Simple chromatographic detection modes for antitumor agent and its degradants

Degradation of active ingredients is common during the production, transportation, and storage of the pharmaceutical preparations. The resulted degradation products can affect the pharmaceuticals’ therapeutic effect. Also, they may have some toxic properties that make them have deleterious effects on patients. Nifuroxazide, antitumor, antimetastasis, and antidiarrheal agent, has been detected in pharmaceutical formulation by two sensitive, selective, and cheap methods. The first method was densitometric thin-layer chromatography technique. The compound was detected in the presence of its degradation products without any interference. Limits of quantification and detection values were 200 and 94.3?ng/band, respectively. The method was linear in the range 0.2–12?µg/band with mean recovery% ±relative standard deviation (RSD)%?=?99.97%?±?1.414. The second method was developed using simple high-performance liquid chromatography technique. The method was successfully able to separate the proposed compound from its degradation forms in the presence of pentoxiftylline as an internal standard without any interference in less than 5?min. The method also detected nifuroxazide degradation products down to 500?ng/mL. Both methods were statistically compared to a reported method with no significant difference in performance.     

Derivatization of organophosphorus nerve agent degradation products for gas chromatography with ICPMS and TOF-MS detection

Separation and detection of seven V-type (venomous) and G-type (German) organophosphorus nerve agent degradation products by gas chromatography with inductively coupled plasma mass spectrometry (GC–ICPMS) is described. The nonvolatile alkyl phosphonic acid degradation products of interest included ethyl methylphosphonic acid (EMPA, VX acid), isopropyl methylphosphonic acid (IMPA, GB acid), ethyl hydrogen dimethylamidophosphate sodium salt (EDPA, GA acid), isobutyl hydrogen methylphosphonate (IBMPA, RVX acid), as well as pinacolyl methylphosphonic acid (PMPA), methylphosphonic acid (MPA), and cyclohexyl methylphosphonic acid (CMPA, GF acid). N-(tert-Butyldimethylsilyl)-N-methyltrifluroacetamide with 1% TBDMSCl was utilized to form the volatile TBDMS derivatives of the nerve agent degradation products for separation by GC. Exact mass confirmation of the formation of six of the TBDMS derivatives was obtained by GC–time of flight mass spectrometry (TOF-MS). The method developed here allowed for the separation and detection of all seven TBDMS derivatives as well as phosphate in less than ten minutes. Detection limits for the developed method were less than 5 pg with retention times and peak area precisions of less than 0.01 and 6%, respectively. This method was successfully applied to river water and soil matrices. To date this is the first work describing the analysis of chemical warfare agent (CWA) degradation products by GC–ICPMS. Figure Illustrated here are six parent organophosphorus nerve agents corresponding to the degradation products analyzed by gas chromatography with ICPMS and ToF-MS detection. The authors would like to thank Daisy-Malloy Hamburg and Kevin M. Kubachka for creating this figure     

Effects of toughening propylene/ethylene graft copolymer on the crystallization behavior and mechanical properties of polypropylene random-copolymerized with a small amount of ethylene

Linear low-density polyethylene (LLDPE) was grafted onto the backbone chains of isotactic polypropylene (iPP) during reactive melt-extrusion to produce a novel toughening modifier, propylene/ethylene graft copolymer (PEGC), to improve the properties of iPP random(-copolymerized with a small amount of ethylene) (PPR). The crystallization behavior as well as the non-isothermal crystallization kinetics of the PEGC modified PPRs were investigated via differential scanning calorimetry (DSC), polarized optical microscopy (POM) and wide-angle X-ray diffraction (WAXD). The fractured surface topography was characterized using scanning electron microscopy (SEM), and the mechanical properties through notched impact and tensile testing as well as dynamic mechanical thermal analysis (DMTA). The results show that, at a PEGC content of 8 wt%, notched impact strength of the PEGC modified PPR increased by 30.6% at low temperature (−25 °C). As regards crystalline morphology, the PEGC, as an effective heterogeneous nucleating agent, fostered nucleation of the PPR to elevate its crystallization temperature as well as rate of crystallization, thus refining the PPR (iPP) spherulites and improving the interfacial structure between iPP spherulites. The Jeziorny approach was unsatisfactory for simulation of the non-isothermal crystallization process of the PEGC modified PPRs; however, the Mo method described consistently the crystallization kinetics over the entire isothermal process.     

计算机辅助三聚氰胺分子印迹聚合物的制备

以三聚氰胺(MAM)为印迹分子,丙烯酰胺(AM)、甲基丙烯酸(MAA)、N,N-亚甲基双丙烯酰胺(MBA)和衣康酸(IA)为功能单体,二乙烯基苯(DVB)、乙二醇双甲基丙烯酸酯(EGDMA)和三羟甲基丙烷三甲基丙烯酸酯(TRIM)为交联剂,采用量子化学密度泛函理论的长程校正方法模拟并探讨了MAM与4种功能单体的成键作用位点、成键数目、印迹反应摩尔比及印迹作用机理.依据结合能(ΔE)优化了功能单体和交联剂,并借助分子中原子理论(AIM)揭示了MAM与功能单体印迹作用的本质.计算结果表明,MAM通过氢键与4种功能单体以摩尔比1∶6进行印迹聚合,其中IA与MAM形成的复合物结合能最低,结构最稳定;与TRIM和EGDMA交联剂相比,DVB与MAM结合能最低,更适合作为MAM-IA印迹聚合物的交联剂.采用沉淀聚合法合成MAM分子印迹聚合物(MAM-MIPs)并测定其吸附性,当MAM与IA印迹摩尔反应比为1∶6时,以DVB为交联剂时制备的MAM-MIPs吸附性最好,其微球平均粒径为195 nm;Scatchard分析结果表明,在所研究的浓度范围内MIPs对印迹分子MAM的结合位点是等价的,其最大表观吸附量Qmax为20.79mg/g,离解平衡常数Kd为58.82 mg/L;与环丙氨嗪(CYR)、三聚氰酸(CYA)和三聚硫氰酸(TRI)在牛奶中的吸附量相比,MAM-MIPs对MAM表现出较强的特异吸附能力.     

Effect of Annealing Temperature on Low-temperature Toughness of β-Nucleated Polypropylene Random Copolymer/Ethylene-Propylene-Diene Terpolymer Blends

In this study, the effect of annealing temperature on the impact toughness of β-nucleated polypropylene random copolymer(PPR) and ethylene-propylene-diene terpolymer(EPDM) blends was investigated by differential scanning calorimetry(DSC), wide-angle X-ray diffraction(WAXD), dynamic mechanical analysis(DMA) and scanning electron microscopy(SEM). Interestingly, the impact strength of β-PPR/20 EPDM blend annealed at 120 ℃ is 1.8 times as high as that of unannealed samples. In addition, the crystalline structure, the relaxation of chain segments and fracture morphology of β-PPR/EPDM blends were also investigated to explore the toughening mechanism related to annealing. The results show that annealing at moderate temperatures results in the improvement of integrity of the crystal structure and the relative content of β-phase. The work provides a possible method to toughen the semicrystalline polymer at low temperatures by annealing.     

Explosive and chemical threat detection by surface-enhanced Raman scattering: A review

Acts of terror and warfare threats are challenging tasks for defense agencies around the world and of growing importance to security conscious policy makers and the general public. Explosives and chemical warfare agents are two of the major concerns in this context, as illustrated by the recent Boston Marathon bombing and nerve gas attacks on civilians in the Middle East. To prevent such tragic disasters, security personnel must be able to find, identify and deactivate the threats at multiple locations and levels. This involves major technical and practical challenges, such as detection of ultra-low quantities of hazardous compounds at remote locations for anti-terror purposes and monitoring of environmental sanitation of dumped or left behind toxic substances and explosives. Surface-enhanced Raman scattering (SERS) is one of todays most interesting and rapidly developing methods for label-free ultrasensitive vibrational “fingerprinting” of a variety of molecular compounds. Performance highlights include attomolar detection of TNT and DNT explosives, a sensitivity that few, if any, other technique can compete with. Moreover, instrumentation needed for SERS analysis are becoming progressively better, smaller and cheaper, and can today be acquired for a retail price close to 10,000 US$. This contribution aims to give a comprehensive overview of SERS as a technique for detection of explosives and chemical threats. We discuss the prospects of SERS becoming a major tool for convenient in-situ threat identification and we summarize existing SERS detection methods and substrates with particular focus on ultra-sensitive real-time detection. General concepts, detection capabilities and perspectives are discussed in order to guide potential users of the technique for homeland security and anti-warfare purposes.     

刚性非共平面的环氧树脂体系的制备及性能研究

基于新型的刚性非共平面二胺4',4″-(2,2-diphenylethene-1,1-diyl)dibiphenyl-4-amine(TPEDA)环氧树脂固化剂,采用动态机械分析(DMA)、热机械分析(TMA)和阻抗分析全面研究了其固化环氧树脂(E51)所制备的环氧固化物(E51/TPEDA)的热、机械和介电等综合性能.并与商业化的固化剂2,4-二氨基二苯甲烷(DDM)、4,4二氨基二苯砜(DDS)固化环氧树脂体系进行对比,结果表明由于TPEDA特有的刚性非共平面结构的引入,E51/TPEDA体系表现了较高的玻璃化转变温度、拉伸强度和较低的热膨胀系数、介电常数与损耗等优异物理性能.因此,基于新型非共平面二胺的环氧树脂固化物表现了在电子封装领域的潜在应用前景.     

高胶质沥青质超稠油降粘剂YZ-31的研究

针对高胶质和沥青质含量超稠油的特点,室内研究了一种高效油溶性稠油降粘剂YZ-31,对不同降粘剂对超稠油降粘效果进行了比较。探讨了超稠油降粘剂YZ-31加量、温度等因素对降粘效果的影响。结果表明:油溶性降粘剂YZ-31对高胶质和沥青质含量的胜利油田郑家超稠油降粘效果明显。在50oC,5 wt%的降粘剂加量下对三种实验超稠油样品的降粘率都在95%以上。     

新型三嗪类氮-硅成炭剂的合成及其热稳定性

以三聚氯氰(1)和γ-氨丙基三乙氧基硅烷(2)为原料,经亲核取代反应合成了一种新型三嗪类氮-硅成炭剂——2-氯-4,6-二(3-三乙氧基硅烷基-1-氨丙基)-1,3,5-三嗪(3),其结构和热性能经1H NMR,IR和TGA表征。考察了溶剂、缚酸剂、原料比和反应温度对3产率的影响。合成3的最佳反应条件为:以丙酮为溶剂,Na2CO3为缚酸剂,1 10 mmol,n(2)∶n(1)=2.4,于50℃反应6 h,产率98.1%。3的初始分解温度为292℃,700℃时成炭率34.5%。     

新型防污剂释放率测试技术研究

建立新型防污剂N-辛基-2-羟基苯甲酰胺释放率测试方法。防污剂用丙酮溶解,通过紫外光谱法建立N-辛基-2-羟基苯甲酰胺的吸光度–浓度标准曲线。将含有防污剂的涂层置于水中,使其释放防污剂,定期获取溶液,利用冷冻干燥除水,然后用丙酮溶解释出的防污剂,进行紫外光谱测试。利用标准曲线法测定防污剂释放量,计算得到释放率。结果表明,在330 nm波长下,防污剂浓度与吸光度线性关系良好,相关系数r2=0.999 1。方法的检出限为5μg/m L,测定结果的相对标准偏差为0.4%(n=5),加标回收率为97%~105%,样品在4 h内稳定。该方法测试稳定性较好,定量准确,操作简便,为防污剂检测提供了可靠的评价方法。