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。     

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。     

Structural studies of the Maillard reaction products of a protein using ion trap mass spectrometry

The early stage products of the Maillard reaction of egg white lysozyme with D-glucose were studied. Incubation with D-glucose at 50 degrees C for 20 days caused reaction on the Lys and Arg residues of lysozyme as follows: all of the six Lys residues and 10 of the 11 Arg residues in lysozyme reacted with D-glucose; Arg 61 did not react with D-glucose. The Lys residues reacted with D-glucose with 1 mol of dehydration per mole of residue, and the Arg residues reacted with 2 mol of dehydration per mole of residue. The major constituent of the Amadori product with the epsilon-amino group of the Lys residue and the D-glucose was found to be the beta-pyranose form. The structure of the early stage product of the Maillard reaction of a protein with a sugar is the same as that of an amino acid with a sugar.     

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%.     

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.     

四环素-铜(Ⅱ)配合物与DNA相互作用的吸收光谱研究

用紫外光谱方法研究了四环素(TC) Cu(II)配合物与DNA的相互作用.吸收光谱研究表明,DNA能与四环素(TC)及Cu(II)形成的配合物发生反应,配合物与DNA的作用方式随着配合物类型及DNA浓度的不同而不尽相同:当四环素与铜形成1∶1型配合物时,较低浓度的DNA能与配合物以嵌插方式相互作用,而较高浓度的DNA与该配合物除了发生嵌插作用外,还存在另外的作用方式;当四环素与铜形成1∶2型配合物时,DNA与该配合物则主要以嵌插方式相互作用,并且这两种配合物与DNA的嵌插作用均是通过四环素配体插入的.     

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.     

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.     

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.     

Steric effects in the aerobic oxidation of pi-allylnickel(II) complexes with N-heterocyclic carbenes

Pi-allylchloro(NHC)nickel(II) complexes were synthesized and their reactions with O2 were studied. Ligand steric effects were found to determine the difference between rapid oxidation of the allyl group to produce bis-mu-hydroxonickel complexes and no observable reaction. The ability of the metal-NHC bond to rotate correlates with the ability of the complex to react with O2. In the limiting cases, conformationally restricted complexes are stable to O2 and complexes with rapid Ni-NHC bond rotation react rapidly with O2. Complexes with intermediate conformational flexibility were found to exhibit lesser reactivity with O2. On the basis of the observed inertness of complexes with saddle-shaped ligands to O2, we propose the adoption of a nonplanar geometry upon reaction with O2 to be required. The issue of conformational flexibility versus rigidity is expected to directly impact the catalytic behavior of metal-NHC complexes.     

The first density functional study on the

The hetero-Diels-Alder reactions of 1,2-diaza-1,3-butadiene with ethylene, methyl vinyl ether, and methyl acrylate have been investigated theoretically with the aid of density functional theory using the Becke3LYP/6-31G(d) computational level. In the reactions with substituted alkenes, the transition states are concerted but asynchronous; the shortest bond-forming distance involves the nonsubstituted carbon of the alkene. In agreement with the experimental results, the reaction with methyl vinyl ether proceeds with high endo stereoselectivity and with complete regioselectivity to form the 6-methoxy cycloadduct. The conformational study of the transition states shows a sharp s-trans preference. In contrast, the [4 + 2]-cycloaddition of 1,2-diaza-1,3-butadiene with methyl acrylate have been found to occur with low regio- and stereoselectivity but with a s-cis preference in the transition structures.     

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.     

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.     

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.     

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.     

卤代苯与水分子间作用的从头算

污染是科学家关注的热点问题,化学污染物是造成水污染的重要因素［１］．在水环境中,卤代苯是一类优先污染物（ｐｒｉｏｒｉｔｙｐｏｌｕｔａｎｔｓ）［２］．这类污染物毒性大,在环境中的半衰期长,美国环保局（ＥＰＡ）已经把它们列入优先污染物之列．Ｖｅｒｓｃｈｎ...     

Catalytic effect of copper on the hexacyanoferrate(III)-cyanide redox reaction-I The uncatalysed and catalysed reactions

A kinetic study of the hexacyanoferrate(III)-cyanide redox reaction has been made in connection with development of a new catalytic method for copper. The reaction kinetics change with time from first- to second-order dependence with respect to hexacyanoferrate(III). The reaction is nearly inverse first-order with respect to hexacyanoferrate(II) and first-order with respect to cyanide. The reaction shows a strong positive primary salt effect, but a very small increase in the reaction rate with temperature is found. A parallel reaction proceeds with a first-order dependence with respect to hydroxide. A tentative mechanism is proposed for the first reaction, involving the formation of cyanogen radicals. The second reaction corresponds to the well-known decomposition of hexacyanoferrate(III) in alkaline medium. The catalysed reaction exhibits similar kinetics with respect to hexacyanoferrate(II) and (III) but is zero-order with respect to cyanide and hydroxide and first-order with respect to catalyst. The proposed mechanism involves two consecutive interactions of the hexacyanoferrate(III) with copper(I) and with copper(II) cyanide complexes respectively, followed by a 2-electron oxidation of a co-ordinatively bridging cyanide group.     

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.     

Reaction of arylsulfonylhydrazones of aldehydes with alpha-magnesio sulfones. A novel olefin synthesis

Reactions of representative tosylhydrazones of aldehydes and ketones with alpha-metalated sulfones were examined in order to develop a practical olefination method. Treatment of aldehyde tosylhydrazone 2 with an excess of alpha-lithiated methyl phenyl or dimethyl sulfones yielded 3a. The reaction of 2 with sterically unhindered lithiated alkyl sulfones gave mixtures of the respective olefination products 3b-d along with the Shapiro fragmentation product 4. Sterically hindered lithiated sulfones afforded Shapiro products exclusively. In contrast, aldehyde tosylhydrazones 2 or 6 in reactions with a variety of alpha-magnesio primary or secondary alkyl sulfones gave olefination products 3a-j and 7a-c in high yields (Tables 1 and 2). beta-Branched alkyl sulfones afforded predominantly (E)-alkenes, whereas unhindered primary sulfones gave mixtures of (E)- and (Z)-alkenes with low selectivity. Reaction of the 2,4,6-triisopropylbenzenesulfonylhydrazone (trisylhydrazone) of cyclodecanone 11c with alpha-magnesio methyl phenyl sulfone afforded the methylidene derivative 12a contaminated with the Shapiro product 13. Tosylhydrazone 2 resisted reaction with i-PrMgCl and gave only a small amount of the addition product in reaction with Bu(2)Mg. Some mechanistic aspects of the reaction of tosylhydrazones with organomagnesium compounds are discussed.