The Chemistry of Chrome Mordanting of Wool

The chemistry of chrome mordanting is discussed under the headings: reaction of wool with chromium(VI) anions; reaction of wool with chromium(III) cations; reduction of chromium(VI) to chromium(IlI); interaction between chromium(Vl) and dye; interaction between chromium(III) and dye; and interaction between chromium(III), dye and wool.     

Homogeneous Catalysis. Mechanisms of Metal Catalysed Claisen Rearrangements of O-allylic-S-methyl dithiocarbonates

A number of catalysts of Pd(II), Pt (II), Rh (I) and Ir(I) induce rearrangements of O-allylic-S-methyl dithiocarbonates at 25° C. For most substrates, the Pd(II) and Pt(II) catalysts cause [3,3] sigmatropic (Claisen) rearrangements but the Rh(I) and Ir(I) catalysts give, in addition, other products depending on the catalyst and the substrate. The Claisen rearrangements observed with the Pd(II) and Pt(II) catalysts are believed to occur by a cyclization induced mechanism, whereas those rearrangements associated with the Rh(I) and Ir(I) catalysts, as well as in one case with the Pd(II) catalyst, appear to involve metal stabilized carbocation intermediates. When cyclic substrates are used retention of configuration is observed predominantly for all catalysts tried.     

芳基取代丙烯腈为骨架的芪类化合物的合成

对合成结构较简单的4种以芳基取代丙烯腈为骨架的芪类化合物的常用合成方法进行了研究。以取代苯甲醛和取代苯乙腈为原料,在氮气保护、甲醇钠作催化剂等条件下,通过一步缩合反应,高收率得到(Z)-2-(3,4-二甲氧苯基)-3-(4-甲氧苯基)丙烯腈(Ⅰ)、(Z)-2-(3,4-二甲氧苯基)-3-(3,4-二甲氧苯基)丙烯腈(Ⅱ)、(Z)-2-(3,4-二甲氧苯基)-3-(4-二甲氨基苯基)丙烯腈(Ⅲ)、(Z)-3-(3,5-二甲氧苯基)-2-(4-甲氧苯基)丙烯腈(Ⅳ),实测收率分别为98.3%、96.0%、83.4%及88.8%。     

服装用静电植绒胶的合成与应用

以丙烯酸丁酯(BA)为软单体、丙烯酸甲酯(MA)为硬单体、2-乙基己烷丙烯酸酯(2-EHA)为特软单体、丙烯酸(AA)为亲水单体、二甲基丙烯酸乙二醇酯(EGDM)为交联剂、平平加(O-25)和十二烷基硫酸钠(SDS)为复合乳化剂、过硫酸钾(KPS)和偏重亚硫酸钠(SM)为氧化还原型引发剂,采用乳液共聚法合成环保型静电植绒胶。结果表明:当m(BA)∶m(MA)∶m(2-EHA)∶m(AA)∶m(EGDM)∶m(0-25/SDS)∶m(KPS/SM)=100∶40∶4∶8∶3∶(26/7)∶(1/1.0)时,胶粘剂稳定性较好;此时静电植绒织物中无游离甲醛含量和APEO含量,其摩擦牢度2 500次且柔软度为4~5级,符合生态服装面料的使用要求。     

Synthesis of the Sulphonate and Phosphonate Derivatives of Mercaptoacetyltriglycine. X-Ray Crystal Structure of Na(2)[ReO(Mercaptoacetylglycylglycylaminomethanesulphonate)].3H(2)O

Mercaptoacetyltriglycine forms complexes with (186/188)Re and (99m)Tc radionuclides that are useful in nuclear medicine because they are substrates of the renal anion transport system. However, the renal clearance of [MO(MAG(3))](2-)(MAG(3) = penta-anionic form of mercaptoacetyltriglycine, M = Re, Tc) complexes are less than ideal. Organic sulphonates are also transported by the renal anion transport system and phosphonates are similar to sulphonates in size and shape. In an effort to develop new ligands that form Re and Tc complexes and have improved renal clearances compared to [MO(MAG(3))](2-) complexes, the sulphonate and phosphonate derivatives of mercaptoacetyltriglycine were synthesized. The dianion [ReO(MAG(2)-AMS)](2-) (MAG(2)-AMS = penta-anionic form of mercaptoacetylglycylglycylaminomethanesulphonic acid) was prepared for characterization by exchange reaction of ReOCl(3)(Me(2)S)(OPPh(3)) and isolated as the disodium salt. The structure of Na(2)[ReO(MAG(2)-AMS)].3H(2)O (6) was determined by X-ray diffraction. The coordination geometry is pseudo square pyramidal, with the nitrogen and sulfur donor atoms forming a square base and the oxo ligand at the apex. The deprotonated sulphonate group has a syn conformation with respect to the oxo ligand. The renal clearances of [(99m)TcO(MAG(2)-AMS)](2-) and [(99m)TcO(MAG(2)-AMP)](3-) were similar in rats and suggest that the difference in total charge between the SO(3) (-) and PO(3) (2-) groups is not important to renal clearance. However, their renal clearances were 40-50% less than that of [(99m)TcO(MAG(3))](2-) suggesting that the size and shape of the large tetrahedral SO(3) (-) and PO(3) (2-) groups of [(99m)TcO(MAG(2)-AMS)](2-) and [(99m)TcO(MAG(2)-AMP)](3-) inhibit recognition by the renal transport system compared to the small planar CO(2) (-) group of [(99m)TcO(MAG(3))](2-).     

The Synthesis of Phthalic Anhydride via Ozonation of Naphthalene

The oxidation of naphthalene (1) (Scheme 1) in dichloromethane or acetonitrile with excess ozone gives phthalic aldehyde (3), 2-formyl benzoic acid (4) and phthalic anhydride (8). Small amounts of the (E)- and (Z)-isomer of 3-phenyl-(2-formyl)-propenal (10) and (11) are also observed in some cases. The reaction is faster in acetonitrile than in dichloromethane owing to the higher solubility of ozone in the former solvent. The reaction is faster on lowering the temperature because of the increase of the concentration of ozone in solution at lower temperature. With a 1:1 or a 1:2 naphthalene:ozone ratio high conversion and low selectivity for the anhydride (8) is observed.     

Hydrothermal Growth of Large Sound Crystals of Zinc Oxide

Large (10 to 20 g) macroscopically sound ZnO crystals suitable for preliminary transducer and other studies have been grown hydrothermally at rates of from 10 to 15 mils per day. The factors found to be important in achieving good growth were (1) base concentration of growth solution, (2) temperature difference between dissolving and growth regions, (3) presaturation of growth solution, (4) warm-up procedure, (5) addition of Li+ to the growth solution to suppress dendrite formation, (6) etching to remove seed damage, and (7) nutrient size. Each of the foregoing factors was studied and is discussed.     

以温度为函数的硝仿系炸药的爆发分解反应动力学参数

用爆发点试验装置测定了6种硝仿系炸药:2,2,2-三硝基乙基-N-硝基-甲胺(TNMA)、二(2,2,2-三硝基乙基-N-硝基)乙二胺(BTNEDA)、4,4,4-三硝基丁酸-2,2,2-三硝基乙酯(TNETB)、二(2,2,2-三硝基乙醇)缩甲醛(BTNF)、1,1,1,3-四硝基丙烷(TETNP)和二(2,2,2-三硝基乙基)硝胺(BTNNA)在不同温度下的爆发延滞期.依据谢苗诺夫方程lnt_(lag,i)=E_α/RT_i-lnA_α,由lnt_(lag,i)对1/T_i的关系,用作图法和最小二乘法计算了爆发分解反应的表观活化能(E_α)、指前因子(A_α)和5 s爆发点.用非线性等转化率积分法所得的表观活化能(E_α)校验了由lnt_(lag,i)～1/_Ti关系得到的Eα值.借助热力学关系式,计算了爆发分解反应的活化热力学参数[活化自由能(ΔG≠),活化焓(ΔH≠)和活化熵(ΔS≠)].结果表明: (1) E_α和作图法所得E_α间的相对误差在±5%以内; (2) E_α与最小二乘法所得E_α相等的事实佐证了不同温度下爆发分解反应延滞期内的分解深度是相等的,所得E_α和A_α值是可接受的,谢苗诺夫方程推导过程中采用A_α>>G(α)的假设是合理的; (3) 以5 s爆发点和ΔG~#为判据,6种硝仿系炸药对热抵抗能力的次序为:TNETB＞BTNF＞BTNEDA＞TETNP＞TNMA＞BTNNA.     

在大孔硅基囊泡材料孔道内原位接枝有机聚合物

以聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物（P123）为模板剂、正硅酸甲酯（TMOS）为硅源,采用水热法合成出孔径大于100 nm的硅基囊泡材料。同时采用两步法合成出带有硅烷偶联基团的有机自由基引发剂2-溴-2-甲基丙酸丁酯基三乙氧基硅烷（BPE）和2-溴-2甲基丙酸丁酯基二甲基氯硅烷（BPCM）。再利用偶联基团与囊泡材料孔道内表面的硅羟基偶联反应将自由基引发剂BPE和BPCM分别接枝到囊泡内表面,元素分析发现BPCM具有更高的接枝效率。然后在囊泡孔道内分别引发烯烃单体甲基丙烯酸甲酯（MMA）和甲基丙烯酸丁酯（BMA）的原子转移自由基聚合（ATRP）反应,使单体在表面自由基上逐一反应形成聚合物刷。透射电镜（TEM）表征结果表明,孔道内表面接枝上了聚合物后囊泡保持较为完好。通过化学方法将聚合物切割下来,凝胶渗透色谱（GPC）分析发现接枝的PMMA和PBMA的数均分子量（M_n）分别为7600和11400,分子量分布指数（PDI）均为1.25。     

全氟羧酸二价盐及全氟羧酸/三价金属盐混合体系表面活性研究

合成一系列全氟辛酸二价盐(M(PFOA)_2,M~(2+)=Mg~(2+),Ca~(2+),Sr~(2+),Ba~(2+))和全氟丁酸二价盐(M(PFBA)_2),并测定其在水、二甲基亚砜(DMSO)和乙二醇(EG)中的表面张力,同时测定了全氟辛酸(PFOA)和全氟丁酸(PFBA)分别与三价金属盐(LaCl_3和FeCl_3)组成的混合物在水溶液中的表面张力。结果表明,与相应的钾盐相比,M(PFOA)_2和M(PFBA)_2具有更高的表面活性,而全氟羧酸(PFOA或PFBA)与三价金属盐的混合物未见表面活性显著提高。M(PFOA)_2可作为降低PFOA盐使用量的重要方法加以应用。     

Effects of Organoantimony(III) Compounds of Sterically Hindered Bifunctional Tetradentate Ligands on the Reproductive System of Male Rats

The antifertility activity of organoantimony(III) complexes PhSb[RC(NC(6)H(4)S)CH(2)(NC(6)H(4)S)CR'] {R' = CH(3) (R(1)) and R = R' = CF(3) (R(2))} derived from corresponding sterically hinlered bifuinctional tetradentate ligands in the male rats was determined. The administration of compounds R(1) and R(2) at the dose level of 20 mg/kg. b. wt. siignificantly reduced the weights of testes and epididymides. Auxiliary glands showed a significant reduction after the treatment of compound R(1) only. Treated animals showed a notable depression of spermatogenesis. The preleptotene spermatocytes were decreased by 76.19 and 47.06; the secondary spermatocytes by 87.4% and 54.87337; and the step-19 spermatids by 72.9 and 46.77% respectively, following the compound R(1) and R(2) treatment. Reduced sperm count and motility resulted in 100% negative fertility in both the treated groups. A significant fall in the content of various biochemical parameters of eproductive tissues was observed after R(1) and R(2) treatment in comparison to controls.     

Effects of processing on quality of soybean oil

The fate of major and minor components of soybean oil is examined at each stage of processing. Relationships are then drawn upon the effect on the quality of finished oil. General topics covered are (a) triglycerides and polyunsaturated fatty acids, (b) free fatty acids, (c) mono- and diglycerides, (d) phospholipids, (e) minor constituents, such as tocopherols, color bodies, and metal ions, (f) rearrangement and decomposition products, (g) foreign or toxic compounds not native to soya and (h) other additives, such as refining aids.     

碳包覆对LiNi_(0.5)Mn_(1.5)O_4电化学性能的影响

以蔗糖为碳源,采用溶液沉积-真空热解法制备了LiNi_(0.5)Mn_(1.5)O_4/C复合材料。用热重与差热分析、X射线衍射分析、扫描电镜分析及电化学测试等手段对LiNi_(0.5)Mn_(1.5)O_4/C的微观结构、表面形貌和电化学性能进行了研究。结果表明,蔗糖热分解后在LiNi_(0.5)Mn_(1.5)O_4颗粒的表面包覆形成了一层无定形碳。无定形碳可以有效阻止LiNi_(0.5)Mn_(1.5)O_4颗粒的聚集,增加电极的导电面积,降低电池极化,从而改善LiNi_(0.5)Mn_(1.5)O_4的电化学性能。与未包覆的LiNi_(0.5)Mn_(1.5)O_4粉末相比,LiNi_(0.5)Mn_(1.5)O_4/C复合材料具有更高的可逆容量、更稳定的循环性能和更好的倍率性能。0.2C放电时,LiNi_(0.5)Mn_(1.5)O_4/C复合材料的首次放电容量达到144.8mA.h.g-1,经60次循环后平均每次循环的容量损失仅为0.0081%。而1.0C和2.0C放电时,LiNi_(0.5)Mn_(1.5)O_4/C复合材料的首次放电容量分别保持在131.9mA.h.g-1和122.4mA.h.g-1。     

Antioxidant Activities of Fractions of Polymeric Procyanidins from Stem Bark of Acacia confusa

The polymeric procyanidins extracted from Acacia confusa stem bark were fractionated with a step gradient of water, methanol and acetone on a Sephadex LH-20 column. The antioxidant activity of the collected fractions was investigated by the 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging and ferric reducing/antioxidant power (FRAP) assays. All fractions possessed potent antioxidant activity with the highest activity observed for fraction F9. The matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and reversed-phase high performance liquid chromatography (RP-HPLC) analyses suggested that the collected fractions consisted primarily of oligomeric and polymeric procyanidins, with different polymer ranges and most abundant polymer size. For each fraction, catechin and epicatechin were present as both terminal and extension units, and epicatechin was the major component in the extended chain. The mean degree of polymerization (mDP) of each fraction differed, ranging from 1.68 (fraction F2) to 17.31 (fraction F11). There was a relationship between antioxidant activity (IC50/DPPH and FRAP) and mDP (R(2) (DPPH) = 0.861, P = 0.006 and R(2) (FRAP) = 0.608, P = 0.038), respectively. However, the highest antioxidant activity of fraction (F9) was not coincident with the maximum mDP of fraction (F11).     

Effects of urea on the microstructure and phase behavior of aqueous solutions of polyoxyethylene surfactants

Membrane proteins are made soluble in aqueous buffers by the addition of various surfactants (detergents) to form so-called protein-detergent complexes (PDCs). Properties of membrane proteins are commonly assessed by unfolding the protein in the presence of surfactant in a buffer solution by adding urea. The stability of the protein under these conditions is then monitored by biophysical methods such as fluorescence or circular dichroism spectroscopy. Often overlooked in these experiments is the effect of urea on the phase behavior and micellar microstructure of the different surfactants used to form the PDCs. Here the effect of urea on five polyoxyethylene surfactants - n-octylytetraoxyethylene (C(8)E(4)), n-octylpentaoxyethylene (C(8)E(5)), n-decylhexaoxyethylene (C(10)E(6)), n-dodecylhexaoxyethylene (C(12)E(6)) and n-dodecyloctaoxylethylene (C(12)E(8)) - is explored. The presence of urea increases the critical micelle concentration (CMC) of all surfactants studied, indicating that the concentration of both the surfactant and urea should be considered in membrane protein folding studies. The cloud point temperature of all surfactants studied also increases with increasing urea concentration. Small-angle neutron scattering shows a urea-induced transition from an elongated to a globular shape for micelles of C(8)E(4) and C(12)E(6). In contrast, C(8)E(5) and C(12)E(8) form more globular micelles at room temperature and the micelles remain globular as the urea concentration is increased. The effects of increasing urea concentration on micelle structure are analogous to those of decreasing the temperature. The large changes in micelle structure observed here could also affect membrane protein unfolding studies by changing the structure of the PDC.     

Synthetic potential of molluscan sulfatases for the library synthesis of regioselectively O-sulfonated D-galacto-sugars

The substrate specificities of three molluscan sulfatases (E.C. 3.1.6.1; snail, abalone, and limpet origins) were investigated with assorted p-nitrophenyl (pNP) di-O-sulfonated beta-D-galactopyranosides and beta-lactosides [3,6-SO(3) Gal (1), 3',6'-SO(3) Lac (2), 4, 6SO(3) Gal (3), 2,6-SO(3) Gal (4), 3,4-SO(3) Gal (5), and 3,6-SO(3) GalNAc (6); Ac, acetyl; Gal, galactose; Lac, lactose] together with mono-O-sulfonated beta-D-galactopyranoside [pNP 3SO(3)-Gal (7)] and tri-O-sulfonated alpha-D-galactopyranoside [2,3,6-SO(3)-alpha-Gal (11)]. Some notable differences between the substrate specificity of the three sulfatases were disclosed; snail sulfatase hydrolyzed the 3O- and 2O-sulfo groups of 1 and 4, respectively, to afford 6SO(3) Gal (9) in high yields, while the abalone enzyme did not act on 4. Only the limpet enzyme could cleave the 3O-sulfo groups of 7 to give pNP beta-galactoside. In contrast, every enzyme could utilize 11 as a good substrate to afford a mixture of 6SO(3)-alpha-Gal (13) and 2,6-SO(3) alpha-Gal (12). None of the enzymes could cleave the O-sulfo groups of 5 and 6, which indicates that a primary 6O-sulfo group tends to promote the enzymatic hydrolysis of O-sulfo groups at the secondary positions.     

4-羟基吡啶等电点和离解常数的测定

两种4-羟基吡啶(HP)的盐酸盐:HP.HCl(A)和(HP)2.HCl.H2O(B)具有不同的晶体结构,但在水溶液中它们应该是同样的HP共轭酸碱体系。为了得到HP合成工艺中需要的等电点(I)和离解常数Ka1两项参数和有必要证明在水溶液中(A)和(B)是同样的共轭酸碱体系,用pH计测定的酸碱滴定法,测定了HP的等电点(I)和离解常数Ka1,证明(A)和(B)是同样的共轭酸碱体系,并对上述参数进行了不确定度评定。     

雄甾烯酮~(13)CNMR谱化学位移的QSSR研究

用原子电性距离矢量(atom ic electronegativity d istance vector,AEDV)和原子杂化状态指数(atom ic hybrid i-zation state index,AHSI)对13个雄甾烯酮化合物中247个碳原子进行了结构表征,并与其核磁共振碳谱(13CNMR)建立了多元线性定量构谱相关(QSSR)模型;运用逐步回归结合统计检测,对模型变量进行了筛选,建模计算值、留一法(leave-one-out,LOO)交互校验(cross-validation,CV)预测值和留分法(leave-molecu le-out,LMO)交互校验预测值的复相关系数(R)分别为0.989 6,0.989 1和0.989 4。结果表明:AEDV,AHSI与13CNMR谱化学位移显著相关。     

A Comparative Study of the Potent Odorants of Different Virgin Olive Oils

The flavour of virgin olive oil was investigated by means of an aroma extract dilution analysis. A comparative study of four oil samples differing in the flavour, indicated that the following odorants were mainly responsible for the odour notes given in brackets: (Z)-3-hexenol, hexanal, (E)-2-hexenal and (Z)-3-hexenal (green), ethyl 2-methylbutyrate, (Z)-3-hexenyl acetate and ethyl cyclohexanoate (fruity), (E,E)-2,4-decadienal, (E)- and (Z)-2-nonenal (fatty) and 4-methoxy-2-methyl-2-butanethiol (black currant-like).     

Insights into the mode of action of the anti-Candida activity of 1,10-phenanthroline and its metal chelates

Metal complexes of malonie acid (metal = Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Ag(I)) were prepared and only the Ag(I) complex inhibited the growth of Candida albicans. Malonate complexes incorporating the chelating 1,10-phenanthroline (1,10-phen) ligand showed a range of activities: good (Mn(II), Cu(II), Ag(I)); moderate (Zn(II)); poor (Co(II), Ni(II)). Metal-free 1,10-phen and Ag(CH(3)CO(2)) were also highly active. The metal-free non-chelating ligands 1,7- phenanthroline and 4,7-phenanthroline were inactive and the Cu(II), Mn(II) and Zn(II) complexs of 1,7-phen displayed only marginal activity. Whereas the Cu(II) malonate/1,10-phen complex induces significant cellular oxidative stress the Zn(II) analogue does not.