方酸1,2—取代衍生物的合成及反应

对近年来以方酸和方酸简单衍生物（如方酰氯,方酸酯等）为原料制备１,２－取代方酸衍生物的反应,合成方法及其相关的特殊合成方法等进行了比较详细的评述。     

The electrochemical oxidation of cyclic alkyl disulfide derivatives of isocyanuric acid

Bicyclic disulfide derivatives of isocyanuric acid—methyl, phenyl and 2-(2-methoxy-phenoxy)ethyl N-substituted derivatives of 8,9-dithia triaza-bicyclo[14.3.1]eicosane and 7,8-dithia triaza-bicyclo[12.3.1]octadecane and 18-methyl-5λ⁴,8^λ4,9,12-tetrathia-1,16,18-triaza-tricyclo[14.3.1.0^5,8]eicosane-17,19,20-trion were studied by cyclic voltammetry and PM3 level molecular modeling. The oxidation involves an electrochemically reversible electron transfer followed by fast potential-determining reaction of second kinetic order and a relatively slow current-determining reaction of first-order (k=0.33-32.7 s⁻¹). Molecular modeling has shown three different types of HOMOs in this reaction series and consequently different oxidation mechanisms. None of the frontier orbitals (HOMO and LUMO) is localized on the isocyanurate heterocycle so it does not intervene directly in redox transformations but it may participate in the stabilization of the positive charge in electrogenerated cation radicals by trans-annular interaction.     

Facile and clean electrochemical synthesis of new acetaminophen derivatives through electrochemical oxidation of acetaminophen in the presence of thiouracil derivatives

The electrochemical oxidation of acetaminophen (1a) is carried out in the presence of thiouracil derivatives (3a–c), as nucleophiles, in an acetate buffer solution (0.15?M, pH 5) mixed with Dimethylformamide (DMF) using cyclic voltammetry and coulometry under a constant potential. The results obtained indicate that N-acetyl-p-benzoquinone-imine derived from acetaminophen participates in a 1,4-Michael-type addition reaction with thiouracils to form the corresponding acetaminophen derivatives (4a–c) in good yields and with high purities using a facile, catalyst-free, and one-pot electrochemical method using three carbon electrodes in an undivided cell under mild conditions. The products obtained were characterized after purification by IR, ¹H NMR, and ¹³C NMR spectroscopies, and by the elemental analysis method.     

Improving the electrochemical properties of polyaniline by co-doping with titanium ions and protonic acid

Polyaniline co-doped with titanium ions and protonic acid was synthesized in aqueous H₂SO₄ solution containing Ti(SO₄)₂ (pH 2), and was characterized via Fourier-transform infrared spectra, UV–vis spectroscopy, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy and cyclic voltammetry. Its conductivity was 2.8 S cm⁻¹ at room temperature (25 °C), which is the same order of magnitude as polyaniline doped with protonic acid (5 S cm⁻¹). Compared with polyaniline doped with protonic acid, it showed a better redox reversibility and cycling stability in aqueous pH 4.0 media, even in an acetate electrolyte (pH 4.0). It could be a promising material for several applications due the increase of the operating pH window of polyaniline in an aqueous environment.     

半胱胺改性叶酸衍生物的制备及其性能研究

在N,N-二环己基碳酰亚胺(DCC)和N-羟基琥珀酰亚胺(NHS)共同催化下制备出半胱胺改性叶酸衍生物,在pH=8的稀氨水溶液中,对纳米金和叶酸衍生物进行偶联。结果表明,叶酸的羧基与半胱胺的巯基发生了反应,叶酸衍生物具有荧光性能,并与纳米金粒子有吸附作用,在叶酸靶向肿瘤诊断治疗方面具有潜在的应用价值。     

环烷酸衍生物的合成与应用

简要介绍了环烷酸衍生物的合成工艺及应用，并对开发该类产品的可行性进行了探讨。     

Preparation and polymerization of isopimaric acid derivatives

Isopimaric acid is a typical rosin compound and can account for 30% of the total mass of slash pine rosin. The molecular structure of isopimaric acid derivatives features an unsaturated double bond at the C13 position, opening up the possibility of their industrial polymerization. In this study, isopimaric acid (95.4%), methyl isopimarate (99.5%), and allyl isopimarate (95.1%) were prepared as highly pure monomers. New experimental results are presented and mechanisms based on the investigation of free-radical polymerization under UV irradiation are proposed. New rosin monomers for potential value-added utilization of woody biomass are also identified. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47817.     

Paired electrochemical synthesis of new organosulfone derivatives

Electrochemical oxidation of “cathodically generated 4-aminocatechol (2)” has been studied in the presence of 4-toluenesulfinic acid (4a) and benzenesulfinic acid (4b) as nucleophiles in aqueous solutions, using cyclic voltammetry and controlled-potential coulometry. The results indicate that the o-benzoquinone derived from 4-aminocatechol (2) participates in Michael addition reaction with 4a or 4b to form the corresponding new organosulfone derivatives (5a and 5b). In this work we have proposed a mechanism for the electrode process. A Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ redox mediator was used for the anodic oxidation of 4-aminocatechol (2) to the corresponding o-quinone 3. The indirect electrochemical process consists of a multi-step such as (a) cathodic reduction of 4-nitrocatechol (1) to 4-aminocatechol (2), (b) chemical oxidation of 4-aminocatechol (2) to 4-aminoquinone (3) with the resulting Fe(CN)₆³⁻, (c) the chemical reaction of 4-aminoquinone (3) with 4-toluenesulfinic acid (4a) or benzenesulfinic acid (4b), and (d) the anodic regeneration of Fe(CN)₆³⁻. The paired electrochemical synthesis of organosulfone derivatives (5a and 5b) has been successfully performed in an one-pot process at carbon rod electrode as a working and platinum as a counter electrode in an undivided cell.     

Experimental and theoretical studies of electrochemical characteristics of 3,4-dihydroxyphenylacetic acid (DOPAC)

The electrochemical behavior of 3,4-dihydroxyphenylacetic acid (DOPAC) in aqueous solutions with different pHs and DOPAC concentrations was studied by cyclic voltammetry at various potential scan rates. The electro-oxidation of DOPAC involves a transfer of two electrons and two protons in solutions of pH < 8.0 and a transfer of two electrons and one proton in solutions of pH > 8.0, in agreement with the one-step two-electron mechanism. The cyclic voltammetry indicated that the process of electro-oxidation of DOPAC follows an E_rC_i mechanism. The standard redox potential, E⁰′, two-proton-two-electron and one-proton-two-electron processes of DOPAC were determined as 0.585 and 0.357 V versus saturated calomel electrode (SCE), respectively. The acidic dissociation constant of DOPAC was also obtained. Also, the diffusion coefficient of DOPAC was calculated as 9.2 × 10⁻⁶ cm² s⁻¹ for the experimental conditions, using chronoamperometric results. The standard reduction potentials and the second acidic constant of DOPAC have been also calculated using standard ab initio calculations at the G3 level of theory in conjunction with a continuum solvation model. The theoretical values are in good agreement with experiment.     

二硫代肼基甲酸配合物及其席夫碱衍生物的合成

合成了二硫代肼基甲酸镉与镍的配合物以及由二硫代肼甲酸与环己酮１，４－双（２’－甲酰基苯基）－１，４－二氧杂丁烷缩合的两种新的含硫席夫碱衍生物，所有化合物都进行了表征，确定了它们的组成，且对两种席夫碱衍生物的性质进行了初步研究。     

维生素C衍生物的制备及其在化妆品中的应用

维生素C衍牛物克服了维生素C易被氧化不稳定的缺点,被广泛用于化妆品中.阐述了维生素C衍生物围内外的研究情况,主要对维生素C的磷酸酯盐、糖苷、棕榈酸酯、乙基醚、甲基硅基等衍生物的制备方法进行了总结.介绍了其在化妆品中的应用情况,指出了维生素C衍生物的发展趋势.     

Influence of process conditions on structural and electrochemical properties of lithium phosphorus oxynitride thin films

Lithium phosphorus oxynitride (LiPON) is the most representative solid electrolyte in thin film battery applications. In addition, it has been used as an interfacial protective layer to improve the stability of cathode and anode materials. In this article, we review the effect of the process conditions on the structural and electrochemical properties of LiPON thin films. A common method to form LiPON thin films is radiofrequency (RF) sputtering; much research has been conducted to optimize the corresponding process parameters, such as RF power density, working pressure in nitrogen atmosphere, substrate temperature, substrate bias power, post-annealing, and sputtering target. Many studies have characterized LiPON films obtained with various process parameters, but significant differences have been observed in the reported trends. The most representative difference involves the N_t/N_d ratio, which has been reported to be either directly or inversely proportional to the ionic conductivity. Recently, controversial results have been obtained on the N-based local structure of LiPON thin films. The structural argument relies on the idea that nitridation promotes cross-linking via the formation of doubly and triply coordinated N bridges between P atoms. In addition to further research to clarify these issues, it is necessary to introduce new methods for the interpretation of data based on it.     

Structure and electrochemical properties of nickel hydroxide electrodes with cobalt additives

In this article,cobalt additives are introduced into nickel hydroxide electrodes by two incorporation methods—co-precipitated cobalt hydroxide during the nickel hydroxide synthesis or post-added CoO with nickel hydroxide. The results of X-ray diffraction, cyclic voltammetry, electrochemical impedance spectroscopy, and charge–discharge tests indicate that (i) the diffraction peaks show a decrease in intensity and increase in the half peak breadths for Ni(OH)₂ with co-precipitated cobalt hydroxide; (ii) the electrochemical activity of nickel hydroxide can be improved by both incorporated cobalt and the effects of post-added CoO are more notable; (iii) CoOOH derived from post-added CoO is not stable in the KOH electrolyte when the potential of the Ni(OH)₂ electrode is lowered and its reduction product may be inactive, thus results in an irreversible capacity loss of nickel-metal-hydride battery after over-discharge-state storage.     

Electrochemistry of chlorogenic acid: experimental and theoretical studies

Cyclic voltammetry, chronoamperometry and rotating disk electrode voltammetry as well as quantum chemical methods, are used for electrochemical study of chlorogenic acid, as an important biological molecule. The standard formal potential, diffusion coefficient, and heterogeneous electron transfer rate constant of chlorogenic acid in aqueous solution are investigated. Acidic dissociation constant of chlorogenic acid is also obtained. Quantum mechanical calculations on oxidation of chlorogenic acid in aqueous solution, using density functional theory are presented. The change of Gibbs free energy and entropy of oxidation of chlorogenic acid are calculated using thermochemistry calculations. The calculations in aqueous solution are carried out with the use of polarizable continuum solvation method. Theoretical standard electrode potential of chlorogenic acid is achieved to be 0.580 V versus standard calomel electrode (SCE) which is in agreement with the experimental value of 0.617 V obtained experimentally in this work. The difference is consistent with the values we previously reported for other quinone derivatives.     

含吡啶基的乙酸衍生物的合成及表征

分别以吡啶-2-甲醛和二吡啶甲基胺为原料,合成了两种含有吡啶环的新型乙酸衍生物-[（6-胺基-己基）-吡啶-2-甲基氨基]乙酸和[二（2-吡啶甲基）-氨基]乙酸.并通过IR、MS（ESI）、^1HNMR和（或）元素分析对两个化合物进行了表征.     

Facile preparation and good electrochemical hydrogen storage properties of chain-like and rod-like Co-B nanomaterials

Chain-like and rod-like Co-B nanomaterials are prepared by chemical reduction method in cetyltrimethylammonium bromide (CTAB) and polyvinylpyrrolidone (PVP) aqueous solution, respectively. XRD patterns demonstrate that the two materials both have amorphous structures. SEM and TEM images show that the chain-like Co-B constructs of one-by-one tactic ball-like particles with nanoflakes on the surface, whereas the rod-like Co-B alloy possesses a porous nanostructure. The results of electrochemical measurements indicate that, as negative electrode materials of Ni-MH batteries, their electrochemical properties are both better than those of regular Co-B alloy. At the discharge current density 25 mA g⁻¹, the discharge capacities of the chain-like and the rod-like Co-B alloys are 314 mAh g⁻¹ and 292 mAh g⁻¹ after 50 cycles, respectively, which are both higher than that of regular Co-B alloy. XRD patterns of the electrodes on different charge-discharge states illustrate that the discharge capacity is attributed to hydrogenation of Co-B alloy.     

Polypyrrole micro- and nanowires synthesized by electrochemical polymerization of pyrrole in the aqueous solutions of pyrenesulfonic acid

Polypyrrole (PPy) micro- and nanowires were synthesized through electrochemical polymerization of pyrrole in the aqueous solutions of 1-pyrenesulfonic acid (PSA), in which PSA acted as both surfactant and dopant. Macroscopic studies (SEM and TEM) indicated that the PPy wires have diameters of 120-500 nm and length of several micrometers. Electrochemical investigation demonstrated that the PPy wires have much stronger electrochemical activity than the conventional flat PPy film because of their higher specific surface area. Furthermore, the PSA doped PPy wires showed strong emission in an aqueous dispersion. A possible micelle guided formation mechanism has been proposed and investigated.     

Li-intercalation electrochemical/electrochromic properties of vanadium pentoxide films by sol electrophoretic deposition

Thin films of orthorhombic V₂O₅ have been prepared by sol electrophoretic deposition (EPD) followed by post-treatment at 500 °C. Their electrochemical and optical performances have been investigated for possible applications in electrochemical/electrochromic devices. Li⁺-intercalation properties of the films have been explored in two voltage ranges: 0.4 to −1.1 V and 0.4 to −1.6 V versus Ag/Ag⁺, respectively. High capacities of over 300 mAh/g are acquired in the wider voltage range at a current density of 50 μA/cm² and moderate capacities of 140 and 110 mAh/g are obtained in the narrower voltage range at a current density of 25 and 50 μA/cm², respectively. Electrochemical measurements have shown that the films demonstrate good cyclability in both voltage ranges. X-ray diffraction, scanning electron microscopy and optical spectra have been used to examine the changes in crystallinity, microstructure, morphology and transmittance of the films during cycling. Films cycled to a deeper voltage of −1.6 V versus Ag/Ag⁺ deliver higher capacity with appreciable morphological change, while films cycled in the narrower voltage range show moderate capacity and maintain the morphology, optical responses and crystalline structure. Voltage range can be optimized in between to acquire both high capacity and stability in structure, electrochemical and optical properties. High Li⁺-intercalation capacity and good cyclic stability are attributed to the porous structure of V₂O₅ films prepared by EPD.     

聚天冬氨酸及其衍生物的合成和性能研究进展

聚天冬氨酸及其衍生物是一种可生物降解的多功能高分子聚合物,因其具有优良的阻垢缓蚀性能而成为极具发展前途的环保型水质稳定剂。综述了国内外有关聚天冬氨酸及其衍生物的合成和性能研究进展,介绍了聚天冬氨酸及其衍生物的应用现状,提出了聚天冬氨酸及其衍生物的研究方向。     

Experimental and theoretical study on amino acid derivatives as eco-friendly corrosion inhibitor on mild steel in hydrochloric acid solution

Amino acid derivatives, namely, 2-(2-oxo-2-phenothiazin-10-yl)ethylamino)-3-mercaptopropanoic acid (OPEM) and 2-(2-oxo-2-phenothiazin-10-yl)ethylamino)acetic acid (OPEA) were synthesized and investigated as inhibitors for mild steel corrosion in 15% HCl solution using the weight loss, polarization, and electrochemical impedance spectroscopy (EIS) techniques. The inhibition efficiency of both the inhibitors increased with increasing the temperature and concentration of inhibitor. The inhibitors OPEM and OPEA show corrosion inhibition efficiency of 97.5 and 95.8%, respectively, in 200?ppm concentration, at 333?K. Polarization studies showed that both studied inhibitors were of mixed type in nature. The adsorption of inhibitors on the mild steel surface obeys Langmuir adsorption isotherm and the surface of inhibited and uninhibited specimens were analyzed by scanning electron microscopy (SEM). The semiempirical AM1 method was employed for theoretical calculations and the obtained results were found to be consistent with the experimental findings.