AMIDO- AND AMINO-ALKYLATION OF SULFIMIDES,SULFOXIMIDES, AND SULFODIIMIDES

Abstract

Sulfimides, Sulfoximides and Sulfodiimides are polyfunctional compounds with nucleophilic/basic nitrogen and acidic hydrogen adjacent to sulfur. From these Mannich-type-reaction products 1 were prepared. For example, amidomethylation on nitrogen was achieved either directly via three-component condensation (pathway (a) or, after conversion of the S-Imide into the sodium salt by treatment with N-chloromethyl-amides (pathway (b)). With highly reactive methylene-iminium halides pathway (b) provided N-aminomethylated sulfoximides, the stability of which mainly depends on the substituents on sulfur. Surprisingly stable, however, are their monoquaternary salts. These are of pharmaceutical interest with respect to anticholinergic and antihistamine activity, which was found in this series and will briefly be discussed. Of similar interest but spasmolytically less active are C-Mannich-bases of type 2 as well as N-aminoalkylated sulfodiimides 3, which were synthesized by different reaction routes.     

NEMATICIDAL,INSECTICIDAL, ANTIFERTILITY,ANTIFUNGAL AND ANTIBACTERIAL ACTIVITIES OF SALICYLANILIDE SULPHATHIAZOLE AND ITS MANGANESE,SILICON AND TIN COMPLEXES

A facile synthesis and studies on the stereochemistry and biochemical aspects of some organosilicon(IV), organotin(IV), and manganese(II) complexes derived from imine having N^∪N^∪O donor system is reported. The imine was prepared by the condensation of salicylanilide with sulphathiazole. This imine reacts with organosilicon(IV)chloride, organotin(IV)chloride, and hydrated manganese(II) chloride to yield compounds having M─O and M←N bonds. The structures of the compounds have been elucidated by physicochemical and spectral (IR, ¹H NMR, ¹³C NMR, ²⁹Si NMR, ¹¹⁹Sn NMR, and ESR) studies, which clearly point to a trigonal bipyramidal geometry around silicon(IV) and tin(IV), and tetrahedral geometry around manganese(II), as the active lone pair of the nitrogen is also included in the coordination sphere. In the search for better fungicides and bactericides, studies were conducted to assess the growth-inhibiting potential of the synthesized complexes against various pathogenic fungal and bacterial strains. These complexes are highly active against nematode (Meloidogyneincognita) and insect (Trogodermagranarium). The activity will be increased with increasing concentration. These studies demonstrate that the concentrations reached levels that are sufficient to inhibit and kill the pathogens. All compounds have also been found to act as sterilizing agents by reducing the production of sperm in male mice.     

POLYHEDRAL METALLOPHOSPHONATES AND -SILICATES: SYNTHESIS,FUNCTIONALIZATION, AND TRANSFORMATIONS

We synthesized molecular cyclic and polyhedral precursors to aluminophosphate and silicate materials and studied their substitution and nonhydrolytic sol-gel reactions.     

四苯氧基酞菁镁、锰、铝和锌的合成和性质

合成了新的酞菁配合物４，４，４，４－四苯氧基酞菁镁［ＴＰｈＯＰｃＭｇ（Ⅱ）］，锰［ＴＰｈＯＰｃＭｎ（Ⅱ）Ａｃ］，铝［ＴＰｈＯＰｃＡｌ（Ⅲ）Ｃｌ］，锌［ＴＰｈＯＰｃＺｎ（Ⅱ）］测定了它们的ＩＲ，ＵＶ－Ｖｉｓ光谱，在ＤＭＦ中的氧化还原半波电势（Ｅ１／２），电子转移速度常数，在乙腈中的荧光性质及锰的配合物在不同电位下的光谱变化情况。     

CHEMOSELECTIVE ACETYLATION OF ALCOHOLS,AMINES, AND THIOLS WITHOUT CATALYST AND SOLVENT

Microwave induced rapid and selective acetylation of alcohols, amines and thiols with acetic anhydride was carried out under non-catalytic and solvent free conditions.     

SOME NEW S-, S,S- AND N,S-SUBSTITUTED 2-NITRODIENES AND BUTADIENYL-SUBSTITUTED PIPERAZINES

Nitrodiene 1 reacted with 2a, b and gave the novel compounds 3a, b, 4a, b, and 5a. Monosubstituted diene compound 3a gave the compounds 9a with morpholine, 11a with piperidine, and 13a with homopiperazine. Compound 3a gives the thioether compound 15 by the reaction with the dithiol (HS─(CH₂)₂─O─(CH₂)₂─SH) in ethanol containing sodium hydroxide.     

COMPLEX FORMATION BETWEEN PYRENE AND THE NUCLEOTIDES GMP, CMP, TMP AND AMP

Pyrene has been found to form ground and excited electronic state complexes of 1:1 stoichi-ometry with GMP, CMP, TMP and AMP. The values of their ground state association constants are 45 M^-1, 13M^-1, 14 M^-1, and 52 M^-1 respectively. The fluorescence of pyrene is strongly quenched by GMP, CMP, and TMP but only slightly by AMP. Fluorescence quenching analysis has yielded the values 87M^-1, 73 M^-1, and 154 M^-1 for the excited state association constants with GMP, CMP, and TMP, respectively. The corresponding values for the excited state second-order rate constant for complex formation are: 3.3 times 10⁹M^-1 s^-1 4.1 times 10⁹M^-1 s^-1, and 4.0 times 10⁹M^-1 s^-1. The probabilities of complex formation per collision between an excited pyrene molecule and a nucleotide are: 0.52, 0.64, and 0.63. The values for the excited state rate constant for dissociation of the complex are: 3.8 times 10⁷s^-1 5.6 times 10⁷s^-1, and 2.6 times 10⁷s^-1. The possibility is discussed that partial transfer of charge from pyrene to nucleotide may be playing a role in the complex formation process.     

COACERVATION,COMPLEX-COACERVATION AND FLOCCULATION

The mechanism of coacervation is reexamined in the light of recent studies on the polar (i.e., hydrogen-bonding) components of interfacial Interactions in aqueous media. The differences and similarities between coacervation, complex coacervation and flocculation are outlined and illustrated with a number of examples.     

COMPARATIVE STUDIES ON THE LETHAL, MUTAGENIC, AND RECOMBINOGENIC EFFECTS OF ULTRAVIOLET-A,-B,-C, AND VISIBLE LIGHT WITH AND WITHOUT 8-METHOXYPSORALEN IN Saccharomyces cerevisiae

Genetic effects of UV-A, UV-B, UV-C, and the combination of 8-methoxypsoralen (8-MOP) with UV-A or visible light were studied in the haploid strain XV185-14C and diploid strain D5 of Saccharomyces cerevisiae. The induction of his+, lys+, and hom+ reverse mutations was measured in strain XV185-14C. In strain D5 we measured the induction of genetically altered colonies, particularly twin spot colonies arising from a mitotic crossing-over. UV-C and UV-B induced point mutations at the three loci in the haploid strain and mitotic crossing-over and other genetic alterations in the diploid strain. UV-C was more mutagenic and recombinogenic than UV-B. UV-A or visible light alone did not induce genotoxic effects at the doses tested. However, UV-A plus 8-MOP produced lethal and mutagenic effects in the haploid strain XV185-14C, although mutagenic activity was less than that of UV-B. Visible light plus 8-MOP also induced genotoxic effects in strain XV185-14C. In the diploid strain D5, UV-A plus 8-MOP induced a higher frequency of genetic alterations than UV-B at comparative doses. Visible light plus 8-MOP was also genetically active in strain D5. The haploid strain was more sensitive to the lethal effects of UV-C, UV-B, UV-A, and impure visible light plus 8-MOP than the diploid strain.     

NMR,PE AND MASS SPECTROSCOPY OF 2-ALKYL- AND 2-ARYL-CARBAMYL- AND THIOCARBAMYL-CYCLOHEXANONES

Abstract

The following β-ketoamides and β-ketothioamides were prepared through Stork reaction.^3–6     

COMPARATIVE STUDIES ON THE LETHAL, MUTAGENIC, AND RECOMBINOGENIC EFFECTS OF ULTRAVIOLET-A,-B,-C, AND VISIBLE LIGHT WITH AND WITHOUT 8-METHOXYPSORALEN IN Saccharomyces cerevisiae

Abstract
Genetic effects of UV-A, UV-B, UV-C, and the combination of 8-methoxypsoralen (8MOP) with UV-A or visible light were studied in the haploid strain XV185–14C and diploid strain D5 of Saccharomyces cerevisiae. The induction of his+, lys+, and horn+ reverse mutations was measured in strain XV185–14C. In strain D5 we measured the induction of genetically altered colonies, particularly twin spot colonies arising from a mitotic crossing-over. UV-C and UV-B induced point mutations at the three loci in the haploid strain and mitotic crossing-over and other genetic alterations in the diploid strain. UV-C was more mutagenic and recombinogenic than UV-B. UV-A or visible light alone did not induce genotoxic effects at the doses tested. However, UV-A plus 8-MOP produced lethal and mutagenic effects in the haploid strain XV185–14C, although mutagenic activity was less than that of UV-B. Visible light plus 8-MOP also induced genotoxic effects in strain XV185–14C. In the diploid strain D5, UV-A plus 8-MOP induced a higher frequency of genetic alterations than UV-B at comparative doses. Visible light plus 8-MOP was also genetically active in strain D5. The haploid strain was more sensitive to the lethal effects of UV-C, UV-B, UV-A, and impure visible light plus 8-MOP than the diploid strain.     

CELLULOSE ACETATE AND EPOXY RESIN BLEND ULTRAFILTRATION MEMBRANES: REPARATION,CHARACTERIZATION, AND APPLICATION

ABSTRACT

Membranes based on cellulose acetate used in ultrafiltration applications lack good, chemical, mechanical and thermal resistance. In order to prepare membranes with improved properties, modification of cellulose acetate with epoxy resin through solution blending was attempted. In the present work, the membrane casting solutions with different polymer blend compositions of cellulose acetate and diglycidyl ether of bisphenol-A (DGEBA) were prepared at 30±2°C. The maximum percent compatibility of the two polymers, cellulose acetate and diglycidyl ether of bisphenol-A, was estimated to be 60/40%. Ultrafiltration blend membranes based on various blend compositions were prepared, characterized in terms of compaction, pure water flux, water content, membrane hydraulic resistance and molecular weight cut-off. The application of these membranes, in rejection of proteins of various molecular weights, are discussed.     

SYNTHESES,STRUCTURES AND REACTIONS OF NEW AND NOVEL FOUR-, FIVEAND SIX-MEMBERED UNSATURATED N,P-HETEROCYCLE COMPLEXES

Metal-assisted heterocyclic ligand syntheses are reported using 2-H-azaphosphirene complex 1 or 7-phosphanorbornadiene complex 7 as starting material. Thermal decomposition of complex 1 led to 1,2dihydro-1,2,3-azadiphosphete complex 2, which was transformed into 2,6-dihydro-1,3,2,6-diazadiphosphinines 5a, b via ring expansion with carbonitriles 3a, b. Insertion of tert-butyl isonitrile into the P─ P bond of 2 at ambient temperature furnished the first Δ ¹ -1,3,5-azadi-phospholene complex 6─P bond of 2 using 7 failed. The 1,2,3,4-azatriphospholene complexes 9a, b were obtained by thermolysis of complex 2 in the presence of functionalized carbonitriles 8a, b.     

钆、铽、铒、铥的乙酰丙酮三水络合物的晶体结构和分子结构

报导了用X射线衍射法测定的钆、铽、铒、铥的四种乙酰丙酮三水络合物的晶体结构。确定了它们的晶体学参数与原子在晶胞中的分数坐标。讨论了晶体结构与分子结构的特征。     

PHOTOCHEMISTRY AND SPECTROSCOPY OF CHLOROPHYLL, BACTERIOCHLOROPHYLL AND BACTERIOVIRIDIN IN MODEL SYSTEMS AND PHOTOSYNTHETIZING ORGANISMS

Abstract— In the system (electron donor—pigment—electron acceptor), the photosensitising pigment transfers an electron (hydrogen) from the donor to the acceptor by converting light energy, absorbed by the pigment, into the potential chemical energy of the products. The dependence of the reaction of excited pigments with electron donors or acceptors on the magnitude of the electron affinity of the reacting molecules, the nature of the medium, and the experimental conditions was observed. The initial photo-process was seen to involve the formation of free radicals, with the subsequent formation of compounds with saturated valencies. The reverse reaction of the photoproducts was accompanied by chemiluminescence. The study of systems containing pyridinenucleotides showed the possibility of photosensitised oxidation—reduction of these compounds by a pigment, and of direct photooxidation of reduced pyridinenucleotides by an electron acceptor of a different kind. In order to understand the specific photo-transfer of an electron in organisms, the spectral properties of pigments in organisms were compared with the properties of model pigments in monomeric and aggregated forms. It was established that the main role in the spectroscopic properties shown by bacteriochlorophyll, bacterioviridin and chloropyll in organisms is played by various types of intermolecular interactions (aggregations). Different forms of pigment may be involved in different stages of the phototransfer of an electron.     

SYNTHESIS,CHARACTERIZATION, AND SURFACE ACTIVITY OF SURFACTANTS DERIVED FROM NONYLPHENOL,ETHYLENE OXIDE AND CARBON DIOXIDE

The synthesis of the nonylphenol poly(ethylene carbonate) surfactants derived from nonylphenol (NP), carbon dioxide and ethylene oxide (EO) were carried out with high yields in the presence of alkali metal salts (K₂CO₃, Na₂CO₃, K₂SnO₃ and zinc glutamate) as base catalysts. The synthesis reactions were carried out in a stainless-steel reactor in the temperature range of 150-200°C under an initial pressure of 800 psi, with an initial molar ratio of CO2/EO = 0·21, catalyst concentration of 1 × 10³ M for a 24 h-period. The surfactants were characterized by FT-IR and by H-NMR. The percentages of carbon dioxide incorporation were between 7 and 16% indicating that the activation of CO₂ is a rather difficult process under the catalytic conditions used L175-200 °C and 800 psi of final pressure)

It was found that the most probable mechanism for the synthesis of the surfactants occurs in two steps. The first reaction involves the role of the base as a catalyst for the formation of the cyclic ethylene carbonate from CO₂ and ethylene oxide. The next step is the reaction of the nonylphenol in the presence of cyclic ethylene carbonate and ethylene oxide to generate the surface active compounds. This mechanism indicates that for each mol of carbon dioxide incorporated, one mol of EO has to be added.

The CMC values of the surfactants decrease (from 200 to 100 mM) with the increase in the molar ratio CO₂/EO (from 0·08 to 0·3) which can be attributted to a decrease in the hydrophilic character of the surfactant heads due to the addition of carbonate groups(-O-C(=0)-0-) to the ethoxylated chains (between I to 3 moles).     

离子色谱法测定饮用和地下水中氟化物、溴酸盐、氯化物、亚硝酸盐、硝酸盐、硫酸盐

建立离子色谱法测定饮用和地下水中F-、BrO3-、Cl-、NO2、NO3和SO42- 6种阴离子.选用IonPac(R)AS19色谱柱(4 mm×250 mm),NaOH梯度淋洗,抑制电导检测,方法检出限为0.01～0.02 mg/L.对水样进行6次平行测定,测定结果的相对标准偏差为1.1％～2.1％,加标回收率为71...     

MECHANICS AND THERMODYNAMICS OF INTERFACES,THIN LIQUID FILMS AND MEMBRANE

First we review some recent studies devoted to the role of surface moments (torques) in the mechanics and thermodynamics of fluid interfaces of arbitrary shape. The presence of bending and torsion moments leads to a difference between the mechanical and thermodynamical surface tensions and shear stresses. Next we review recent results in the mechanics of thin liquid films and the transition region film-Plateau border. Line and transversal tensions are assigned as excesses on the contact line. The transversal tension accounts for the attractive forces in the transition zone. Experiments with floating bubbles show that the movement of the contact line can lead to non-equilibrium values of the line tension, which can be interpreted in terms of a plastic deformation.