金蒲抑瘤片在鼻咽癌的临床应用研究

为探讨鼻咽癌患者放疗期间合并应用金蒲抑瘤片治疗对细胞免疫功能及血中微量元素硒、锌、铜的影响，经病理证实鼻咽癌患者58例，随机分为放疗服药组30例和单纯放疗组28例。两组放疗前后抽静脉血测定T细胞亚群（CD3＋，CD4＋，CD8＋，CD4＋／CD8＋），血中微量元素硒，锌，铜并与30例健康者（正常对照组）进行比较。结果表明，鼻咽癌患者血中微量元素硒，锌，铜及CD3＋，CD4＋，CD4＋／CD8＋显著低于健康人，放疗期间合并应用金蒲抑瘤片治疗后血中微量元素硒，锌，铜及CD3＋，CD4＋，CD4＋／CD8＋较服药前显著升高。提示鼻咽癌患者细胞免疫功能低下，血中微量元素硒，锌，铜显著低于健康人。金蒲抑瘤片能提高鼻咽癌患者因中微量元素硒，锌，铜含量，使低下的细胞免疫功能迅速恢复。     

Photoaddition of ketones to imidazoles,thiazoles, isothiazoles and isoxazoles. Synthesis of their oxetanes

Imidazole itself did not undergo photoaddition reactions with ketones. However, irradiation of 1-acetyl and 1-benzoylimidazole, and 1,1-carbonyldiimidazole with benzophenone yielded oxetanes. On irradiation with carbonyl compounds, 1,2-dimethylimidazole and 1-benzylimidazole did not give oxetanes but a hydroxyaryl or hydroxyalkyl derivative. Thiazole itself did not yield any photoaddition product, but 2,4-dimethylthiazole afforded oxetanes on irradiation with benzophenone and with 3-benzoylpyridine. Irradiation of 2,4-dimethylthiazole with acetophenone led to the formation of a dimeric material. On irradiation with benzophenone, 4-methylisothiazole did not yield an oxetane but rather a hydroxyphenyl derivative. 3,5-Dimethylisoxazole on irradiation with benzophenone and with 3-benzoylpyridine gave oxetanes. Irradiation of 4,5-dimethylisoxazole yielded similarly an oxetane with benzophenone     

乳腺癌术前灰阶超声与彩色多普勒超声联合应用对预后的预测价值

目的探究乳腺癌术前灰阶超声与彩色多普勒超声联合应用对预后的预测价值。方法选取温州医科大学附属第一医院2013年5月—2015年5月期间收治的乳腺癌患者83例,治疗前均行灰阶超声与彩色多普勒超声检查,分析患者超声检查结果、临床征象与术后随访2年期间患者预后的关系,从而分析术前灰阶超声与彩色多普勒超声联合应用对乳腺癌患者预后的预测价值。结果乳腺癌肿块边界清晰、边界不清晰、边界恶性晕的患者2年无瘤生存率依次降低,边界恶性晕与边界不清晰患者死亡率均显著高于边界清晰患者(P0.05);肿瘤≥2 cm患者2年无瘤生存率显著低于2 cm患者;淋巴结转移患者2年无瘤生存率显著低于无转移患者(P0.05);血流分级Ⅱ级患者2年无瘤生存率明显低于0级(P0.05),Ⅲ级患者2年无瘤生存率显著低于0级和Ⅰ级(P0.05)。结论乳腺癌患者术前联合应用灰阶超声与彩色多普勒超声检查可确定肿瘤边界、大小及淋巴转移等征象,其与患者无瘤生存率、死亡率等预后指标密切相关,可作为预测乳腺癌患者预后的重要方法。     

合成聚芳酯树状分子的新方法

以３，５－二羟基 苯甲酸为起始原料，经甲醇酯化保护羧基，与苯甲酰氯反应，得到３，５－二苯甲酰氧基苯甲酸甲酯用ＡｌＣｌ３．ＮａＩ去掉保护基甲基，以高收率得到３，５－二苯甲酰氧基苯甲酸。其结构均是由ＩＲ，＾１ＨＮＭＲ，ＥＡ等方法证实。     

Aryl- and alkenyllithium preparations and copper-catalyzed reaction between the derived magnesium reagents and the monoacetate of 4-cyclopentene-1,3-diol

[reaction: see text] Aryl- and alkenyllithiums, prepared by halogen-lithium exchange with lithium, exchange with n-(or t-)BuLi, stannane-lithium exchange with n-BuLi, and direct lithiation with n-BuLi, were transformed into magnesium reagents with MgCl2 and subjected to CuCN-catalyzed reaction with the title monoacetate. Except for the halogen-lithium exchange with n-BuLi, the other preparations of the lithium anions were found to be compatible with the CuCN-catalyzed reaction to afford S(N)2-type products efficiently.     

N-去甲万古霉素的亲和吸附

通过交联聚丙烯酸甲酯与乙醇胺反应,形成聚(N-羟乙基丙烯酰胺)树脂,在酸催化作用下与环氧氯丙烷反应,形成含有α-羟基氯乙基的树脂.含α-羟基氯乙基的树脂与D-丙氨酸、L-丙氨酸或甘氨酸反应,分别得到含有这3种氨基酸的吸附剂.这3种吸附剂吸附N-去甲万古霉素的结果表明,含D-丙氨酸的吸附剂的吸附量最大,含甘氨酸的吸附剂的吸附量次之,而含L-丙氨酸的吸附剂不吸附N-去万古霉素.说明前两种吸附剂对N-去甲万古霉素存在亲和吸附作用.含D-丙氨酸吸附剂的最佳吸附pH值为5.8,当吸附液中的盐(NaCl)浓度增加时,吸附量降低.用0.4mol/LNa₂CO₃/CH₃CN(摩尔比7∶3,pH=9.5)作为洗脱剂可完全脱附被吸附的N-去甲万古霉素.     

Extraction behaviour of uranium,zirconium and ruthenium with gamma-irradiated sulfoxides and tri-n-butyl phosphate

The extraction, scrubbing and stripping behaviour of uranium, zirconium and ruthenium with di-n-hexyl and di-n-octyl sulfoxides in Solvesso-100 and tri-n-butyl phosphate (TBP) in shell Sol-T irradiated by various gamma doses (0–169 Mrads) have been investigated. 2M HNO₃ was used for extraction and scrubbing and 0.01M HNO₃ for stripping purposes. Results indicate that the extraction of uranium with TBP increases and that with sulfoxide decreases with dose. This is reflected in their corresponding scrubbing percentages too. The stripping percentage of uranium with TBP decreases with dose while the reverse is the case with sulfoxide. The extraction of zirconium with TBP increases sharply with dose as compared to sulfoxides. The extraction scrubbing and stripping of ruthenium remain almost unaffected by dose both in the case of TBP and sulfoxides. These results lead to much higher overall decontamination factors for uranium with respect to zirconium as well as ruthenium with irradiated sulfoxides as compared to those with irradiated TBP.     

Reaction features of 2,3,4-trichloro-1-butene with phosphoric and nitrogen nucleophiles

Reaction of 2,3,4-trichloro-1-butene with phosphoric and nitrogen nucleophiles was carried out. In the reaction with allyldiphenylphosphine 1,4-bis-(allyldiphenylphosphoniochlorido)-1,3-butadiene was obtained, with tributylphosphine, allyldimethylamine and trimethylamine respective 1,4-bis-onium salts with 2-chloro-2-butenylene group. Reaction with trimethylamine proceeded with formation of monoammonium salt with 3,4-dichloro-2-butenyl group. It is noteworthy that 1,4-splitting of 1,4-bis-(trimethylammoniochlorido)-2-butene at the action of sodium methoxide occurs with involvement of the less labile hydrogen atom.     

Synthesis of branched copolysilanes from trichlorosilanes

Soluble polymers and copolymers have been prepared from monosubstituted trichlorosilanes via thermal reductive coupling with sodium in toluene. Phenyltrichlorosilane has been copolymerized with methylphenyl dichlorosilane, with n-hexyltrichlorosilane, with tetrachlorosilane and with tetrakis(chlorodimethylsilyl)silane. n-Hexyltrichlorosilane has been copolymerized with methylphenyldichlorosilane, with phenyltrichlorosilane and with silicon tetrachloride. Soluble polymers and copolymers with molecular weight in the range ≈ 2,000 to ≈ 10⁶ have been obtained. The absorption and emission spectra of the resulting polymers are strongly affected by the presence of trisilyl- and tetrasilylsubstituted silicon atoms. © 1995 John Wiley & Sons, Inc.     

Fluorometric assay of ultramicro quantities of glucose with somogyi filtrate and hexokinase

A procedure is described for the determination of glucose in 3 μl of serum or plasma. It is based on the phosphorylation of glucose with ATP mediated by hexokinase. The TPNH generated with glucose-6-phosphate dehydrogenase is measured fluorometrically.Sensitivity is greatly improved over the corresponding procedure using UV absorption for the determination of NADPH. Bilirubin does not interfere. Interference from hemolysis is eliminated by precipitation with Zn(OH)₂ Blood taken with fluoride can be utilized. Fluoride interference is removed with the Zn(OH)₂ and with excess Mg in the substrate. Positive interference by fructose is negligible with some enzyme preparations but is appreciable with others.The results correlate well with those obtained with an ortho toluidine method, after protein precipitation with trichloroacetic acid. The method is especially useful in the Pediatric Laboratory.     

Effective 1,5-, 1,6- and 1,7-remote stereocontrol in reactions of alkoxy- and hydroxy-substituted allylstannanes with aldehydes

Alk-2-enylstannanes with 4-, 5- and 6-alkoxy- or -hydroxy-substituents are transmetallated stereoselectively with tin(iv) halides to generate allyltin trihalides which react with aldehydes to give (Z)-alk-3-enols with useful levels of 1,5-, 1,6- and 1,7-stereocontrol. Alk-2-enylstannanes with a stereogenic centre bearing a hydroxy or alkoxy group at the 4-, 5- or 6-position, react with overall (Z)-1,5-, 1,6- and 1,7-syn-stereoselectivity with respect to the hydroxy and alkoxy substituents. The analogous reactions of alkoxy- and -hydroxyalk-2-enylstannanes with a methyl bearing stereogenic centre at the 4- or 5-position react with overall (Z)-1,5- and 1,6-anti-stereoselectivity with respect to the hydroxy and methyl substituents.     

Monte Carlo simulations of systems of rodlike molecules with semiflexible terminal groups

The results of Monte Carlo simulations of systems of rodlike molecules with semiflexible terminal groups are compared with those of systems with terminal groups at a fixed angle τ with respect to the rigid core and with those of a system containing the rigid cores alone in the same total volume. The nematic/isotropic transition temperature decreases with increasing flexibility or with increasing τ. For semiflexible groups, the transition is coupled with a conformational change favouring more extended conformations in the nematic phase. The results of the simulations are discussed in connection with those obtained for similar models in the recent literature and with the predictions of the Maier‐Saupe and Flory‐Ronca‐Irvine theories.     

Comparison of electrothermal atomization diode laser Zeeman- and wavelength-modulated atomic absorption and coherent forward scattering spectrometry

Atomic absorption and coherent forward scattering spectrometry by using a near-infrared diode laser with and without Zeeman and wavelength modulation were carried out with graphite furnace electrothermal atomization. Analytical curves and limits of detection were compared. The magnetic field was modulated with 50 Hz, and the wavelength of the diode laser with 10 kHz. Coherent forward scattering was measured with crossed and slightly uncrossed polarizers. The results show that the detection limits of atomic absorption spectrometry are roughly the same as those of coherent forward scattering spectrometry with crossed polarizers. According to the theory with bright flicker noise limited laser sources the detection limits and linear ranges obtained with coherent forward scattering spectrometry with slightly uncrossed polarizers are significantly better than those obtained with crossed polarizers and with atomic absorption spectrometry. This is due to the fact that employing approaches of polarization spectroscopy reduce laser intensity fluctuations to their signal carried fractions.     

Influence of substituents on selectivity and efficiency of chiral separations of anions containing single nido-7,8-dicarbaundecaborane cluster with alpha-cyclodextrin

In background electrolyte (BGE) with the optimal methanol concentration of 30% (v/v), the ion with -NCS group bonded to a cluster boron atom exhibits the strongest interaction with alpha-cyclodextrin and the highest separation selectivity. Interaction of ions with alkyl or thioalkyl group weakens with the increasing substituent size. The ion with phenyl group exhibits the weakest interaction. Bonding of a group to boron atom weakens the ion interaction with alpha-cyclodextrin. Second substituent further weakens the interaction with alpha-cyclodextrin. Separation efficiency is lower at the presence of alpha-cyclodextrin than at its absence. This separation efficiency loss, amounts up to 90%.     

表面等离子体子共振传感器用于研究不同材质包裹的磁性纳米粒子性质

利用自行设计组装的以白色发光二极管为光源的表面等离子体子共振传感器实验装置, 检测了不同材质包裹的磁性纳米粒子连接靶向DNA与生物素化DNA探针的结合程度. 结果表明, 与聚苯乙烯磁性微球连接的靶向DNA相比, Fe3O4@SiO2核壳式纳米微球连接的靶向DNA与生物素化的DNA探针结合速率较快, 且其相对标准偏差较小.     

Chemistry of N-Boc-N-tert-butylthiomethyl-protected alpha-aminoorganostannanes: diastereoselective synthesis of primary beta-amino alcohols from alpha-aminoorganostannanes

Reaction of N-Boc-N-tert-butylthiomethyl-protected alpha-aminoorganostannanes with n-BuLi generates the corresponding alpha-aminoorganolithiums. Reactions of these organolithiums with aromatic aldehydes provides N-protected beta-amino alcohols with diastereoselectivities up to >99:1 anti/syn; with aliphatic aldehydes, diastereoselectivities were typically 1:1. Diastereoselectivities varied depending on the amount of aldehyde used. The N-protected beta-amino alcohols could be deprotected to primary amines by treatment with NaH to generate oxazolidinones followed by basic hydrolysis. Alternatively, treatment of the protected amino alcohols with acid furnished cyclic acetals that could be deprotected to primary amines with BF(3).OEt(2) and HS(CH(2))(3)SH. Transmetalation of enantiomerically enriched organostannanes with n-BuLi at -95 degrees C provided organolithiums that, although less configurationally stable than N-Boc-N-methyl-protected alpha-aminoorganolithiums, could be trapped with aldehydes with near-complete retention of configuration.     

Hydrosilylation reactions catalyzed by rhodium complexes with phosphine ligands functionalized with imidazolium salts

Hydrosilylation reactions of styrene with triethoxysilane catalyzed by rhodium complexes with phosphine ligands functionalized with imidazolium salts are reported. In comparison with Wilkinson’s catalyst, Rh(PPh₃)₃Cl, all of the present rhodium complexes with phosphines functionalized with imidazolium salts exhibit higher catalytic activity and selectivity.     

Effectiveness of universal pre-enrichment broth for recovery of Salmonella from selected dairy foods

The relative efficiencies of 2 Bacteriological Analytical Manual (BAM) pre-enrichments, lactose broth (LAC) and brilliant green water (BGW), were compared with Universal Pre-enrichment (UP) broth for the recovery of individual Salmonella serovars from instant nonfat dry milk (NFDM), dry whole milk (DWM), lactic casein (LC), and liquid whole milk (LWM). BGW was compared with UP broth for the analysis of NFDM and DWM but not with the other 2 matrixes. LAC was compared with UP broth for the analysis of LC and LWM. UP broth was made both from a commercial dehydrated preparation (UPC) and from individual ingredients (UPI). Bulk quantities of the selected dairy foods were inoculated with Salmonella serovars at levels intended to produce fractionally positive results, where at least half of the test portions analyzed, with one of the methods being evaluated, would be shown to be Salmonella-positive. For NFDM, in 6 of 9 experiments, with 2 different Salmonella serovars, BGW was significantly more productive than either UPI or UPC broth (p < 0.05). Salmonella was recovered from 118 of 180 test portions with BGW, from 25 of 180 test portions with UPC, and from 14 of 180 test portions with UPI. For DWM, in 2 of 4 experiments, with 2 different Salmonella serovars, BGW was significantly more productive than either UPI or UPC broth (p < 0.05). Salmonella was recovered from 67 of 80 test portions with BGW, from 36 of 80 test portions with UPC, and from 37 of 80 test portions with UPI. For LWM, in 9 of 9 experiments, with 3 different Salmonella serovars, there were no significant differences among the broths. Salmonella was recovered from 120 of 180 test portions with LAC, from 135 of 180 test portions with UPC, and from 129 of 180 test portions with UPI. For LC, in 5 of 7 experiments, with 2 different Salmonella serovars, both UPI and UPC broth were significantly more productive than LAC (p < 0.05). Salmonella was recovered from 42 of 140 test portions with LAC, from 114 of 140 test portions with UPC, and from 114 of 140 test portions with UPI. In addition, overall results showed that UPC and UPI broths were equivalent for the recovery of Salmonella from the foods tested, without regard to their performance in comparison with either LAC or BGW.     

Modification of supercapacitor electrodes with polymer metallocomplexes: Methods and results

A procedure for electrochemical modification of carbon materials with high specific surface was developed. The materials were modified with polymeric nickel complexes with Schiff bases. The prototype of a hybrid double-layer Faraday supercapacitor with a positive carbon electrode modified with a polymeric complex was studied. Modification of this type doubled the energy stored by the hybrid capacitor compared with the similar double-layer capacitor.     

Polymerization of allyl(vinyl phenyl) ethers and reactions of the resulting polymers

Solution polymerizations of allyl(o-vinyl phenyl)ether and allyl(p-vinyl phenyl)ether with cationic and radical initiators were investigated. Soluble polymers were formed in polymerizations with boron trifluoride etherate and with benzoyl peroxide. In polymerization with azobisisobutyronitrile the polymerization in dilute solution gave a soluble polymer, whereas that in concentrated solution gave a crosslinked, insoluble one. For informationon the polymerization behavior some infrared and ultraviolet spectroscopic investigations of the soluble polymers were made. From these results it appears that polymers with pendant allyl groups are formed in polymerization with boron trifluoride etherate at low temperature, and polymers containing pendant vinyl groups and allyl groups are obtained with the two types of radical initiator. Copolymerizations of these monomers with ethyl vinyl ether and styrene with the use of boron trifluoride etherate were sucessfully effected. Such reactions as Claisen rearrangement, crosslinking induced with radical initiators, and epoxidation with perbenzoic acid were examined for the polymers prepared in the polymerization with boron trifluoride etherate. Good results were obtained for the former two reactions. However, the latter was unsuccessful.