Synthesis,characterization, and biological activity of [2‐oxo‐2‐(4‐acetyl) phenyl amino] ethylene methacrylate and its derivatives

A new type of methacrylate monomer, [2‐oxo‐2‐(4‐acetyl) phenyl amino] ethylene methacrylate (APEMA), was synthesized. The oxime, 2,4‐dinitrophenylhydrazone, and thiosemicarbazone derivatives of poly{[2‐oxo‐2‐(4‐acetyl) phenyl amino] ethylene methacrylate} [poly(APEMA)] were prepared with hydroxylamine hydrochloride, 2,4‐dinitrophenylhydrazine, and thiosemicarbazone hydrochloride, respectively. The radical homopolymerization of APEMA was performed at 65 °C in a 1,4‐dioxane solution with benzoyl peroxide as an initiator. The monomer and its homopolymer were characterized with Fourier transform infrared and NMR techniques. The thermal stabilities of poly(APEMA) and its derivatives were investigated with thermogravimetric analysis and differential scanning calorimetry. The ultraviolet stability of the polymers were compared. The solubility and inherent viscosity of the polymers were also determined. The number‐average and weight‐average molecular weights and polydispersity index of the polymers were determined with gel permeation chromatography. The antibacterial and antifungal effects of the monomer and the polymer and its derivatives were also investigated on various bacteria and fungi. The activation energies of the thermal degradation of the polymers were calculated with the Ozawa method. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3157–3169, 2004     

FeIII in a high-spin state in bis(5-bromosalicylaldehyde 4-ethylthiosemicarbazonato-κ3O,N1,S)ferrate(III) nitrate monohydrate,the first example of such a cationic FeIII complex unit

The synthesis and crystal structure (100 K) of the title compound, [Fe(C₁₀H₁₁BrN₃OS)₂]NO₃·H₂O, is reported. The asymmetric unit consists of an octahedral [Fe^III(HL)₂]⁺ cation, where HL^? is H-5-Br-thsa-Et or 5-bromosalicylaldehyde 4-ethylthiosemicarbazonate(1?) {systematic name: 4-bromo-2-[(4-ethylthiosemicarbazidoidene)methyl]phenolate}, a nitrate anion and a noncoordinated water molecule. Each HL^? ligand binds via the thione S, the imine N and the phenolate O atom, resulting in an Fe^IIIS₂N₂O₂ chromophore. The ligands are orientated in two perpendicular planes, with the O and S atoms in cis and the N atoms in trans positions. This [Fe(HL)₂](anion)·H₂O compound contains the first known cationic Fe^III entity containing two salicylaldehyde thiosemicarbazone derivatives. The Fe^III ion is in the high-spin state at 100 K. In addition, a comparative IR spectroscopic study of the free ligand and the ferric complex is presented, demonstrating that such an analysis provides a quick identification of the degree of deprotonation and the coordination mode of the ligand in this class of metal compounds. The variable-temperature magnetic susceptibility measurements (5–320 K) are consistent with the presence of a high-spin Fe^III ion with a zero-field splitting D = 0.439 (1) cm^?1.     

Novel and Rapid Deep Eutectic Solvent (DES) Homogeneous Liquid–Liquid Microextraction (HLLME) with Flame Atomic Absorption Spectrometry (FAAS) Detection for the Determination of Copper in Vegetables

Novel and fast deep eutectic solvent (DES)-based homogeneous liquid–liquid microextraction (HLLME) was applied for the extraction of copper from vegetable samples followed by flame atomic absorption spectrometry (FAAS). 1,5-diphenyl carbazone (DPC) was used as the chelating agent, and a DES was used as the extraction media. The utilized DES was based on benzyl triphenyl phosphonium bromide and ethylene glycol in a 1:8?mole ratio. The phase separation phenomenon was occurred by changing of sample temperature. Several factors influencing the extraction efficiency were investigated and optimized. Under the optimized conditions, an enhancement factor of 64 was obtained. The limit of detection, based on three signal-to-noise ratio, and limit of quantification were found to be 0.13?µg L^?1 and 5.0?µg L^?1, respectively. The calibration curve was linear within the range of 5.0–250?µg L^?1 with r² > 0.9957. Intra- and inter-day relative standard deviations (%) of 2.1% and 2.6% were obtained at the concentration of 25?µg L^?1. The accuracy of the proposed method was evaluated by analyzing a tomato leaves certified reference material and the results were to be in agreement with the certified value. Finally, the feasibility of the method was successfully confirmed by determination of copper in spinach, lettuce, broccoli, potato, carrot and parsley samples.     

铅(镉)-二-(邻-甲苯基)硫卡巴腙配合物吸附极谱波法连续测定铅和镉的研究

研究了二－（邻－甲苯基）硫卡巴腙（简写为Ｈ２ＤＭＢＤｚ）与Ｐｂ（Ⅱ）和Ｃｄ（Ⅱ）配合物体系的二阶导数吸附极谱波。在ｐＨ６．０的ＨＡｃ－ＮａＡｃ介质中,Ｐｂ（Ⅱ）－（Ｈ２ＤＭＢＤｚ）和Ｃｄ（Ⅱ）－（Ｈ２ＤＭＢＤｚ）２配合物分别于－０．５２Ｖ（υｓ．ＳＣＥ）和－０．６５Ｖ（υｓ．ＳＣＥ）电位处产生一良好的可逆吸附极谱波。峰电流Ｉ″ｐ１和Ｉ″ｐ２分别与Ｐｂ（Ⅱ）的浓度ｃ１和Ｃｄ（Ⅱ）的浓度ｃ２在０．０１     

Syntheses of 4‐(5‐oxo‐1,2,4‐triazol‐3‐yl)‐sydnones and 4‐(4‐arylamino‐5‐oxo‐1,2,4‐triazol‐3‐yl)‐sydnones from Sydnone Derivatives and Their Fragments

4‐(5‐oxo‐1,2,4‐triazol‐3‐yl)‐sydnones 11 and 4‐(4‐arylamino‐5‐oxo‐1,2,4‐triazol‐3‐yl)‐sydnones 13 have been obtained from a‐chloroformylarylhydrazine hydrochloride 2 . Moreover, the intermediates, including 3, 4 , 9 and 10 , in this study are synthetically informative and valuable. It is also noteworthy that three reactants, 1, 2 and sydnonecarbaldehydes, were prepared from sydnone derivatives and their fragments. The oxidative cyclizations of sydnonecarbaldehyde semicarbazones 9 and carbazones 10 with two different oxidizing agents (Cu(ClO₄)₂ and Fe(ClO₄)₃) have been extensively examined. The reaction time and the yields of cyclizations were affected by the substituents of semicarbazones 9 and carbazones 10.     

Synthesis,characterization, and biological activity of N‐(4‐acetylphenyl)maleimide and its oxime,carbazone, thiosemicarbazone derivatives and their polymers

A new type of maleimide monomer, N‐(4‐acetylphenyl)maleimide (NAPMI), was synthesized. The oxime, carbazone, and thiosemicarbazone derivatives of NAPMI were prepared with hydroxylamine hydrochloride, semicarbazide hydrochloride, and thiosemicarbazide hydrochloride, respectively. Radical homopolymerization of NAPMI and its derivatives were prepared at 60 °C in dimethyl sulfoxide solution with azobisisobutyronitrile as an initiator. The monomers and theirs homopolymers were characterized with Fourier transform infrared and NMR techniques. The glass‐transition temperatures, thermal stability, and ultraviolet stability of the polymers are compared. The activation energies of the thermal degradation of polymers were calculated by the Kissinger method. The antibacterial and antifungal effects of the monomers and polymers were also investigated on various bacteria and fungi. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1942–1951, 2003     

Diorganozinn(IV)-Komplexe dreizähniger Carbazone – Strukturuntersuchungen im festen Zustand und in Lösung

Diorganotin(IV) Complexes of Tridentate Carbazones – Structural Investigations in Solid State and in Solution The structures of the products from the reaction of diphenyltin oxide with O-methyl-β-N-(salicylmethyliden)-carbazone H₂I , di-n-butyltin oxide, respectively, and neophyl-phenyl-tin oxide with 2[(2-methoxycarbonyl)-hydrazono]-propionic acid H₂II were solved with X-ray crystal-structure analyse and multinuclear NMR spectroscopy in solution. IR investigations support the statements. While Ph₂Sn-I is found as a trigonal bipyramidal coordination polyhedron we demonstrated an increased coordination number for the tin atom in n-Bu₂Sn-II and NeoPhSn-II by formation of dimers. The coordinated carboxylate oxygen atom acts as bridging donor atom with bond lengths of Sn1–O3 2,353(2) Å, Sn1–O3 a 2,579(2) Å ( n-Bu₂Sn-II ) and Sn1–O3 2,369(2) Å, Sn1–O3 a 2,721(3) Å ( NeoPhSn-II ). In addition the dimers are stabilized by intermolecular hydrogen bonds.