splitting of vibration band of W-Oc-W. Solid-state photoluminescence properties of compounds 1−4 have been investigated.     

Voltammetric sensing of paracetamol, dopamine and 4-aminophenol at a glassy carbon electrode coated with gold nanoparticles and an organophillic layered double hydroxide

A differential pulse voltammetric method was developed for the simultaneous determination of paracetamol, 4-aminophenol and dopamine at pH 7.0 using a glassy carbon electrode (GCE) coated with gold nanoparticles (AuNPs) and a layered double hydroxide sodium modified with dodecyl sulfate (SDS-LDH). The modified electrode displays excellent redox activity towards paracetamol, and the redox current is increased (and the corresponding over-potential decreased) compared to those of the bare GCE, the AuNPs-modified GCE, and the SDS-LDH-modified GCE. The modified electrode enables the determination of paracetamol in the concentration range from 0.5 to 400???M, with a detection limit of 0.13???M (at an S/N of 3). The sensor was successfully applied to the stimultaneous determination of paracetamol and dopamine, and of paracetamol and 4-aminophenol, respectively, in pharmaceutical tablets and in spiked human serum samples.

Electrodeposition of cobalt oxide nanoparticles on carbon nanotubes, and their electrocatalytic properties for nitrite electrooxidation

We describe a modified glassy carbon electrode (GCE) for the sensitive determination of nitrite in waste water samples. The GCE was modified by electrodeposition of cobalt oxide nanoparticles on multi-walled carbon nanotubes (MWCNTs) deposited on a conventional GCE. Scanning electron microscopy and electrochemical techniques were used for the characterization of the composite material which is very uniform and forms a kind of nanoporous structure. Electrochemical experiments showed that the modified electrode exhibited excellent electrocatalytic properties for nitrite. Amperometry revealed a good linear relationship between peak current and nitrate concentration in the 0.5 to 250???M range with a detection limit of 0.3???M (S/N?=?3). The method has been applied to the amperometric detection of nitrite. The modified electrode displays good storage stability, reproducibility, and selectivity for a promising practical application.

Generation of anti-trenbolone monoclonal antibody and establishment of an indirect competitive enzyme-linked immunosorbent assay for detection of trenbolone in animal tissues, feed and urine

Trenbolone (TRE) is a steroid used by veterinarians on livestock to increase appetite and body weight. The use of TRE has been restricted because of its harmful side effect for consumers. To effectively control TRE residue in food and food product, a rapid and convenient immunoassay was developed by preparing an anti-TRE monoclonal antibody. The immunogen and coating antigen were prepared by coupling TRE hapten with carrier proteins via 1-ethyl-3-(dimethylaminopropyl)carbodiimide hydrochloride (EDC) method. The optimized method gave an average IC₅₀ value of 0.323 ng mL⁻¹ towards TRE and an average detection limit (LOD) of 0.06 ng mL⁻¹, which is much lower than the maximum residue levels (2.0 ng g⁻¹) accepted by the Joint FAO/WHO Expert Committee on Food Additives (JECFA). The specificity of the antibody was evaluated by measuring cross-reactivity of six structurally related compounds, including 19-nortestosterone (9.7%), testosterone (0.13%), methyltestosterone (<0.01%), methandrostenolone (<0.01%), (+)-dehydroisoandrosterone (<0.001%) and β-estradiol (<0.001%). The recovery rates of the test in detection of TRE-fortified animal tissue, urine and animal feed samples were in the range of 81.3-89.4%, while the intra- and inter-assay coefficients of variation were less than 12.0%.     

含氟香豆素基哌嗪荧光探针的合成及其性能研究

以7-羟基-4-三氟甲基香豆素和哌嗪为原料,首次合成了具有双荧光侧臂的新型香豆素类荧光探针化合物,研究发现其中间隔基较少的化合物对Cu2+具有较高的选择性,并且对Cu2+的识别不受其它金属离子的干扰.Cu2+在2.0×10-6～1.0×10-4mol/L范围内,探针的荧光强度与其浓度有较好的线性关系.     

Isotopic turnover of a submersed macrophyte following transplant: the roles of growth and metabolism in eutrophic conditions

Stable isotopic turnover with isotopic change due to growth and metabolic tissue replacement associated with a change in environmental conditions is a critical aspect of the use of stable isotope analyses as time-integrating tracers of resource-consumer interactions. However, stable isotopic turnover in plants remains poorly understood compared with those of animals, and here we used continuous flow elemental analyzer-isotopic ratio mass spectrometry (EA-IRMS) to analyse the turnover of stable carbon and nitrogen isotopes in a submersed macrophyte (Vallisneria natans) after transplantation to hypereutrophic and mesoeutrophic treatments in a field mesocosm experiment. The direction and magnitude of the isotopic shifts of V. natans were suggested to be determined by the inorganic nutrient availability and its isotopic content in the different treatments. Based on the modelling results of turnover, the contribution of growth to the isotopic turnover was as high as those observed in various aquatic ectotherms. However, the contribution of metabolism was also considerable, especially for nitrogen in the hypereutrophic treatment, which was argued to be a response, co-occurring with growth inhabitation and biochemical disorder of V. natans, to the stress induced by the eutrophication. Our results indicated that isotope turnover in a macrophyte is a feasible technique for estimating its ecophysiological conditions in the natural environment, and that it may facilitate understanding of isotopic data in field studies of food web and habitat restoration under eutrophic conditions.     

Syntheses, structures, and reactivities of homometallic rare-earth-metal multimethyl methylidene and oxo complexes

Unsolvated, trinuclear, homometallic, rare-earth-metal multimethyl methylidene complexes [{(NCN)Ln(μ(2)-CH(3))}(3)(μ(3)-CH(3))(μ(3)-CH(2))] (NCN = L = [PhC{NC(6)H(4)(iPr-2,6)(2)}(2)](-); Ln = Sc (2a), Lu (2b)) have been synthesized by treatment of [(L)Ln{CH(2)C(6)H(4)N(CH(3))(2)-o}(2)] (Ln = Sc (1a), Lu (1b)) with two equivalents of AlMe(3) in toluene at ambient temperature in good yields. Treatment of 1 with three equivalents of AlMe(3) gives the heterometallic trinuclear complexes [(L)Ln(AlMe(4))(2)] (Ln = Sc (3a), Lu (3b)) in good yields. Interestingly, 2 can also be generated by recrystallization of 3 in THF/toluene, thereby indicating that the THF molecule can also induce C-H bond activation of 2. Reaction of 2 with one equivalent of ketones affords the trinuclear homometallic oxo-trimethyl complexes [{(L)Ln(μ(2) -CH(3))}(3) (μ(3)-CH(3))(μ(3)-O)] (Ln = Sc(4a), Lu(4b)) in high yields. Complex 4b reacts with one equivalent of cyclohexanone to give the methyl abstraction product [{(L)Lu(μ(2) -CH(3) )}(3) (μ(3) -OC(6)H(9))(μ(3)-O)] (5b), whereas reaction of 4b with acetophenone forms the insertion product [{(L)Lu(μ(2)-CH(3))}(3){μ(3)-OCPh(CH(3))(2)}(μ(3)-O)] (6b). Complex 4a is inert to ketone under the same conditions. All these new complexes have been characterized by elemental analysis, NMR spectroscopy, and confirmed by X-ray diffraction determination.     

镍氢电池正极大电流充放电性能及最佳配方

采用化学共沉淀法制备了镍铝和钴铝2种层状氢氧化物[ Ni4Al(OH)10]OH和[Co4Al(OH)10]NO3.将前者作为电极活性材料,后者及石墨作为正极导电添加剂,通过单纯形重心设计研究了正极中3种物质的最佳配比,使其大电流充放电性能得到有效地提高.结果表明,电极的性能与电极配方密切相关.当[ Ni4Al(OH)...     

Development of a simple and stability-indicating RP-HPLC method for determining olanzapine and related impurities generated in the preparative process

A simple and stability-indicating reverse phase high performance liquid chromatographic (RP-HPLC) method was developed and validated for the determination of olanzapine (OLN) and related impurities in bulk drugs. Eight impurities were characterized respectively, and particularly a new process impurity from OLN synthesis was structurally confirmed as 1-(5-methylthionphen-2-yl)-1H-benzimidazol-2(3H)-one (Imp-7) by X-ray single crystal diffraction, MS, (1)H NMR, (13)C NMR and HSQC. A mechanism of formation pathway for Imp-7 was proposed. Optimum separation for OLN and eight related impurities was carried out on an Agilent Octyldecyl silica column (TC-C(18), 4.6 mm × 250 mm, 5 μm) using a gradient HPLC method. The method was validated with respect to specificity, linearity, accuracy, precision, LOD and LOQ. Regression analysis showed good correlation (r(2) > 0.9985) between the investigated component concentrations and their peak areas within the test ranges for OLN and eight impurities. The repeatability and intermediate precision, expressed as RSD, were less than 1.74%. The proposed stability-indicating method was suitable for routine quality control and drug analysis of OLN in bulk drugs.     

Immobilization of MP-11 into a mesoporous metal-organic framework, MP-11@mesoMOF: a new platform for enzymatic catalysis

Microperoxidase-11 has for the first time been successfully immobilized into a mesoporous metal-organic framework (MOF) consisting of nanoscopic cages and it demonstrates superior enzymatic catalysis performances compared to its mesoporous silica counterpart.