丙硫菌唑原药中3个主要杂质合成及产生历程分析

为获得丙硫菌唑原药中脱氯丙硫、脱硫丙硫和甲基化丙硫3个主要杂质,分别以氯化苄、丙硫菌唑原药为起始原料,设计合成路线并对3个杂质进行了合成,杂质含量>97%,其结构经LC-MS和1H NMR等结构表征确证。基于丙硫菌唑原药合成路线和相关文献资料调查,分析推测了3个杂质产生的可能历程。研究结果可为丙硫菌唑研究、工艺开发提供基础与指导。     

高效氯氟氰菊酯原药及其主要杂质的气-质联机分析

采用气相色谱-质谱(GC–MS)联用对高效氯氟氰菊酯原药主要成分及主要杂质进行分离分析,并结合高效氯氟氰菊酯的合成工艺,确定了主要成分及主要杂质的结构。     

吡唑醚菌酯原药的主要杂质及合成研究

吡唑醚菌酯原药中含有3个在生产过程产生的含量较高的杂质,以吡唑醚菌酯原药为原料,合成了这些杂质,NMR和MS表征了其结构,并通过对原药重结晶纯化制得标准品,为吡唑醚菌酯原药合成工艺的控制和全组分分析提供支持。     

噁嗪草酮分析方法述评

总结了文献中报道的嗪草酮的分析方法。噁嗪草酮的分析方法主要采用高效液相色谱法和气相色谱法,分别用于噁嗪草酮原药和残留物的分析。     

气-质联用技术分析苯氰菊酯原药及其杂质

采用气相色谱-质谱联用技术(GC-MS)对苯氰菊酯原药及其杂质进行分析研究。结合苯氰菊酯的合成工艺,对苯氰菊酯原药中含量在0.1%以上的11个杂质进行了定性分析,并确定了结构。     

野麦畏原药主要杂质及仲胺中间体的制备

野麦畏原药中含有3个结构相似的在生产过程中产生的主要杂质(TEITC,TPITC和TDITC),采用醛酮还原胺化法合成了高纯度(质量分数)仲胺中间体,并制备得到这3个相关杂质,其纯度均在99%以上,为野麦畏原药合成反应的控制和全组分分析提供了支持。     

丙硫菌唑原药杂质全分析

[目的]对丙硫菌唑原药进行全分析,明确质量分数大于0.1%的有机杂质的结构及含量。[方法]采用液质联用仪和气质联用仪分别对丙硫菌唑进行定性分析,以高效液相色谱和气相色谱等分析手段对原药及杂质进行定量分析或最低被检测质量分数。[结果]丙硫菌唑原药杂质为甲苯、杂质307和杂质309,而相关杂质硫酮菌唑的最低被检测质量分数为0.002%。[结论]试验不仅提供了一种丙硫菌唑全组分分析,而且对该产品的合成优化具有重要参考价值。     

氧乐果原药中主要杂质的GC/MS定性分析

利用气相色谱-质谱联用仪对氧乐果原药中所含主要杂质进行了定性分析,据GC／MS结果和氧乐果生产工艺推断其两种主要杂质为O,O-二甲基亚磷酸酯和O,O-二甲基-S-(甲氧基羰基甲基)硫代磷酸酯,合成杂质标样,由保留时间及质谱图确证了推断的杂质组成和结构,推测其质谱裂解途径,为氧乐果的分析及生产提供依据。     

甲基嘧啶磷及其杂质的GC-MS分析研究

采用气相色谱-质谱联用法对甲基嘧啶磷原药进行分离鉴定。采用HP-5MS(30 m×0.25 mm,0.25μm)毛细管柱,以EI源为离子源,得到甲基嘧啶磷及其8个杂质的质谱图,根据合成路线,推断出上述杂质结构,并讨论了甲基嘧啶磷的质谱裂解规律。实验结果有利于控制甲基嘧啶磷原药的杂质,提高产品质量。     

啶氧菌酯原药中主要杂质的制备、鉴定和定量分析

建立了啶氧菌酯杂质制备和分析的方法。采用酯交换方法合成杂质,并通过柱层析法提纯,采用液相-质谱联用和液相色谱方法对啶氧菌酯杂质进行定性和定量分析。制备了啶氧菌酯原药中的主要杂质标准品,含量为97.0%。建立了啶氧菌酯主要杂质的定量分析方法,添加回收率为99.13%。当杂质的浓度为8.2~164.9 mg/L时,方法的线性相关系数为0.997 5。本方法建立了啶氧菌酯原药中主要杂质的制备、定性和定量的分析方法,为啶氧菌酯原药质量分析和控制提供了依据。     

25%嗪草酮·高效氟吡甲禾灵·砜嘧磺隆可分散油悬浮剂高效液相色谱分析

[目的]建立一种对25%嗪草酮·高效氟吡甲禾灵·砜嘧磺隆可分散油悬浮剂进行分离和测定的高效液相色谱分析方法。[方法]采用ZORBAX SB-C18反相柱,以甲醇和水(0.1%磷酸水溶液)为流动相,流速为1.0 mL/min,在254 nm条件下对试样中的嗪草酮、高效氟吡甲禾灵和砜嘧磺隆同时进行定量分析。[结果]经分析方法验证,嗪草酮、高效氟吡甲禾灵和砜嘧磺隆的线性相关系数分别为0.9995、0.9999、1,标准偏差分别为0.057、0.033、0.005,变异系数分别为0.26%、0.64%、0.32%,平均回收率分别为100.2%、99.7%、100.5%。[结论]该方法简便、快速、分离效果好,适用于复配制剂中嗪草酮、高效氟吡甲禾灵和砜嘧磺隆的定量分析。     

Determination of metallic impurities in high-purity type IIa diamond grown by high-pressure and high-temperature synthesis using neutron activation analysis

Metallic impurities in high-purity type IIa and conventional type Ib diamond single crystals grown by high-pressure and high-temperature (HPHT) synthesis were determined by neutron activation analysis using thermal neutrons. Metallic impurities of Fe, Co, Cr and other minor elements were detected in the high-purity type IIa diamond crystal. The typical quantities of these metallic impurities were a few ppb. The influence of these metallic impurities on the electrical properties of the type IIa diamond crystal was practically negligible compared with nitrogen and boron impurities behaving as a donor and an acceptor, respectively. In addition to the impurities detected in the type IIa diamond crystal, Ni impurities of several hundreds of ppb were detected in conventional type Ib diamond crystals. A difference in molten metal solvents used in the synthesis of each diamond crystal resulted in the difference in metallic impurities.     

传统法制备嗪草酮印迹聚合物

农药嗪草酮应用广泛,它的残留问题引起了人们的普遍关注,发展快速准确的检测方法势在必行。而分子印迹技术因其独特的优点使它成为痕量残留快速检测的一种较好的方法。采用传统法制备嗪草酮印迹聚合物,以甲基丙烯酸(MAA)为功能单体,N,N-亚甲基双丙烯酰胺为交联剂,甲苯为溶剂,在50℃时聚合得到选择性、吸附性最佳的印迹聚合物。     

乙草胺和嗪草酮混合悬乳剂的气相色谱分析

本文报道了乙草胺和嗪草酮混合悬乳剂的气相色谱分析方法，在４％ＯＶ－２２５／Ｃｈｒｏｍｏｓｏｒｂ Ｗ－ＨＰ（８０－１００目）色谱柱上乙草胺、嗪草酮和内标物癸二酸二丁酯的保留时间分别为１０．４５，１７．２４和１２．９分钟，实现了良好手分离。乙草胺的标准偏差、变异系数和回收率分别为０．１０９、０．５６％和９９．６％；嗪草酮的标准偏差、变异系数和回收率分别为０．３１４、１．５２％和１００．１％。     

The Development of a New Synthesis Process for 3,3′‐Diamino‐4,4′‐azoxyfurazan (DAAF)

Process optimization studies were performed for the preparation of the high explosive 3,3′‐diamino‐4,4′‐azoxyfurazan (DAAF). These process studies were pursued to address issues such as problematic waste generation products, particle size, impurities, and manufacturability. This paper describes the original synthesis method and inherent issues. An optimization process was designed to investigate the issues with purity and manufacturability. Particle size effects were addressed by adding a recrystallization step to the synthesis. Ultimately, a complete solution to all observed issues was found with a new synthesis process, which now allows DAAF to be prepared without any impurities, with good particle size and without the need for recrystallization. Importantly, the new synthesis process can be performed in an environmentally friendly manner, with the production of non‐hazardous waste.     

35%精异丙甲草胺·嗪草酮乳油防除马铃薯田间杂草试验

[目的]明确35%精异丙甲草胺·嗪草酮乳油对马铃薯田间杂草防除效果及对马铃薯生长发育的安全性。[方法]马铃薯苗前采用35%精异丙甲草胺·嗪草酮乳油.960 g/L精异丙甲草胺乳油、70%嗪草酮可湿性粉剂的不同剂量处理进行土壤喷雾,评估其药效和安全性。[结果]35%精异丙甲草胺·嗪草酮乳油787.5-2100 ga.i./hm²对马铃薯田杂草的防治效果明显,药后45 d,对3种杂草鲜重防效在89.08%以上,其中787.5,1050,1312.5 ga.i./hm²鲜重总草防效分别为90.07%,93.60%.96.57%,好于2个单剂对照,且有一定的增产效果,对马铃薯生长没有不良影响。[结论]35%精异丙甲草胺·嗪草酮乳油对马铃薯安全,杂草田间防治效果良好,推荐使用剂量为150-250 mL/667m²(制剂用量)或787.5-1312.5ga.i./hm²(有效成分含量)。     

酶法7-ACA酰化液的除杂工艺研究

7-ACA是合成头孢菌素的关键中间体,其生产工艺已逐渐由化学法被酶法所取代。因酶法工艺较化学法酰化液存在蛋白、色素等杂质多的问题,需结晶前进行除杂。介绍了炭脱、超滤、萃取等各种除杂方法,将各种除杂方法及其各种组合方式对产品质量的影响进行了比较,确定双膜法除杂工艺为最佳方式。该除杂工艺能有效去除蛋白、色素等杂质,产品纯度、色级、内毒素等质量指标明显提高。     

异戊巴比妥的杂质研究和化学合成

使用中国药典2010版HPLC方法对异戊巴比妥进行分析,可以检测到两个明显的杂质。依据生产工艺对杂质进行了结构推断和产生原因分析并对杂质进行了合成。通过对合成杂质与异戊巴比妥杂质HPLC和MS分析比对,确定异戊巴比妥中主要杂质为异戊巴比妥的同分异构体[5-乙基-5-(2-甲基丁基)巴比妥酸]和双异戊巴比妥[5,5-二(3-甲基丁基)巴比妥酸]。     

Lignin‐polyethylene glycol matrices and ethylcellulose to encapsulate highly soluble herbicides

The blending of lignin with polyethylene glycol (PEG) allowed us to obtain formulations with controlled release properties in which metribuzin have been successfully trapped with encapsulation efficiency higher than 85%. Moreover, the modification of the lignin's viscoelastic properties by the addition of PEG led to obtain herbicide formulations with active ingredient contents lower than 15%, suitable for its application in soil. Fourier transformed infrared spectroscopy and differential scanning calorimetry studies indicated the compatibility between polymers and metribuzin in lignin‐based controlled release formulations (CRFs). Lignin‐based formulations were coated in a Wurster‐type fluidized‐bed equipment using ethylcellulose and dibutylsebacate. Scanning electron microscope pictures showed a homogeneous film in ethylcellulose‐coated CRFs. The kinetic release studies showed that the release rate of metribuzin was mainly controlled either by selecting the granule size of controlled release lignin‐PEG matrixes, or by changing the thickness of coating film for ethylcellulose coated CRFs. These results could help to increase the efficiency of delivery of the highly soluble herbicide metribuzin and prevent the environmental pollution derived from its use. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41422.     

Hydrothermal conversion of rice husk ash to faujasite-types and NaA-type of zeolites

The faujasite-type of zeolites (NaX and NaY) and NaA-type of zeolite were synthesized from rice husk ash (RHA) via the hydrothermal conditions. The combustion of rice husk at controlled temperature of 600 °C for an hour in open air produce more than 90% of amorphous silica in the ash which was reactive towards the synthesis of zeolites. The formation of zeolite NaY from RHA is metastable and thus, the seeding and ageing effects in the synthesis of zeolite NaY were investigated to avoid the formation of zeolite A or P as the impurities in zeolite NaY. Zeolites NaX and NaA were also successfully synthesized with high purity, absence of impurities and other phases, and high reproducibility. Thus, the amorphous forms of silica in RHA can be used as a source of silica for the synthesis of faujasite-types and NaA-type of zeolites.