Development of an amperometric sensor for simultaneous determination of uric acid and ascorbic acid using 2-[bis(2-aminoethyl)amino]ethanol, 4,4′-bipyridine bridged dicopper(II) complex

Binuclear copper complex (2-[bis(2-aminoethyl)amino]ethanol, 4,4′-bipyridine bridged dicopper(II) complex) was grafted onto the surface of a glassy carbon electrode (GCE) using the cyclic voltammetric method in a phosphate buffer solution (PBS). The modified electrode resulted in efficient electrocatalytic activity for anodic oxidation of uric acid (UA) and ascorbic acid (AA) via a substantial decrease in anodic over-potentials for both compounds. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) using this modified electrode result in two well-resolved anodic waves for the oxidation of UA and AA in mixed solution, making possible the simultaneous determination of both compounds. Linear analytical curves were obtained in the ranges 5.0–300.0 μM and 5.0–160.0 μM for UA and AA concentrations through DPV methods, respectively. The detection limits were 2.0 μM of UA and AA. This electrode was used for UA and AA determinations in urine samples with satisfactory results.     

Some lanthanide (III) complexes of (S,S)-(+)-2,3-dimethoxyl-N,N′-dimethyl-1,4-diaminobutane

Four new optically active complexes of the composition LnL₃Cl₃ (where, L=(S,S)-(+)-2,3-dimethoxyl-N,N^′-dimethyl-1,4-diaminobutane, Ln=La³⁺, Sm³⁺, Pr³⁺ and Nd³⁺) were prepared and characterized on the basis of their chemical analyses, molar conductance, magnetic properties, CD, XPS, visible and IR spectra. It is found that the complexes behave as non-electrolytes in DMSO and in methanol solution and possess the stoichiometric ratio of Ln:C:N:O:Cl =1.1:24.0:6.1:6.0:3.1 which is consistent with the analyses data. The magnetic moments of the complexes show little deviation from the Van Vleck values, indicating that 4f electrons do not participate in bond formation in these chelates. The thermal analysis revealed that all the complexes are anhydrous. Their dominant conformers were determined from CD spectra. A nine-coordinated model was proposed for these complexes.     

Measurement and Correlation for Solubility of (S)-(+)-2,2-Dimethyl-cyclopropane Carbox Amide in Different Solvents

1 INTRODUCTION (S)-(+)-2,2-dimethylcyclopropane carbox amide [(+)-DMCPCA, Fig.1] is a key intermediate of Cilas- tatin, an inhibitor of dehydropeptidase-I. As the syner- gist of imipenem (an antibiotic drug), cilastatin is widely used in clinical applications and has prosper- ous prospects[1]. In industrial manufacture[2―6], as the optical intermediate, the chemical and optical purity of (+)-DMCPCA would affect the quality of cilastatin. So, the separation and purification are impo…     

Synthesis of (S)-α-amino oleic acid

An efficient synthesis of (S)-α-amino oleic acid was developed. The fully protected FA derivative was obtained in four steps starting from methyl (2S)-2-[bis(tert-butoxycar-bonyl)amino]-5-oxopentanoate. These steps are (i) olefination of the starting aldehyde with the appropriate phosphonate anion, (ii) hydrogenation of the double bonds, (iii) controlled reduction of ω-ethyl ester to an aldehyde in the presence of α-methyl ester, and (iv) a Wittig reaction of the latter aldehyde with the suitable ylide. Free α-amino oleic acid was prepared after deprotection of the amino group followed by saponification in a total yield of 24%. N-tert-Butoxycarbonyl-protected amino oleic acid and the corresponding amino alcohol were prepared in high yield. The structures of the products have been established by various spectroscopic techniques.     

Development of an (S)-1-{2-[tris(4-methoxyphenyl)methoxy]ethyl}piperidine-3-carboxylic acid [(S)-SNAP-5114] carba analogue inhibitor for murine γ-aminobutyric acid transporter type 4

A series of GABA uptake inhibitors related to (S)-1-{2-[tris(4-methoxyphenyl)methoxy]ethyl}piperidine-3-carboxylic acid [(S)-SNAP-5114], the most potent mGAT4 inhibitor known so far, were synthesized and biologically evaluated for their inhibitory potency at the four GABA uptake transporters mGAT1-4 stably expressed in HEK-293 cell lines. New analogues were developed with potencies that are similar to or slightly higher than those of current mGAT4 inhibitors, but with distinctly improved chemical stability. (S)-Nipecotic acid derivatives possessing a 2-[1-(4-methoxy-2-methylphenyl)-1,1-bis(4-methoxyphenyl)methoxy]ethyl (DDPM-859) or a 4,4,4-tris(4-methoxyphenyl)but-2-en-1-yl moiety (DDPM-1457) were found to exhibit pIC(50) values of 5.78 and 5.87, respectively. Thus, as mGAT4 inhibitors, these compounds compare well with (S)-SNAP-5114 (pIC(50) =5.71), but are far more stable than the latter. Moreover, DDPM-859 displays a more favorable subtype selectivity for mGAT4 versus mGAT3 than does (S)-SNAP-5114.     

Coevolution of the Activity and Thermostability of an ϵ-Keto Ester Reductase for Better Synthesis of an (R)-α-Lipoic Acid Precursor

In this work, we have identified a significantly improved variant (S131Y/Q252I) of the natural ϵ-keto ester reductase CpAR2 from Candida parapsilosis for efficiently manufacturing (R)-8-chloro-6-hydroxyoctanoic acid [(R)-ECHO] through co-evolution of activity and thermostability. The activity of the variant CpAR2_S131Y/Q252I towards the ϵ-keto ester ethyl 8-chloro-6-oxooctanoate was improved to 214 U mg⁻¹—from 120 U mg⁻¹ in the case of the wild-type enzyme (CpAR2_WT)—and the half-deactivating temperature (T₅₀, for 15 min incubation) was simultaneously increased by 2.3 °C in relation to that of CpAR2_WT. Consequently, only 2 g L⁻¹ of lyophilized E. coli cells harboring CpAR2_S131Y/Q252I and a glucose dehydrogenase (GDH) were required in order to achieve productivity similar to that obtained in our previous work, under optimized reaction conditions (530 g L⁻¹ d⁻¹). This result demonstrated a more economical and efficient process for the production of the key (R)-α-lipoic acid intermediate ethyl 8-chloro-6-oxooctanoate.     

Enantioselective hydrogenation of (E)-α-phenylcinnamic acid with cinchonidine-modified Pd/TiO2: influence of solvents and additives

Both the enantioselectivity and activity of the hydrogenation of (E)-α-phenylcinnamic acid with cinchonidine-modified Pd catalysts are strongly solvent dependent; polar solvents with higher solubility for the substrate are preferable. The simultaneous increases in the enantioselectivity and activity, also induced by the addition of either a small amount of water to aprotic solvents or an amine such as benzylamine, indicate that preferential acceleration of the selective reaction has occurred, thus strongly suggesting the importance of the product desorption step on the modified sites. This revised version was published online in June 2006 with corrections to the Cover Date.     

(1R,2R)-(+)-1,2-DPEN-modified Wang resin: An efficient catalyst for the asymmetric Michael addition of acetone to β-nitroolefins

Wang resin was modified by (1R,2R)-(+)-1,2-DPEN by means of a triazine ring. The catalyst was characterized by thermogravimetric (TG) analysis, elemental analysis, and Fourier transform infrared spectroscopy (FT-IR). Subsequently, this catalyst was employed for the asymmetric Michael addition of acetone to β-nitrostyrene. Under optimized conditions, 76.6% of β-nitrostyrene conversion and 82.8% enantioselectivity of Michael adduct were obtained. On the basis of the characterization of the catalyst by X-ray photoelectron spectroscopy (XPS), the mechanism of catalysis was proposed. In addition, the generality of the catalyst was evaluated with Michael additions of acetone to β-nitroolefins. Finally, the continuous reaction was realized in a fixed-bed reactor.     

(S)-(+)-N,N-二甲基-3-(1-萘氧基)-2-噻吩基丙胺的合成研究

以2-乙酰噻吩为原料,经Mannich反应、还原反应、手性拆分、光延反应合成(S)-(+)-N,N-二甲基-3-(1-萘氧基)-2-噻吩基丙胺。对反应物配料比、反应时间和温度等工艺影响因素进行了研究,总收率达40.26%(以2-乙酰噻吩计),其结构经1H NMR和MS确证。     

Studies on the Dehydrogenative Polymerizations of Monolignol β‐Glycosides. Part 1. Syntheses of Monolignol β‐glycosides, (E)‐Isoconiferin, (E)‐Isosyringin,and (E)‐Triandrin

Abstract

(E)‐4‐O‐Acetyl coniferyl alcohol was synthesized by the reduction of (E)‐4‐O‐acetyl ferulic acid with sodium borohydride and N,N‐dimethylchloromethylenium chloride in 80.2% yield. The glycosylation of (E)‐4‐O‐acetyl coniferyl alcohol with trichloroacetimidoyl 2,3,4,6‐tetra‐O‐pivaloyl‐α‐D‐glucopyranoside in the presence of BF₃-Et₂O in anhydrous CH₂Cl₂, followed by deacylation gave (E)‐isoconiferin in high yield. This synthetic method could be applied to the syntheses of other monolignol β‐glycosides. As a result, (E)‐isoconiferin, (E)‐isosyringin, and (E)‐triandrin were synthesized from vanillin, syringaldehyde, and p‐hydroxybenzaldehyde, respectively, by five reaction steps in high overall yield.     

Synthesis and Evaluation of N,N′-dimethyl-N,N′-dicyclohexyl-Malonamide (DMDCMA) as an Extractant for Actinides

A malonamide based extractant, i.e., N,N′-dimethyl-N,N′-dicyclohexyl-malonamide (DMDCMA) was synthesized in a single step and tested for the extraction of several actinide ions such as Am(III), U(VI), Np(IV), Np(VI), Pu(IV), Pu(VI), etc., from nitric acid medium. The extractant was soluble in phenyltrifluoromethylsulphone (PTMS or FS-13) unless stated otherwise. The effect of various experimental parameters, such as the aqueous phase acidity (0.01–3 M HNO₃), nature of the acid, oxidation states of the metal ions, ligand concentration, nature of the diluent and temperature on the extraction behavior of metal ions was studied. The extracted Am(III) species was determined from slope analysis method as [Am(NO₃)₃(DMDCMA)₂]. The extraction of the metal ions was found to increase with the aqueous phase acidity. The temperature variation studies allowed the calculation of the heat of the two-phase extraction reaction as well as the corresponding extraction constants. These studies revealed that DMDCMA showed good extraction for all the actinide metal ions investigated, and have the advantage of single stage synthesis and easier purification protocol.     

Production of 8,11,14,17-cis-eicosatetraenoic acid (20:4ω-3) by a Δ5 and Δ12 desaturase-defective mutant of an arachidonic acid-producing fungus Mortierella alpina 1S-4

A Δ5 and Δ12 desaturase-defective mutant of an arachidonic acid-producing fungus, Mortierella alpina 1S-4, produced 8,11,14,17-cis-eicosatetraenoic acid (20:4ω3) intracellularly when grown with linseed oil. Dihomo-γ-linolenic acid was the only C₂₀ polyunsaturated fatty acid (4.9 wt% of total mycelial fatty acids) other than 20:4ω3. AA and 5,8,11,14,17-cis-eicosapentaenoic acid were not detected. The mycelial lipids consisted of 82.2% (by mol) triacylglycerol (TG), 7.1% diacylglycerol, 8.9% phospholipids (PL), and 1.9% free fatty acids. The percentage of 20:4ω3 was higher in PL (30.1%) than in TG (11.6%), and highest in phosphatidylcholine (38.9%). Under the optimal conditions with a 5-L jar fermenter, 20:4ω3 production amounted to 97.4 mg/g dry mycelia with a mycelial yield of 23 g/L on the twelfth day (corresponding to 2.24 g/L medium and 37.1% of total mycelial fatty acids).     

Extraction and recovery of cadmium(Ⅱ) using phosphine-oxide,tris[(dibutylamino)methyl]-(7CI,8CI) from nitric acid solutions

In the present article, a new separation system was employed for the extraction of cadmium from nitric acid solutions for the first time. Phosphine oxide, tris[(dibutylamino)methyl]-(7CI,8CI),which contains nitrogen atoms and phosphorus atom in molecular, was used as extractant. The influence of the following parameters was investigated: the organic/aqueous phase ratio (O/A), pH, contact time, temperature, the concentration of extractant, cadmium (Ⅱ), sodium nitrate and sodium chloride. Results demonstrated that quantitative extraction of cadmium was feasible from 50 mg/L cadmium feed solution in a single stage at pH 3.0, 15 min and O/A phase ratio 1:5 with 20% extractant in cyclohexane diluent. The cadmium extraction isotherm under different cadmium ion concentrations was established. The loaded cadmium could be stripped by 4 mol/L ammonium chloride aqueous solutions. A contrast study was carried out, and the results indicated that phosphine oxide, tris[(dibutylamino)methyl] –(7CI,8CI), could take the place of commercial organo-phosphorous extractants in the process of cadmium(II) extractions for its effectivity, stability and low price.     

Preparation and phase change performance of Na_2HPO_4·12H_2O@poly(lactic acid) capsules for thermal energy storage

Micro-encapsulated phase-change materials(micro PCMs) with Na_2 HPO_4·12 H_2 O encapsulated in poly(lactic acid)(PLA) shell were prepared by a solvent evaporation–precipitation method that involves the use of a coaxial needle. The effects of PLA concentration, stirring speed, injection rate of core and shell solutions, and polyvinyl alcohol(PVA) concentration on phase change properties were investigated. The thermal properties of microP CMs were characterized by differential scanning calorimetry(DSC). The capsules prepared under the optimal conditions are about 2 mm in diameter and show a latent heat of up to 122.2 J·g~(-1).     

New catalyst systems for the polymerization of substituted acetylenes: M(CO)6—Lewis acid—hv (M=W,Mo)

Summary A new catalyst system prepared by UV irradiation of a toluene solution of W(CO)₆ and a Lewis acid polymerized phenylacetylene (e.g., polymer yield 50%, M _n 5.0×10⁴ with SnCl₄ (0.5 equivalent to W(CO)₆) as Lewis acid). This catalyst afforded high molecular weight polymers M _n 4×10⁵ – 5×10⁵) from phenylacetylenes with ortho-substituents (e.g., o-Me₃Si and o-CF₃). The Mo(CO)₆-based counterpart was rather effective to acetylenes having electron-withdrawing groups (e.g., ClC Cph). Polymerization of phenylacetylene occurred as well when SnCl₄ was added after UV irradiation of a toluene solution of W(CO)₆ and the monomer; this suggests that the polymerization proceeds via metal carbenes having coordinated SnCl₄.     

The corrosion inhibition of maraging steel under weld aged condition by 1(2E)-1-(4-aminophenyl)-3-(2-thienyl)prop-2-en-1-one in 1.5?M hydrochloric acid medium

The influence of 1(2E)-1-(4-aminophenyl)-3-(2-thienyl)prop-2-en-1-one (ATPI) on the corrosion behavior of weld aged maraging steel in 1.5 M hydrochloric acid was studied by potentiodynamic polarization method and AC impedance (EIS) technique at different temperatures. The results showed that the inhibition efficiency of ATPI increased with the increase in the concentration of inhibitor and decreased with the increase in temperature. ATPI acts as a mixed type inhibitor without affecting the mechanism of the hydrogen evolution reaction or iron dissolution. The adsorption of ATPI on a weld aged maraging steel surface obeys the Langmuir adsorption isotherm equation. Both activation and thermodynamic parameters were calculated and discussed. ATPI inhibits the corrosion through both physisorption and chemisorption on the alloy surface. The surface morphology of the weld aged maraging steel specimens in the presence and the absence of the inhibitors was studied by the respective SEM images.     

Study on the Crystallization,Miscibility, Morphology,Properties of Poly(lactic acid)/Poly(ε-caprolactone) Blends

A series of blends of poly(lactic acid) (PLA) and poly(ε-caprolactone) (PCL) with different mass ratio were prepared by means of the melt blending method to study their crystallization, miscibility, morphology, and thermal and mechanical properties. The result of DSC tests showed that the melting temperatures of PLA and PCL shifted toward each other, and that the largest shift appeared at the PLA₇₀PCL₃₀ blend. This result reveals that the PLA₇₀PCL₃₀ blend gives the strongest interaction intensity among the blends. Combined the result of dynamic mechanical analysis and SEM morphologies, it was found that PLA and PCL form a partial miscible blend, in which an amount of amorphous PCL (amorphous PLA) is dissolved in the PLA-rich phase (PCL-rich phase), leading to a depression of the T_g. value. The polarized optical micrographs showed that PCL can serve as a nucleating agent to promote PLA crystallization in the PLA/PCL blend. Moreover, the PLA₇₀PCL₃₀ blend gave the largest growth rate of PLA spherulite. Finally, the mechanical property of PLA/PCL blends indicated that PLA can easily be tuned from rigid to ductile by the addition of PCL.     

Forcespinning technique for the production of poly(d,l-lactic acid) submicrometer fibers: Process–morphology–properties relationship

This work addresses a systematic study for the process development and optimization of poly(d ,l -lactic acid) (PDLLA) submicrometer fibers utilizing the centrifugal spinning technique known as Forcespinning. This study analyzes the effect of polymer concentration (8, 10, and 12 wt %) and angular speed on the fiber morphology, diameter distribution, and fiber yield. The increase in polymer concentration and angular speed favored the formation of continuous and homogeneous submicrometer fibers with an absence of bead formation and higher output. The optimal conditions were established considering the morphological characteristics that exhibit a greater surface area (homogeneous and submicrometer fibers); and they were achieved at a polymer concentration of 10 wt % at an angular speed ranging from 8000 to 10 000 rpm. Optimization of PDLLA submicrometer fiber fabrication lays the groundwork for scaling up the process and serves as a platform to further develop promising applications of PDLLA nonwoven mats, particularly in the biomedical area such as in scaffolds for tissue engineering. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47643.     

Structure–property relationship for poly(lactic acid) (PLA) filaments: physical,thermomechanical and shape memory characterization

Physical, thermomechanical, and shape memory properties of two different samples of poly(lactic acid) (PLA) multifilament yarns were determined using various complementary techniques. The birefringence and crystalline fraction of one sample was higher than the other filaments sample indicating higher molecular orientation and compactness. For both filaments, two distinct morphological features with different sizes in the order of few nanometers (less than 50 nm) were found using AFM and SAXS techniques. The glass transition temperature (T_g) of the samples were ranged from 61 °C to 76 °C depends on the sample and the methods of measurement. Partial storage modulus (E′) increase above T_gas well as additional small peak in loss modulus (E″) of the lower crystallinity sample was assigned to recrystallization. The multiple overlapped peaks in the E″ and tan δ curves and subsequent crystallization along with exothermic peak right after T_g suggests the existence of both relaxed and oriented amorphous regions. The rigid crystalline regions prevented the shrinkage and enhanced dimensional stability. Multifilament yarn with higher crystallinity and total molecular orientation showed higher modulus (both dynamic and static) and strength and lower elongation at break. The oriented non-crystalline regions in the multifilament yarn sample led to moderate modulus and strength along with high elongation at break. The shape recovery of both samples with different structural parameters stayed almost constant (~50 %) upon the deformation temperature rise.     

Characterization of N,N′-dimethyl-3,4,9,10- perylenetetracarboxylic acid diimide and phthalocyaninatozinc(ii) in electrochemical photovoltaic cells

As a direct comparison to all-solid state photovoltaic cells, photoelectrochemical cells consisting of n-type N,N-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide (MePTCDI) and p-type phthalocyaninatozinc(ii) (PcZn) thin film electrodes vapour-deposited onto ITO have been investigated in aqueous ferri/ferrocyanide, p-benzoquinone/hydroquinone or I3–/I– electrolytes. The ferri/ferrocyanide cell has been studied in more detail, and the results are discussed with regard to the HOMO-, LUMO- and Fermi-energies of the materials used. A setup of the electrodes in a tandem cell could increase the efficiency of the cell due to improved light harvesting. Saturation of the photocurrent with increasing ferri/ferrocyanide electrolyte concentration at single PcZn or MePTCDI electrodes is discussed using a model of reactant adsorption prior to the charge transfer step. In addition, a decrease observed for the open-circuit voltage of the entire cell with increasing ferri/ferrocyanide concentration leads to an optimum concentration of 10–3 moldm–3.