Study on the Built-up Effect of Inorganic Compounds to Flame Retardant Containing Organophosphorus in Suppression of Smoke

The built-up effect of inorganic compounds containing more active metal ions, such as Ca^2＋ , Al^3＋ , Cu^2＋ , and Zn^2＋ , as additives adding to phosphorus-containing flame retarding systems in suppression of smoke was studied. The data presented herein suggested that the amount of smoke in the burning process can be better suppressed after the cotton fabric finishing with built-up system was burnt. Some general principles were identified, and the likely causes of the observed effects were analyzed according to test data.

STUDIES ON ORGANOPHOSPHORUS COMPOUNDS 69.A NOVEL SYNTHESIS OF 5-SUBSTITUTED 3-(1'-DIETHOXYPHOSPHORYLALKYL)-2-ISOXAZOLINES

Additions of diethyl phosphite to α-nitroalkenes followed by the introduction of trimethylchlorosilane and an activated alkene, gave the corresponding title compounds via regioselective 1,3-dipolar cycloaddition in moderate yield.

STUDIES ON ORGANOPHOSPHORUS COMPOUNDS 86 SOME NEW ASPECTS ON THE SYNTHESIS OF DIALKYL 1-ISOCYANO-BENZYL-AND/OR ALKYL-PHOSPHONATES

1-Isocyano substituted benzylphosphonates were prepared by dehydration of 1-N-formylamino substituted benzylphosphonates,which were obtained by a tricomponental condensation described by us.Mean- while addition of diethyl phosphite to N-trityl aldimine followed by deprotection,formylation and dehydration gave corresponding 1-isocyano alkylphosphonates in one-pot procedure.

Electrochemical Biosensors for Determination of Organophosphorus Compounds: Review

In last few decades there is exponential increase in use of organophosphorus (OP) compounds as pesticides and insecticides leading to adverse effect on human population and live stock. There is a great need to develop portable analytical tools that are amenable for remediation and bioremediation process monitoring, where rapid analysis of large number of samples is essential. Determination of various organophosphorus compounds has been achieved by integrating biocomponents with different transducers. The close integration of the biological events with the generation of a signal offers the potential for fabricating compact and easy-to-use analytical tools of high sensitivity and specificity. With the availability of new materials, associated with new sensing techniques has led to remarkable innovations in the design and construction of organophosphorus biosensors. The present review describes the specifications of most of the electrochemical Organophosphorus biosensors reported till date.

EMPIRICAL RULES FOR ^(31)p-NMR OF ORGANOPHOSPHORUS COMPOUNDS

The substituent effects on ^(31)P-NMR chemical shifts, are determined by five empirical rules. The proposed rules are based on that the shielding (upfield shift) of resonance nucleus is governed by the spherical symmetry of the electron cloud.

Improving Sensitivity of Enzyme to Organophosphorous Compounds by Combining Experiment and Theory Methods

In this paper,we compared the sensitivities of AFEST（a thermophilic esterase from the archaea Archaeoglobus fulgidus） and acetylcholinesterase（AChE） towards five organophosphorus compounds（OPs） by means of molecular docking,and found that only the docking energy between AFEST and dichlorvos is lower than that between AChE and dichlorvos.Via the docking model of AFEST and dichlorvos,Arg43 was found to play an important role in the interaction between AFEST and dichlorvos by means of stabilizing the complex.Then mutant R43S was constructed,the IC 50（the concentration required to reduce virus-induced cytopathicity by 50% is estimated as 50% inhibitory concentration） of which to dichlorvos was lower than that of the wild type AFEST by a factor of 1.56,indicating the enhanced sensitivity of mutant R43S to dichlorvos.Combining of theory with experiment,we have obtained important structure-function information of AFEST,which will be helpful to the further studies of esterase.

STUDIES ON ORGANOPHOSPHORUS COMPOUNDS XXXV——SUBSTITUENT EFFECT OF ORGANOPHOSPHORUS COMPOUNDS ON ^(31)P NMR SPECTROSCOPY

The linear relationship between the chemical shift of the resenant nucleus and the localvan der Waals steric energy calculated by molecular mechanics with MM2 force field wasextended to various organophosphorus compounds including alkyl-phosphates, -phosphonates,-phosphinates as well as -phosphine oxides. The conformational equilibria of a series of alkylO,O-1,3--propylene-and O, O-1,4-butylenephosphonates were studied by the molecular mechanicscalculations and the dynamic ^(31)P NMR spectroscopic method. As shown by these experimentaldata, the former existed in a chair form, and the latter in a twist boat form with an equatorialalkyl group in both configurations, either in gaseous state or in non-polar solvent.

Studies on organophosphorus compounds 52.Structure-reactivity studies of organophosphorus compounds by MNDO calculations

MNDO and MM2(85)methods were used to study the conformation and the structure- reactivity relationship of neutral and acidic phosphorus esters.The calculation results indicate that for the most stable conformation,the charge density of phosphoryl oxygen(q_O)is determined not only by the electronegativity of the substituents,but also by the conformation of the alkoxyl groups on the phosphorus atom.Meanwhile,the conformation of the alkoxyl group provides,as a rule, more important influence on the charge density of the phosphoryl oxygen.However,the energy of the highest occupied molecular orbital(EHOMO)is basically dependent on the eletronegativity of the substituents,while the donating ability or the withdrawing ability of the neutral phosphorus com- pounds is mainly governed by the EHOMO but not the q_O.This is also true for other kinds of the neutral oxygen-containing compounds.

Prediction of gas chromatographic retention indices of organophosphorus compounds by holographic QSRR

A new molecular structure representation, molecular hologram, is employed to investigate the quantitative relationship between gas chromatographic retention indices and molecular structures for 41 methylesterified organophosphorus compounds (OPs). The quantitative structure-retention relationship (QSRR) model has been constructed for GC-RI of the selected OPs through partial least squares regression, which shows high statistical quality and predictive value with non-cross validation correlation coefficient r2 of 0.994, and cross validation correlation coefficient q2LOO values of 0.984. In order to verify the robustness and prediction capacity of the model, 30 OPs were randomly selected from the database as the training set, while the rest were used as the testing set. The result of PLS regressive analysis of the training set yields r2 of 0.995 and q2LOO of 0.982, suggesting the excellent ability to predict the GC-RIs of OPs in the testing set. Furthermore, the retention behavior of the compounds in GC stationary phase is discussed, and the effects of different groups on the OP side-chain in the interaction between OPs and the stationary phase are explored using HQSAR color code, which provides useful guideline for the retention rules of OPs and related compounds.

An efficient synthesis of substituted alkyl acrylates using α-keto amides

The addition of α-keto amides as a NH-acid to alkyl propiolates and dialkyl acetylenedicarboxylates in the presence of a catalytic amount of triphenylphosphine gives the corresponding substituted alkyl acrylates.

Co/MOF-808(Zr)复合材料的制备及其对有机磷化合物的降解性能

为了解决普通单金属MOFs材料几乎不能直接将双(4-硝基苯)磷酸酯(BNPP)直接降解为毒性更低的对氨基苯酚(4-AP)的问题,通过油浴法制备出MOF-808(Zr)后,采用后修饰法将草酸钴负载于MOF-808(Zr)上,制备出Co/MOF-808(Zr)复合材料,并对所制材料进行XRD和TEM表征。结果表明:MOF-808(Zr)具有高晶体结构稳定性,Co/MOF-808(Zr)的粒径在250 nm左右且分布均匀;Co/MOF-808(Zr)通过级联反应成功将有机磷神经毒剂模拟物BNPP直接降解为毒性更低的4-AP,而非一般的毒性较高的降解产物对硝基苯酚(4-NP)。其最佳级联降解反应条件为:温度45℃,Co/MOF-808(Zr)剂量为2 mg/mL,底物BNPP为0.6 mmol/L,硼氢化钠0.06 mmol/L。实践得出,Co/MOF-808(Zr)在将有机磷化合物直接降解为毒性更低的4-AP方面表现出良好的应用潜力。

有机磷水解酶异源表达纯化及抗乙基对氧磷中毒能力初步评价

目的异源表达纯化有机磷水解酶(OPH),初步评价其动物体内抗乙基对氧磷中毒能力。方法构建OPH的大肠杆菌表达菌株,采用镍柱亲和色谱及凝胶过滤色谱进行纯化,对纯化产物进行蛋白质谱鉴定;以乙基对氧磷为底物测定酶活力及其动力学常数K_(m),V_(max),k_(cat)和k_(cat)/K_(m);12只SD大鼠随机分为OPH组和溶剂对照组,OPH组按1 mg·kg^(-1)剂量iv给予OPH溶液,对照组给予等体积生理盐水,给药后2组立刻sc给予2倍半数致死量(LD_(50))乙基对氧磷(0.86 mg·kg^(-1))染毒,观察大鼠状态,对中毒症状进行评分。对存活大鼠每隔24 h重复sc给予2倍LD_(50)乙基对氧磷,根据大鼠存活情况与中毒症状分别绘制生存曲线与症状评分图,评价OPH的抗有机磷中毒能力。结果成功构建了OPH的大肠杆菌表达菌株,经过两步纯化后由十二烷基硫酸钠-聚丙烯酰胺凝胶电泳表征得单一条带,OPH纯度较高,经蛋白质谱测定制备蛋白与目标蛋白序列一致;以乙基对氧磷为底物时,OPH的Km=7.5×10^(-5)mol·L^(-1),V_(max)=2.2×10^(-7)mol·L^(-1)·s^(-1),k_(cat)=158.4 s^(-1),k_(cat)/K_(m)=2.1×10^(6) L·mol^(-1)·s^(-1);对照组大鼠sc给予2倍LD_(50)乙基对氧磷后,出现严重中毒症状,15 min内全部死亡,实验组大鼠在首次染毒后均未出现中毒症状,连续染毒后中毒症状逐渐加重直至第4天全部死亡。结论成功制备高纯度OPH,且OPH在大鼠体内能有效对抗乙基对氧磷中毒。

气相色谱法测定鱼和肉中有机磷农药残留量

采用气相色谱法测定鱼和肉中有机磷农药残留量,对国标法作了部分改进,从而使可测的有机磷农药组份增加一个甲基对硫磷,且灵敏度和分辨率均有所提高,同时使国标法中未完全分离的马拉硫磷和对硫磷得到完全分离。

急性中重度有机磷农药中毒对认知功能的影响

目的探讨急性中重度有机磷农药中毒对认知功能的影响。方法选取2010年11月—2014年10月在安徽医科大学第二附属医院急诊内科住院且符合纳入标准的急性中重度有机磷农药中毒患者29例作为研究组,另选取本院同期体检健康者29例作为对照组。研究组患者均给予及时洗胃等相应治疗。采用蒙特利尔认知评估量表(Mo CA)评价所有患者的认知功能,比较对照组入组时及研究组治疗后1周、1个月及6个月的Mo CA各维度评分及总分。结果研究组治疗后1个月、6个月Mo CA总分均高于治疗后1周(P<0.05);研究组治疗后6个月Mo CA总分高于治疗后1月(P<0.05)。研究组治疗后1周、1个月Mo CA总分低于对照组(P<0.05);研究组治疗后6个月Mo CA总分与对照组比较,差异无统计学意义(P>0.05)。研究组治疗后1个月、6个月命名、注意、抽象、延迟回忆、定向评分均高于治疗后1周,治疗后6个月视空间与执行功能、语言评分高于治疗后1周(P<0.05);研究组治疗后6个月视空间与执行功能、注意、语言、抽象、延迟回忆、定向评分高于治疗后1个月(P<0.05)。对照组视空间与执行功能、命名、注意、语言、抽象、延迟回忆、定向评分均高于研究组治疗后1周(P<0.05);对照组注意、语言、延迟回忆、定向评分均高于研究组治疗后1个月(P<0.05);对照组注意、延迟回忆评分高于研究组治疗后6个月,语言评分低于研究组治疗后6个月(P<0.05)。结论急性中重度有机磷农药中毒可导致患者认知功能损伤,治疗后6个月Mo CA总分虽然恢复正常,但注意及延迟回忆功能仍较差。

阿托品抢救急性有机磷农药中毒208例分析及对患者预后的影响

目的:观察阿托品抢救急性有机磷农药中毒208例及对患者预后的影响.方法:对我院2005-01/2007-12急性有机磷农药中毒的患者208例进行回顾性分析,Ⅰ组为服毒后3h内达到阿托品化103例,Ⅱ组为服毒3h后达到阿托品化105例,比较两种并发症和病死率的发生率.结果:与Ⅰ组相比,Ⅱ组病死率高(18.1%vs7.8%,P<0.05),并发症发生率高.结论:阿托品抢救急性有机磷农药中毒时阿托品化达到的时间越早,患者的治疗效果和预后越好,病死率发生越少.

具有生物活性的有机磷化合物的研究V，α－［（取代）芳氧基乙酰氧基］烷基膦酸酯的合成和性质

过取代苯氧乙酰氯和α－羟基烷基胰酸酯的缩合反应合成了８种标题化合物，用元素分析，红外，核磁及质谱作了表征，测定了它们的除草活性和植物生长调节活性。

北京市蔬菜、水果中有机磷农药残留现状调查

为了解北京市蔬菜、水果中有机磷农药残留情况 ,2 0 0 2年在北京市抽检样品 35 4件进行 13种有机磷监测 ,其中蔬菜 2 81件 ,水果 73件。检测结果显示 7 6 %的检品不符合国家标准。叶菜类(14 ,占 9 3% )和根茎类 (8,占 17 4 % )蔬菜的不合格率明显高于瓜菜、果菜类 (2 ,占 2 4 % )蔬菜和水果 (3,占 4 1% )。 13种有机磷检测出 12种 ,其中禁用农药占 5 3%。本市种植的蔬菜、水果与外埠进京产品的有机磷农药残留情况无显著差别 ,超市、集贸市场、批发市场销售的产品的不合格率亦无显著差别。

α-(2-苯并噻唑氧基)烃基膦酸酯的合成性质和生物活性

α—芳(杂环)氧基羧酸衍生物是一类具有良好除草活性的化合物,近年来又发现含氮杂环氧基羧酸衍生物显示了更优异的除草活性,为了探索它们的含磷类似物的生物活性。

兔血清中对氧磷酶的提取和纯化

目的从兔血清中提纯对氧磷酶并纯化。方法采用液相色谱的方法,从兔血清中提取对氧磷酶并进行部分纯化。比色法检测待测样品中对氧磷酶的活性,垂直板电泳的方法检测纯化的对氧磷酶的纯度。采用体外解毒的方法,以1.5倍的LD50的敌敌畏(75 mg/kg)同对氧磷酶粗酶(10 U/kg)混合后,给予小鼠腹腔注射,初步验证对氧磷酶的解毒活性。结果纯化后的对氧磷酶比活性为11.54 IU/mg,较纯化前的比活性(0.058 IU/mg)提高了近200倍,产出率约为10%。部分纯化的对氧磷酶对于有机磷类农药有较好的催化水解作用。染毒大鼠的死亡率为0。结论采用液相色谱的方法,可以从兔血清中部分提取并纯化对氧磷酶。

有机磷缓蚀剂研究进展

论述了有机磷缓蚀剂的种类、合成方法及应用 。