结合三维静电势参数研究二取代苯的定量结构－疏水性关系

对含有常见取代基的92个二取代苯化合物进行了结构优化和静电势及其导出参数的计算,运用多元线性回归方法对化合物的疏水常数与分子的结构参数进行了关联.结果表明,分子表面负静电势的加和ΣV－S、分子空间内最负的静电势Vmin、表面最大静电势Vs,max以及分子体积V、极性表面积APS和分子的偶极密度μ/V这六个参数,可以很好地用于表达这些化合物疏水性与分子结构间的定量关系,而不用具体考虑分子中极性基团间的相互作用.用建立起来的QSPR(quantitative structure-property relationship)关系式对111个类似化合物的疏水性进行了预测,获得了满意的结果.     

GC-FPD、GC-MS法分析血液样品中的毒鼠强

采用液-液提取方法及GC—FPD定量、GC—MS定性检测手段，对血液样品中毒鼠强的提取和检测方法进行了研究。时提取毒鼠强的溶剂类型、溶剂用量及质谱分析参数等因素进行了考察，建立了一种回收率高、重现性好、灵敏度佳、干扰少的毒鼠强分析方法。毒鼠强工作曲线的线性范围为0．01-0．2μg／μL，相关系数r=0．9999，空白血液的加标平均回收率为93．6％，测定结果的相对标准偏差为5．27％。该方法满足司法鉴定中生物样品的定性、定量检验要求。     

Chromatographic separation and mass spectrometric identification of positional isomers of polyethylene glycol-modified growth hormone-releasing factor (1-29)

A one-step chromatographic method capable of separating all isomers of polyethylene glycol (PEG)-growth hormone-releasing factor (GRF) (1-29) conjugates was developed. The unmodified GRF (1-29) and seven different isomers of PEG-GRF (1-29) conjugates were separated by using a simple reversed-phase HPLC method depending on the differences of hydrophobicity due to the number and site of PEG attachment. The PEGylation sites of all isomers of PEG-GRF (1-29) conjugates were identified by determining the molecular masses of the Lys-C digested fragments with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. This study is a first report for the separation of all PEG-conjugate isomers and would be useful for further studies to find the promising conjugate by evaluating biological activity and stability of each isomer.     

Preparation d'alcools acetyleniques et propargyliques F-alkyles

A number of α-β acetylenic carbinols R_FCCC(OH)RR′, in which the acetylenic proton was substituted by a F-alkyl group, were first prepared, from a classical reaction of (F-alkynyl)- lithium derivatives R_FCCLi upon various carbonyl compounds.On another hand, the reaction of propargyl bromide metallic complexes (organoaluminic, or ultrasonic irradiation activated organozinc) upon some polyfluorinated ketones R_FCOR led to the formation, in convenient yields, of the propargylic carbinols HCCCH₂C(OH)RR_F.The synthesis and properties of these series of new (F-alkyl) substituted acetylenic and propargylic alcohols are described and discussed.     

Molecular recognition properties of salicylic acid-imprinted polymers

Summary Two molecularly imprinted polymers (MIP) have been prepared using the acidic drug salicylic acid, which can form intramolecular hydrogen bond, as the template and acrylamide or 4-vinylpyridine as the functional monomer. HPLC was used to evaluate the binding performance of the MIP for the template and for several analogues. The results showed that the MIP (P₂) prepared using acrylamide as the functional monomer had no molecular imprinting effect whereas that (P₁) prepared using 4-vinylpyridine as the functional monomer had a significant molecular imprinting effect. The reason the molecular imprinting effect was different for the two MIP was elucidated and the molecular recognition properties of P₁ were studied in detail. It was confirmed that electrostatic interaction played an important role in the molecular recognition of P₁. Scatchard analysis showed that two types of binding site with distinctly different affinity were formed in P₁. Their dissociation constants were estimated to be 7.6×10⁻⁵ mol L⁻¹ and 3.2×10⁻³ mol L⁻¹, respectively. Because P₁ has high affinity and selectivity for salicylic acid not only in organic systems but also in water-containing systems, it gives P₁ the potential for use in the enrichment, separation, and detection of salicylic acid in biological fluids.     

水与氯冉酸的荷移反应及其分析应用

用分光光度法研究了氯冉酸与水的荷移反应, 探讨了反应机理, 确定了反应条件. 氯冉酸与水形成紫色络合物的最大吸收波长为530 nm. 水量在0.13%～6%范围内呈线性关系, 检出限为体积分数0.13%, 相对标准偏差小于2%. 用本法测定乙醇、面粉及香料中的微量水, 与标准方法测定值相符, 回收率为97%～102%.     

明胶膜的性能研究进展

明胶膜具有良好的生物相容性和可降解性,并且其物化性质能被调节,因而应用比较广泛.本文综述了不同添加剂和制备条件对明胶膜的机械性能、阻隔性能、生物可降解性等的影响.通常增塑剂可以改善明胶膜的脆性,减小其机械强度和热稳定性.交联能有效提高明胶膜的机械性能和热稳定性,减缓明胶的降解速率.交联包括化学交联、生物相容性交联和物理交联.明胶与蛋白质、糖类、脂类复合,其性能得以改进,并且将明胶与高聚物共混、共聚改性,可以改善明胶膜的性能以满足不同领域的应用.     

Cancer cells undergoing epigenetic transition show short-term resistance and are transformed into cells with medium-term resistance by drug treatment

To elucidate the epigenetic mechanisms of drug resistance, epigenetically reprogrammed H460 cancer cells (R-H460) were established by the transient introduction of reprogramming factors. Then, the R-H460 cells were induced to differentiate by the withdrawal of stem cell media for various durations, which resulted in differentiated R-H460 cells (dR-H460). Notably, dR-H460 cells differentiated for 13 days (13dR-H460 cells) formed a significantly greater number of colonies showing drug resistance to both cisplatin and paclitaxel, whereas the dR-H460 cells differentiated for 40 days (40dR-H460 cells) lost drug resistance; this suggests that 13dR-cancer cells present short-term resistance (less than a month). Similarly, increased drug resistance to both cisplatin and paclitaxel was observed in another R-cancer cell model prepared from N87 cells. The resistant phenotype of the cisplatin-resistant (CR) colonies obtained through cisplatin treatment was maintained for 2–3 months after drug treatment, suggesting that drug treatment transforms cells with short-term resistance into cells with medium-term resistance. In single-cell analyses, heterogeneity was not found to increase in 13dR-H460 cells, suggesting that cancer cells with short-term resistance, rather than heterogeneous cells, may confer epigenetically driven drug resistance in our reprogrammed cancer model. The epigenetically driven short-term and medium-term drug resistance mechanisms could provide new cancer-fighting strategies involving the control of cancer cells during epigenetic transition.Subject terms: Tumour heterogeneity, Epigenetics     

Performance of hollow-fiber flow field-flow fractionation in protein separation

Since hollow-fiber flow field-flow fractionation (HF FIFFF) utilizes a cylindrical channel made of a hollow-fiber membrane, which is inexpensive and simple in channel assembly and thus disposable, interests are increasing as a potential separation device in cells, proteins, and macromolecules. In this study, performance of HF FIFFF of proteins is described by examining the influence of flow rate conditions and length of fiber (polyacrylonitrile or PAN in this work) on sample recovery as well as experimental plate heights. The interfiber reproducibility in terms of separation time and recovery was also studied. Experiments showed that sample recovery was consistent regardless of the length of fiber when the effective field strength (equivalent to the mean flow velocity at the fiber wall) and the channel void time were adjusted to be equivalent for channels of various fiber lengths. This supported that the majority of sample loss in HF FIFFF separation of apoferritin and their aggregates may occur before the migration process. It is finally demonstrated that HF FIFFF can be applied for characterizing the reduction in Stokes' size of low density lipoproteins from blood plasma samples obtained from patients having coronary artery disease and from healthy donors.     

Separation of carbon nanotubes by frit inlet asymmetrical flow field-flow fractionation

Flow field-flow fractionation (flow FFF), a separation technique for particles and macromolecules, has been used to separate carbon nanotubes (CNT). The carbon nanotube ropes that were purified from a raw carbon nanotube mixture by acidic reflux followed by cross-flow filtration using a hollow fiber module were cut into shorter lengths by sonication under a concentrated acid mixture. The cut carbon nanotubes were separated by using a modified flow FFF channel system, frit inlet asymmetrical flow FFF (FI AFIFFF) channel, which was useful in the continuous flow operation during injection and separation. Carbon nanotubes, before and after the cutting process, were clearly distinguished by their retention profiles. The narrow volume fractions of CNT collected during flow FFF runs were confirmed by field emission scanning electron microscopy and Raman spectroscopy. Experimentally, it was found that retention of carbon nanotubes in flow FFF was dependent on the use of surfactant for CNT dispersion and for the carrier solution in flow FFF. In this work, the use of flow FFF for the size differentiation of carbon nanotubes in the process of preparation or purification was demonstrated.