毛细管电泳-单链构象多态性分析检测K-ras基因突变

K ras癌基因的点突变在结直肠癌的发生起重要作用。以异丙醇为聚合反应链转移剂,水相法合成 特性粘度为0.70×10-3m3/kg,分子量为6.5×104的低粘度短链线性聚丙烯酰胺。以6%线性聚丙烯酰胺为 筛分介质,分离温度27℃,分离电压9kV为电泳条件,建立了检测K ras基因突变的毛细管电泳 单链构象多 态性方法。利用该方法检测36例结直肠癌患者肿瘤组织,发现12例K ras基因突变。结果表明:该方法具有 快速、高灵敏的优点,为大规模进行结直肠肿瘤的早期诊断提供了可靠方法。     

Charge-discharge Behavior of Surface-coated LiMn2O3.95F0.05 Cathode Materials at High Temperature

With inorganic salts such as LiNO3, Li2CO3, surface-coated LiMn2O3.95F0.05 were prepared by melt-impregnation method. When these surface-coated LiMn2O3.95F0.05 were used as cathode materials, their charge-discharge characters were carefully compared. As a result, they exhibited good charge-discharge properties at 50℃ high temperature. Especially, LiNO3 surface-coated LiMn2O3.9F50.05 retained nearly 80% initial reversible capacity after 130 cycles at 50℃.     

Analysis of tamoxifen and its metabolites in synthetic gastric fluid digests and urine samples using high-performance liquid chromatography with electrospray mass spectrometry

We report on the transformation of tamoxifen at 37 degrees C in synthetic gastric fluid as studied by high-performance liquid chromatography with triple quadrupole mass spectrometry. The major transformation products detected were (E)-isomer of tamoxifen, metabolite D, and several unidentified components having m/z 404. Addition of pepsin to the gastric fluid inhibited formation of all of these products. We analyzed several urine samples from breast cancer patients undergoing tamoxifen treatment. Metabolite D was identified in the urine samples and in the gastric fluid digest at a retention time of 22.0 min eluting from a reversed-phase HPLC column. Although several metabolites were found in all the urine samples of patients, some metabolites were detected in one sample but not others, suggesting tamoxifen metabolism varies in patients.     

镉（Ⅱ）—4—甲醛基重氮氨基偶氮苯显色反应的研究

本文研究了Cd(Ⅱ)与4-甲醛基重氮氨基偶氮苯的显色反应。试验结果表明:在TritonX-100的存在下,pH9.50的Na_2B_4O_7-NaOH缓冲体系中,显色反应的灵敏度高,络合物的最大吸收峰在525nm处,表观摩尔吸光系数为1.33×10~5L·mol~(-1)·cm~(-1),Cd(Ⅱ)浓度在0～10μg/25ml范围内符合比耳定律。利用阴离子交换树脂(717)小柱分离干扰离子后,测定地质试样中微量镉,结果满意。     

A new type of noncovalent surface–π stacking interaction occurring on peroxide-modified titania nanosheets driven by vertical π-state polarization

Noncovalent π stacking of aromatic molecules is a universal form of noncovalent interactions normally occurring on planar structures (such as aromatic molecules and graphene) based on sp²-hybridized atoms. Here we reveal a new type of noncovalent surface–π stacking unusually occurring between aromatic groups and peroxide-modified titania (PMT) nanosheets, which can drive versatile aromatic adsorptions. We experimentally explore the underlying electronic-level origin by probing the perturbed changes of unoccupied Ti 3d states with near-edge X-ray absorption fine structures (NEXAFS), and find that aromatic groups can vertically attract π electrons in the surface peroxo-Ti states and increase their delocalization regions. Our discovery updates the concept of noncovalent π-stacking interactions by extending the substrates from carbon-based structures to a transition metal oxide, and presents an approach to exploit the surface chemistry of nanomaterials based on noncovalent interactions.

A new type of noncovalent surface–π stacking interaction occurring on a transition metal oxide, titania, is reported, which is different from the traditional forms on sp²-hybridized planar structures like graphene.     

C12-s-C12•2Br和C12En混合水溶液的胶团化行为

季铵盐二聚表面活性剂C12 s C12•2Br（s=2、3、4、6）和非离子表面活性剂C12E10或C12E23在水溶液中生成混合胶团.其临界胶团总浓度cmcT值介于二元复配体系中各组分的临界胶团浓度和之间.当添加少量非离子型表面活性剂（在水溶液中的摩尔分数α2=0.1）时,混合胶团中C12E10或C12E23的摩尔分数均已超过0.35;随着溶液中非离子型表面活性剂含量的增大,混合胶团中逐渐以C12E10或C12E23成分为主.     

镓(Ⅲ)-茜素红体系的吸附伏安法

本文对镓(Ⅲ)与茜素红络合物在悬汞电极上的吸附伏安法作了研究,确定了电极过程.在HAc-NH_4Ac(pH4.06)缓冲溶液中茜素红存在下,用1.5阶微分吸附伏安法测定镓,其线性范围是1×10~(-10)～1×10~(-7)mol/L,其检测限为1×10~(-10)mol/L,并用此法测定了中草药中的痕量镓.     

Rapid and sensitive determination of protein by light-scattering technique with Eriochrome Blue Black R

Based on the interaction between Eriochrome Blue Black R (EBBR) and proteins, which causes a strong light-scattering signal with the maximum scattering peak located at 398 nm, a simple, rapid, sensitive and selective method is developed for the determination of proteins by the light-scattering technique using a common spectrofluoremeter. Under proper experimental conditions, the protein determination can be performed in the range of 0.1-25, 0.1-20 and 0.25-25 μg ml⁻¹ for bovine serum albumin (BSA), human serum albumin (HSA) and human immunoglobulin G (IgG), respectively. The detection limit, calculated as 3 times the S.D. of nine blank measurements, are 33 μg l⁻¹ for BSA, 25 μg l⁻¹ for HSA and 38 μg l⁻¹ for IgG. Moreover, there is no significant difference among the scattering signals yielded by HSA, IgG and BSA, and almost no interference of many amino acids and metal ions. The method has been satisfactorily applied to the direct determination of the total protein in human serum, saliva and urine samples. The results obtained from the studies on the binding characteristics of EBBR to BSA indicated that an electrostatic force existed in the binding system, and the binding constant (K) and the number of the binding sites (n) at 25 °C are 1.69×10⁵ l mol⁻¹ and 0.946, respectively.     

Quantitation of agmatine by liquid chromatography with laser-induced fluorescence detection

A high performance liquid chromatography (HPLC) method is described for the determination of agmatine, an endogenous neuromodulator. The method involves pre-column derivatization of the sample with a fluorescent tagging reagent, 7-fluoro-4-nitrobenzoxadiazole (NBD-F). The resulting agmatine derivative is stable and can be readily extracted into ethyl acetate at pH 8.5. The extraction enhances the quantification of low level agmatine because it eliminates chromatographic peaks caused by endogenous amino acids. The HPLC separation is carried out on a C₈ reversed phase column and completed in less than 10 min. With laser-induced fluorescence (LIF) detection, the detection limit is 5×10⁻⁹ M agmatine. Method precision (coefficient of variation) is 5% for agmatine in human plasma at the sub-μM level. This method has been validated by determination of agmatine in biological samples including human plasma and rat brain and stomach tissues.     

Remote substituent effects on bond dissociation energies of para-substituted aromatic silanes

UB3LYP/6-31G(d) and ROMP2/6-311++G(d,2p) methods were used to calculate the Si-X bond dissociation energies (BDEs) of a number of para-substituted aromatic silanes (4-Y-C(6)H(4)-SiH(2)X, where X = H, F, Cl, or Li). It was found that the substituent effect on the Si-H BDE of 4-Y-C(6)H(4)-SiH(3) was small, as the slope (rho(+)()) of the BDE- regression was only 0.09 kJ/mol. In comparison, the substituent effect on the Si-F BDE of 4-Y-C(6)H(4)-SiH(2)F was much stronger, whose rho(+ )()value was -2.34 kJ/mol. The substituent effect on the Si-Cl BDE of 4-Y-C(6)H(4)-SiH(2)Cl was also found to be strong with a rho(+)() value of -1.70 kJ/mol. However, the substituent effect on the Si-Li BDE of 4-Y-C(6)H(4)-SiH(2)Li was found to have a large and positive slope (+9.12 kJ/mol) against. The origin of the above remarkably different substituent effects on the Si-X BDEs was found to be associated with the ability of the substituent to stabilize or destabilize the starting material (4-Y-C(6)H(4)-SiH(2)X) as well as the product (4-Y-C(6)H(4)-SiH(2)* radical) of the homolysis. Therefore, the direction and magnitude of the effects of Y-substituents on the Z-X BDEs in compounds such as 4-YC(6)H(4)Z-X should have some important dependence on the polarity of the Z-X bond undergoing homolysis. This conclusion was in agreement with that from earlier studies (for example, J. Am. Chem. Soc. 1991, 113, 9363). However, it indicated that the proposal from a recent work (J. Am. Chem. Soc. 2001, 123, 5518) was unfortunately not justified.