Enzymatic Synthesis and Polymerization of Cyclic Trimethylene Carbonate Monomer with/without Methyl Substituent

The direct enzymatic synthesis of a cyclic trimethylene carbonate (1,3‐dioxane‐2‐one) monomer with/without a methyl substituent was carried out using dimethyl or diethyl carbonate and 1,3‐diol with the objective of producing aliphatic poly(trimethylene carbonate), a typical biodegradable synthetic plastic. The lipase‐catalyzed condensation of dimethyl or diethyl carbonate with aliphatic 1,3‐diols using immobilized Candida antarctica lipase (lipase CA) in an organic solvent at 70 °C afforded the corresponding methyl‐substituted and unsubstituted cyclic trimethylene carbonates. The cyclic trimethylene carbonates obtained by the reaction of dimethyl or diethyl carbonates with 1,3‐propanediol and 2‐methyl‐1,3‐propanediol were polymerized by lipase to produce the corresponding polycarbonates.

Total TMC yield as a function of the reaction time.     

Quantum chemical study of alternating N/B and N/C π bonds in (un)charged even‐membered 4n and 4n+2 cyclic systems and their related open systems

With semi‐empirical MO and ab initio calculations at different levels, we investigated the π conjugation of alternating X? Y bonds with X? Y for N/B and N/C combinations in an open and cyclic arrangement. Although the intrinsic symmetry is lost for the acyclic even‐membered compounds, the alternation is still reflected in its geometry and electron‐density transfer. For the cyclic π compounds, we focused our attention on borazine N₃B₃H₆ (D_3h symmetry), which is isoelectronic with benzene (D_6h symmetry). Specific attention is given to the electrophilic behavior of borazine with respect to CH and SiMe. The dynamics based on the results of FT‐ICR mass spectrometry was studied in more detail. In addition, the results of the cyclic systems with 4n and 4n+2 π electrons concerning their geometries are compared with the corresponding carbon compounds. Attention is also given to the dication of borazine, because of the corresponding triplet ground state of the benzene dication. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Synthesis, crystal structure and studies on properties of trisodium 5,3′,5′-trisulfonate-2,3,4,4′-tetrahydroxy-deoxybenzoin

A new water soluble compound trisodium 5,3′,5′-trisulfonate-2,3,4,4′-tetrahydroxy-deoxybenzoin (TTDB) was synthesized and characterized by IR, UV, ¹H NMR, and elemental analysis. The single crystal of TTDB was determined by X-ray single crystal diffraction. The scavenging effect of compounds on hydroxy radicals was detected by fluorescent spectrophotometry. The electrochemical behavior of compounds in nonaqueous solution DMF was carried out by means of cyclic voltammetry. The experimental result shows that the crystal [C₁₄H₁₇Na₃O₁₈S₃] belongs to monoclinic, space group C2/c with unit cell constants a = 1.4223(4) nm, b = 2.4327(8) nm, c = 1.3596(4) nm, α = 90°, β = 113.044(5)°, γ = 90°, Z = 8, V = 4.329(2) nm³, D _c = 1.925 mg/m³, F(000) = 2568, F _w = 638.43, R ₁ = 0.0950, wR ₂ = 0.2648. The half effective concentration EC₅₀ of scavenging hydroxy radicals of compound THDB is 53.1 μmol/L, while that of scavenging hydroxy radicals of compound TTDB is 47.3μmol/L. The electrochemistry redox processes of THDB and TTDB are different from each other. __________ Translated from Chemical Journal of Chinese Universities, 2005, 26(9) (in Chinese)     

Copper passivity and its breakdown in sodium bicarbonate solutions: A scanning electron microscopy and x-ray photoelectron and auger spectroscopy study

Effect of bicarbonate ions on the copper passivity and its local breakdown is studied by cyclic voltammetry, Auger spectroscopy, x-ray photoelectron spectroscopy, and scanning electron microscopy. Comparing data for solutions with various sodium bicarbonate concentrations shows copper to undergo pitting in 0.02 M NaHCO₃, whereas it remains stably passive in 0.10 M NaHCO₃. Independent studies suggest that carbonates play a protective role in stabilization of the oxide-hydroxide passive film on copper.     

交流示波极谱法中i_f～E曲线的研究 Ⅳ.示波极谱氧化还原滴定法

在i_f～E曲线的测量方法中,由于氧化和还原剂都具有电化学活性,因此,这两种试剂的量就可以通过不同电极电位处的法拉第电流峰敏锐地反映出来。当利用i_f～E曲线指示氧化还原滴定终点时,终点的示波图形,不仅反映氧化和还原剂电流峰的出现和消失,而且反     

Determination of dissolved manganese in natural waters by differential pulse cathodic stripping voltammetry

A procedure based on differential pulse cathodic stripping voltammetry on the graphite electrode is described for the determination of dissolved manganese in natural waters buffered at pH about 6.5 with acetate solution. In order to avoid interference of iron(II) the addition of fluoride is used. The limit of detection is 3 g/l for a deposition time of 6 min. Acidification and UV-irradiation are recommended for samples containing dissolved organic matter. Results of manganese determination in table mineral waters are reported and the possibility of manganese speciation is discussed.     

Determination of BHT in the presence of surfactants using a cellulose acetate coated electrode and square wave voltammetry

A direct voltammetric method for the rapid determination of butylated hydroxytoluene has been developed. The procedure utilizes a hydrolyzed cellulose acetate film in intimate contact with a glassy carbon electrode and square wave voltammetry. The coated electrode prevents passivation due to adsorption of polymeric oxidation products by way of a size exclusion principle. BHT solutions containing lipid-like surfactants can be analyzed without the need for frequent resurfacing of the electrode.     

Ruthenium cluster compounds containing 1,1′-bis(diphenylphosphino)ferrocene (dppf): an electrochemical analysis and the crystal structure of [Ru3(CO)11]2(μ-dppf)

The electrochemistry of 1,1′-bis(diphenylphosphino)ferrocene (dppf) derivatives of Ru₃(CO)₁₂ was investigated. Two known compounds [Ru₃(CO)₈(μ-dppf)₂ (1) and Ru₃(CO)₁₀dppf (2)] and a new compound [Ru₃(CO)₁₁(μ-dppf)Ru₃(CO)₁₁ (3)] were prepared. Compound 3 was characterized spectroscopically and an X-ray crystal structure was obtained. The reductive electrochemistry of 1 and 2 showed an irreversible reduction and a follow-up oxidation, similar to Ru₃(CO)₁₂. The electrochemistry of compound 3 showed two irreversible waves and a follow-up oxidation. A trend in the reduction potential vs. the number of coordinated phosphorus atoms was noted. The oxidative electrochemistry of 1-3 showed a dppf-based chemically reversible wave, and an irreversible wave similar to that of Ru₃(CO)₁₂. Trends were also noted between the oxidation potential and the number of coordinated phosphorus atoms.     

The Electrochemical Behavior of α‐Ketoglutarate at the Hanging Mercury Drop Electrode in Acidic Aqueous Solution and Its Practical Application in Environmental and Biological Samples

The voltammetric behavior of α‐ketoglutarate (α‐KG) at the hanging mercury drop electrode (HMDE) has been investigated in acetate buffer solution. Under the optimum experimental conditions (pH 4.5, 0.2 M NaAc‐HAc buffer solution), a sensitive reductive wave of α‐KG was obtained by linear scan voltammetry (LSV) and the peak potential was ?1.18 V (vs. SCE), which was an irreversible adsorption wave. The kinetic parameters of the electrode process were α=0.3 and k_s=0.72 1/s. There was a linear relationship between peak current i_{p, α‐KG} and α‐KG concentration in the range of 2×10^?6–8×10^?4 M α‐KG. The detection limit was 8×10^?7 M and the relative standard deviation was 2.0% (C_α‐KG=8×10^?4 M, n=10). Applications of the reductive wave of α‐KG for practical analysis were addressed as follows: (1) It can be used for the quantitative analysis of α‐KG in biological samples and the results agree well with those obtained from the established ultraviolet spectrophotometric method. (2) Utilizing the complexing effect between α‐KG and aluminum, a linear relationship holds between the decrease of peak current of α‐KG Δi_p and the added Al concentration Cequation/tex2gif-inf-5.gif in the range of 5.0×10^?6–2.5×10^?4 M. The detection limit was 2.2×10^?6 M and the relative standard deviation was 3.1% (Cequation/tex2gif-inf-6.gif=4×10^?5 M, n=10). It was successfully applied to the detection of aluminum in water and synthetic biological samples with satisfactory results, which were consistent with those of ICP‐AES. (3) It was also applied to study the effect of Al^III on the glutamate dehydrogenase (GDH) activity in the catalytically reaction of α‐KG+NH +NADH?L ‐glutamate+NAD⁺+H₂O by differential pulse polarography (DPP) technique. By monitoring DPP reductive currents of NAD⁺ and α‐KG, an elementary important result was found that Al could greatly affect the activity of GDH. This study could be attributed to intrinsic understanding of the aluminum's toxicity in enzyme reaction processes.     

Determination of Azidothymidine – an Antiproliferative and Virostatic Drug by Square‐Wave Voltammetry

The 3′‐azido‐3′‐deoxythymidine (AZT, Zidovudine) is an antiproliferative and virostatic drug widely used in human immunodeficiency virus type 1 (HIV‐1) infection treatment. With respect to side effects of high doses and a short half‐life of AZT, a fast and simple detection method for this agent could be helpful. The aim of our study was to determine AZT levels in natural samples (urine, serum, whole blood, and cell cultures, such as the HaCaT line of keratinocytes) without their mineralization and/or purification, by means of electrochemical methods using hanging mercury drop electrode (HMDE). On this electrode, AZT undergoes irreversible reduction at the peak potential near E_p?1.1 V (vs. Ag/AgCl/3 M KCl). Reduction AZT signals were measured by cyclic voltammetry (CV), differential pulse voltammetry (DPV), square‐wave voltammetry (SWV), and constant current chronopotentiometric stripping analysis (CPSA). In phosphate buffer (pH 8) the SWV yielded the best AZT signal with the detection limit of 1 nM. The determination of AZT concentration in biological materials is affected by electroactive components, such as proteins and DNA. For monitoring the influence of these compounds, AZT reduction was performed in the presence of 10 μg/mL calf thymus ssDNA and/or 100 μg/mL bovine serum albumin. In these cases, the detection limit increased to 0.25 μM. Also studied was the AZT concentration in keratinocyte cells (HaCaT line) during cell cultivation. It has been shown that the SWV may be considered as a useful tool for the determination of AZT concentration in cell cultures, and for monitoring AZT pharmacokinetics.