硒催化羰基化合成甲苯-2,4-一氨基甲酸甲酯

报道了一种绿色、简易的合成甲苯-2,4-二氨基甲酸甲酯的方法.以廉价易得的非金属硒作催化剂,CO作羰基化试剂,通过硒催化2,4-二氨基甲苯和甲醇在一氧化碳和氧气存在下经“一锅法”的氧化羰基化反应来直接合成目标产物甲基-2,4-二氨基甲酸甲酯.并提出了硒催化羰基化合成甲苯-2,4-二氨基甲酸甲酯的机理.     

Synthesis of 2,4-dibromo-5-fluorobenzonitrile

2,4-Dibromo-5-fluorobenzonitrile has been synthesized for the first time (81.5% yield). It may be used in synthesizing 2,4-dibromo-5-fluorobenzoic acid, the intermediates of fluoroquinolones. The ammoxidation procedure for preparation of the nitrile has been described in detail. Zheng Qiong: born in 1945, Associate professor     

Yb(OTF)3催化2,4-二氨基甲苯与碳酸二甲酯甲氧羰基化合成2,4-甲苯二氨基甲酸甲酯

研究了Yb（OTF），催化剂对2，4-二氨基甲苯（TDA）与碳酸二甲酯甲氧羰基化反应合成2，4-甲苯二氨基甲酸甲酯（TDC）的催化活性，考察了反应温度和反应时间对Yb（OTF），催化活性的影响。在该催化剂的作用下，反应温度453K，反应时间5h时TDA转化率可达100％，TDC的产率达到23、6％，同时考察了Yb（OTF）3催化剂的寿命，经4次重复使用催化剂基本不失活。Ln（OTF）3（Ln=La，Nd，Yb）催化活性的比较表明催化剂Lewis酸性的强弱与TDC的产率成正比。     

氧气浓度对EB法处理2，4-D的影响

通过高能电子束辐照(high-energy electron beam,EB)法研究了氧气浓度对2,4-D降解的影响,结果表明:与饱和空气条件下对比,辐照过程中充入氧气明显提高2,4-D的降解效率,在饱和氧气和4kGy的辐照剂量条件下,2,4-D去除率达到92.5%,Cl-释放量为30.0～35.4mg/L,TOC去除率为22.9%.辐照过程中溶液的pH值与辐照剂量和氧气浓度关系不明显,均由9降为4左右.     

流动注射-鲁米诺-铁氰化钾化学发光体系测定环境水体中痕量2,4-二氯苯酚

基于中性介质中,2,4-二氯苯酚对鲁米诺-铁氰化钾化学发光体系有明显的增敏作用,提出了流动注射化学发光法测定痕量2,4-二氯苯酚的方法.在优化的试验条件下,2,4-二氯苯酚的化学发光强度与其浓度在1.0×10-7~1.0×10-5 mol/L范围内呈线性关系,方法的检出限(3S/N)为1.060×10-8 mol/L.对浓度为1.0×10-5mol/L2,4-二氯苯酚溶液连续测定11次,测定值的相对标准偏差为2.1%.取工业废水水样,经固相萃取后用该法测定其中痕量2,4-二氯苯酚含量,同行业推荐标准方法对比,结果相近.     

分光光度法测定2，4-二羟基二苯甲酮的含量

建立了测定2,4-二羟基二苯甲酮含量的分先先度法。实验表明,在pH为10的B—R缓冲溶液中,2,4-二羟基二苯甲酮在404nm波长下有最大吸收,8=4．36×10^4L／（m01．em）．于1．0×10^-5mol／L～3．0×10^-4mol／L范围内其吸光度与浓度呈良好的线性关系,其线性回归方程为A=0．4361×10^4c（mol／L）＋0．0083,相关系数为r=0．9996．用加入回收法进行试验,回收率为98．1％～104.7％．     

Characterization of nanoscale iron and its degradation of 2,4-dichlorophenol

Nanoscale iron was detected by TEM, X-ray diffraction and X-ray photoelectron spectroscopy. It was found that the size of the nanoscale iron particles is in the range of 30–40 nm according to TEM image, and it contains abundant Fe₃O₄ as passivating layers on the surface of the core-shell structure. To improve its performance, dilute HCl was used for the removal of the passivating layers, and the degradation of 2,4-dichlorophenol (2,4-DCP) was measured for the nanoscale iron samples treated and untreated. Experimental results demonstrated that the removal of 2,4-DCP by untreated nanoscale iron is mainly due to the adsorption of 2, 4-DCP by nanoscale iron, and there are no degradation products detected by HPLC in the process. However, excellent dechlorination of 2,4-DCP was gained by HCl-treated nanoscale iron, and 2-chlorophenol, 4-chlorophenol and phenol were detected during the process. It was concluded that dechlorination is the key reaction pathway for the degradation of 2,4-DCP by activated nanoscale iron, and phenol is found to be the main product.     

2，4-二羟基苯乙酮缩氨基硫脲的微波固相合成及晶体结构

用2,4-二羟基苯乙酮和氨基硫脲为原料,在微波辅助作用下固相合成了2,4-二羟基苯乙酮缩氨基硫脲,利用红外光谱及单晶X射线法对目标化合物进行了表征,该化合物为单斜晶系,空间群为C2／c,晶体学参数n=2．0900（2）nm,b=0．79290（8）nm,c=1．32481（14）nm;β=100．2090（10）°;F（000）=944,Z=8,V=2·1607（4）nm3,Dc=1．365g·cm^-3,Mr=225．27,最终结构偏离因子R=0．0460,Rw=0．1309,S=1．031,最终差值电子密度的最大值和最小值分别为401nm^-3。和-247nm^-3．     

Detection of 2,4-dinitrotoluene using hydrogen-bond acidic polymer coated SAW sensor

A strong hydrogen-bond acidic （HBA） polymer linear fluoroalcoholic polysiloxane （PLF）, synthesized by one-step hydrosilylation, was introduced for 2,4-dinitrotoluene （2,4-DNT） detection using surface acoustic wave （SAW） devices. FT-IR spectra and 1H NMR spectra char- acterizations confirmed its molecular structure. Then, PLF was dissolved in chloroform, and spray coated onto a 434 MHz SAW device. And subsequently, the sensitivity and selectivity of the fabricated sensor were studied based on a SAW test platform. To 2,4-DNT of 1 ppm and 100 ppb （for DNT, 1 ppm = 8.1 mg/m3; 1 ppb = 8.1 ;tg/m3）, the responses of the sensor rose 7.7 and 1.5 kHz, respectively. Furthermore, compared with some common interference vapors at 10 mg/m3, the response of the sensor to 2,4-DNT at 1 ppm was 5 times stronger. The sensitive property was attributed to the hydrogen bond interaction between the hexafluoroisopropanol （HFIP） group in PLF and the basic lone electron pairs of nitro-groups in 2,4-DNT. Comparison between the PLF sensor and hydroxyl group functionalized polymer （carbowax and MOBCD）-coated sensors was investigated, and the results showed that the PLF sensor exhibited better sensitivity. In a word, the PLF sensor exhibited fast response, negligible baseline drifts and excellent reversibility, indicating good candidates of HFIP group functionalized HBA polymers for practical nitroaromatic explosives detection.     

气相色谱-质谱联用仪测定柑橘类水果中2,4-滴的 残留量

建立一种用气相色谱质谱联用仪（GC-MS）测定柑橘类水果中2,4-滴残留量的方法。 在酸性条件下采用乙醚提取,硫酸作为催化剂,用正丁醇将2,4-滴衍生成2,4-滴丁酯,使用气相色 谱-质谱联用仪测定柑橘中2,4-滴的残留量（外标法定量）。结果表明,2,4-滴在0～0.5 µg/mL范 围内线性良好,相关系数（R2 ）大于0.999,方法检出限为0.002 5 mg/kg,定量限为0.005 mg/kg。对沃 柑分别添加 0.005、0.01 和 0.1 mg/kg 3 个水平的 2,4-滴进行加标回收试验,回收率为 86.61%～ 99.32%,相对标准偏差为2.08%～4.46%（n = 6）。该方法灵敏度高,回收率稳定,定性定量准确,适 用于柑橘类水果中2,4-滴的测定。     

竹炭对溶液中2,4-二硝基氯苯的吸附与回收研究

本研究了竹炭对溶液中2,4-二硝基氯苯（CDNB）的吸附行为。研究确定竹炭对CDNB的吸附平衡时间、最佳吸附pH以及吸附温度、吸附剂用量等因素对吸附效果的影响。实验结果表明：CDNB初始浓度c0=0.05mg/mL,T=298K,pH=5.0,吸附时间t=12h时,竹炭对CDNB的吸附率E可达到97.6%;用乙醇作洗脱再生剂,洗脱率可达95.2%;且脱附的CDNB可用蒸馏重结晶法回收,回收率可达86.4%。因此,竹炭是废水中CDNB吸附处理的材料。     

3-O-烯丙基-6-O-乙酰基-2,4-二-O-苯甲酰基-α-D-葡萄吡喃糖基三氯乙酰亚氨酯的合成

以3-O烯丙基葡萄糖1为原料,设计合成了尚未见报道的3-O烯丙基6-O乙酰基2,4二O苯甲酰基αD葡萄糖三氯乙酰亚氨酯7.其组成和结构已由元素分析、IR、1HNMR和13CNMR表征.     

纳米铁系金属制剂用于类Fenton氧化降解2,4-二氯苯酚

研究了3种纳米铁系金属制剂(nZVI、nZVI/Ni、nZVI/Pd)在类Fenton氧化法中对水中2,4-二氯苯酚(2,4-DCP)降解效率的影响,同时与纳米铁系金属制剂还原脱氯降解2,4-DCP效果比较.结果表明:1.0 g· L-1 Fe、100 mg·L-12,4-DCP,反应180 min,nZVI,nZVI/Ni,nZVI/Pd和Fe2+对水中2,4-DCP去除率分别为6.48％,6.80％,15.95％和5.02％;而在类Fenton氧化法中,nZVI,nZVI/Ni,nZVI/Pd和Fe2+对2,4-DCP去除率分别是57.87％,34.23％,27.94％和19.61％,清楚表明纳米双金属有催化还原脱氯活性,但在类Fenton法中,由于纳米双金属的催化活性导致H2O2分解,使得nZVI更有利于类Fenton氧化降解2,4-DCP.SEM、EDS和XRD表征说明:由于Fe2+溶出,nZVI在类Fenton反应前后的表面微观结构发生微小变化;FTIR与TOC(矿化率30.71％)结果进一步证明2,4-DCP被氧化降解.此外,条件实验发现pH和2,4-DCP初始质量浓度对类Fenton法降解2,4-DCP有较大的影响,其氧化降解过程符合伪一级动力学,是一个扩散控制过程.     

Dechlorination of 2,4-dichlorophenol by nickel nanoparticles under the acidic conditions

Metal nanoparticles are effective for remediation of contamination with a range of compounds including chlorinated organics.However,the sorption process of the passivation oxide layers on the metal nanoparticle surfaces may result in incomplete degradation of contaminants.This phenomenon can be prevented by an acidic washing procedure or reaction in an acidic medium.In this paper,nickel nanoparticles manufactured via the carbonyl powder process were analyzed using scanning electron microscopy,transmission electron microscopy,X-ray diffraction and energy-dispersive X-ray spectroscopy.The sorption and degradation of 2,4-dichlorophenol (2,4-DCP) by nickel nanoparticles under acidic conditions was then investigated.Transmission electron microscopy and XRD results showed that the nickel nanoparticles range in size from 10 to 20 nm,and a thin passivation layer of NiO is present on the surface.This oxide layer can be removed by pretreatment washing with acidic solutions.It was indicated that dechlorination was the key reaction pathway for degradation of 2,4-DCP by nickel nanoparticles under acidic conditions.The main degradation products were 4-Chlorophenol,2-Chlorophenol,and Phenol,and among these,Phenol was dominant.The acidic medium promoted degradation by providing an appropriate pH,and H+ may be involved in the reaction.Dechlorination of 2,4-DCP by nickel nanoparticles under the acidic condition follows the second order kinetic model,and the rate constants at 298,306,316 K are 0.02,0.2 and 0.3 (g L h)-1,respectively.     

生物淋洗法修复2,4-DNT-3-SA污染土壤

采用静态生物淋洗法处理含2,4-二硝基甲苯-3-磺酸钠(2,4-DNT-3-SA)的土壤。考察供氧条件、土水比及温度对2,4-DNT-3-SA去除效果的影响,结果表明,在好氧、37oC、土水比为10:5的条件下,2,4-DNT-3-SA去除率最高,达到98.75%。采用高通量测序法分析土壤中微生物菌落结构及多样性,结果表明,土壤中的优势菌属主要为假单胞菌属、鞘脂菌属和芽孢乳杆菌属。     

A new technique for synthesis of 2,4-dichloro-thieno[3,2-d]pyrimidine

3-Amino-2-methoxycarbonylthiophene used as the main raw material,an intermediate(thiofuran siamese) 2,4-dichloro-thieno[3,2-d]pyrimidine was synthesized.The prod-uct was characterized by nuclear magnetic resonance(NMR).The first step yield was 84%(190 ℃) and the second step yield was 81.4%(105 ℃,m(intermediate):m(phosphorus oxychloride) = 1:6.4).The raw product was refined with a unique refining process,which can enhance the purity up to 99.5% to meet the requirement of condi-tions for the development and research of thiofuran siamese as a new medicine of anticarcinogen.Contrasted with the traditional technique,this process featured with cheap raw materials,possible for solvent recovery and reuse,low comprehensive cost,and suit-able for production on certain scale.     

十二烷基苯磺酸纳改性的镁铝水滑石吸附2,4-D除草剂的性能研究

采用共沉淀法合成了镁铝摩尔比分别为2∶1、3∶1、4∶1的镁铝水滑石.利用十二烷基苯磺酸钠对其进行改性,并研究了改性前后水滑石对2,4-D除草剂的吸附性能.实验结果表明:改性后水滑石的对2,4-D的吸附量增加了5-9倍.     

基于磁性荧光双探针基础上的2,4-二氯苯氧乙酸残留的快速免疫检测体系的建立(英文)

建立了一个基于磁性荧光双探针基础上的免疫快速检测体系,以实现液相中快速检测食品中2,4-二氯苯氧乙酸(2,4-D)残留.该体系将2,4-D抗体结合Fe3O4@SiO2-NH2得到的复合物作为磁性探针和固相载体,2,4-D-OVA被标记CdTe@SiO2-NH2作为荧光探针以产生荧光信号,通过荧光探针与磁性探针复合物与2,4-D抗体竞争结合实现免疫快速检测.探讨了荧光探针最佳优化条件,在p H值8.2,2,4-D-OVA加入量为500μL,偶联时间为70 min时,偶联得到的荧光信号最强,双探针检测后得到该检测体系最低检测限为3.55×10-8.得到金磁、量子点荧光双探针免疫系统,绘出标准曲线,得到最低检测限达3.55×10-8.该检测体系与传统ELISA方法相比,可以大大缩短检测时间,放大检测信号.     

油菜BnCYP83B1基因的克隆与生长素相互作用的研究

为了探寻油菜BnCYP83B1基因的序列特征以及是否在IAA生长素代谢途径中发挥作用.采用克隆测序技术获得BnCYP83B1基因序列,编码区序列全长1500bp,编码一个含有499个氨基酸残基的蛋白质,全长基因内含有一个152bp的非正常剪接GU-AG内含子.采用Real-time PCR技术检测经2,4-D生长素类似物处理的油菜种子内BnCYP83B1基因的表达水平,发现在2,4-D处理下与对照相比存在显著的表达差异.BnCYP83B1基因可能拥有其他十字花科植物相同的功能极其可能在IAA代谢中发挥重要作用.     

2，4－二硝基苯肼法对三种蔬菜维生素 C 含量的测定

采用2,4－二硝基苯肼法,测定了西红柿、甘蓝、青椒三种蔬菜中维生素 C 的含量．在波长500 nm 处,蔬菜维生素 C 提取液吸光度达到最大值的条件是：水浴时间3 h、活性炭用量1．0 g 和温度37℃,为最佳测定条件．西红柿、甘蓝、青椒提取液维生素 C 质量浓度与吸光度的线性回归方程分别为 y ＝0．0215x ＋0．0785,y ＝0．0206x ＋0．0703,y ＝0．0201 x ＋0．0716;相关系数分别为 r2＝0．9959,r2＝0．9993,r2＝0．9977．西红柿、甘蓝、青椒中维生素 C 含量的测定结果分别为为4．07g ／kg、3．94 g ／kg、7．18 g ／kg．