基于4-羟基间苯二甲酸和含氮杂环配体的Zn(Ⅱ)配合物的合成、晶体结构与荧光性质研究

在水热法条件下,4-羟基间苯二甲酸(H 2HPHA)和锌离子分别与1,2二(吡啶-4-基)乙烯(dpee)及4,4′-联吡啶(4,4′-bpy)反应得到了2个三维的配位聚合物[Zn(HPHA)(dpee)·(DMA)2]n(配合物1)和[Zn(HPHA)2(4,4′-bpy)2·DMA]n(配合物2)。用X射线单晶衍射测定了配合物的晶体结构,结果显示:配合物1属于单斜晶系,C2空间群,每个不对称单元由一个锌离子,一个4-羟基间苯二甲酸配体及一个1,2-二(吡啶-4-基)乙烯组成;配合物2属于单斜晶系,P12/c1空间群,每个不对称单元由两个锌离子,两个4-羟基间苯二甲酸配体及两个4,4′-联吡啶配体组成。荧光光谱分析结果表明:配合物1的最强激发峰和发射峰在分别在251和397 nm,配合物2的最强激发峰和发射峰分别在415和513 nm。热重分析表明两个配合物在室温下稳定。

光催化水还原4-氯硝基苯制备4,4′-二氯氧化偶氮苯

以便宜无毒的水为还原剂,实现了4-氯硝基苯的还原,发展了1种合成4,4′-二氯氧化偶氮苯的绿色方法。反应在光照和无催化剂条件下进行,避免了传统工艺中加热和污染性还原剂及催化剂的使用。研究了多种条件对反应的影响.结果表明:1,4-二氧六环是最佳溶剂;在光功率和波长分别为75 W和365 nm时,目标产物的产率最高,达到92%。

糠醛渣活性炭对4,4′-硫代二苯酚和双酚F的吸附性能

以固废糠醛渣为原料,水蒸气活化法制备糠醛渣活性炭(FRAC),研究其对水体中4,4′-硫代二苯酚(TDP)和双酚F(BPF)的吸附性能,探讨了吸附时间、FRAC用量、pH值、温度以及TDP和BPF溶液的初始浓度对吸附过程的影响。研究结果表明:Sips和Koble-Corrigan等温模型可以很好地描述FRAC对TDP和BPF的吸附平衡数据,FRAC对TDP和BPF的吸附均是自发的放热过程。FRAC对TDP和BPF的吸附过程均符合准二级动力学模型。另外,TDP和BPF在FRAC上的吸附主要受到氢键、疏水作用、静电作用和π—π相互作用的共同影响。在298 K时,FRAC吸附TDP和BPF的最大吸附量分别为5.4083 mmol/g和3.6955 mmol/g,表明FRAC在处理内分泌干扰物废水上具有广泛的应用前景。

3,3',4,4'-联苯四胺改性邻苯二甲腈树脂及其复合材料性能

采用3,3',4,4'-联苯四胺(LBS)与联苯型邻苯二甲腈树脂(BPh)进行预聚反应制备改性联苯型邻苯二甲腈树脂预聚物(BLBS)。利用红外光谱法、差示扫描量热仪、旋转流变仪和热重分析对BLBS的固化行为、流变性能和耐温性能进行研究。结果表明,BLBS最低可在240℃前开始固化,但仍需要较高的温度才能固化完全;BLBS-3固化物在氮气和空气氛围中的质量损失5%时的温度(Td5)分别为549.4℃和555.6℃。石英纤维增强BLBS复合材料(QF/BLBS)具有优异的力学性能和耐热性能,玻璃化转变温度(T_(g))大于500°C,室温弯曲强度和层间剪切强度分别为711.5 MPa和48.5 MPa,400℃热处理2 h后弯曲强度和层间剪切强度分别为680.5 MPa和31.3 MPa。

新颖无限三股螺旋钴配位聚合物{[Co(4,4'-bipyridine)(4,4'azobispyridine)_2(NCS)_2]·H_2O}_n的合成、结构和性质的研究(英文)

The novel complex {[Co(bipy)(azpy)2(NCS)2]· H2O}n (where bipy=4,4′ bipyridine, azpy=4,4′ azobisp yridine) has been synthesized and characterized by elemental analyses, IR, UV, thermal analyses, and variable temperature magnetic susceptibility. The crystal (C32H26CoN12OS2, Mr=717.70) belongs to the orthorhombic, space group Pnna, a=2.21312(16)nm, b=1.40403(10)nm, c=1.14237(8)nm, V=3.5497(4)nm3, Z=4, Dc=1.343g· cm- 3, μ =0.645mm- 1, F(000)=1476, and final R1=0.0691, wR2=0.1129 for 231 parameters and 1674 observed reflections [I >2.00σ (I)]. The Co(Ⅱ) atom is, in a distorted octahedral geometry, coordinated by six nitrogen atoms from two bridging bipy, two monodentate azpy, and two thiocyanate groups. The bridging ligand bipy links Co(Ⅱ) atoms to form the infinite “ rod" with terminal coordination azpy ligand acting as sidearms. Unprecedented three parallel interpenetrating two dimensional (4,4) networks and novel infinite triple helices are formed via hydrogen bonding interactions. CCDC: 155588.

基于表面增强拉曼光谱技术测定聚亚苯基砜奶瓶中4,4′-联苯二酚的迁移量

目的基于Ag纳米粒子(Ag nanoparticles,AgNPs)的表面增强拉曼光谱(Surface enhanced Raman spectroscopy,SERS)技术,建立测定聚亚苯基砜奶瓶中4,4′-联苯二酚迁移量的方法。方法参照GB 31604.1—2015、GB 5009.156—2016,对聚亚苯基砜奶瓶中4,4′-联苯二酚的迁移行为进行研究,将获得的迁移液经0.22μm滤膜过滤后,与AgNPs混合,然后进行SERS测试,并采用高效液相色谱法(High performance liquid chromatography,HPLC)进行验证。结果所制备的AgNPs分布均匀、重现性好,针对4,4′-联苯二酚的最低检测质量浓度可达1 mg/L。在质量浓度范围1~50 mg/L内,1278 cm−1处的峰强度与4,4′-联苯二酚的浓度具有良好的线性关系,相关系数为0.9904。在聚亚苯基砜奶瓶中4,4′-联苯二酚的回收率为88.6%~92.8%,相对偏差为4.02%~6.50%,且与HPLC方法的结果基本一致。结论该方法具有快速、准确、操作简单等优点,可为食品接触材料及制品中的4,4′-联苯二酚检测提供技术参考。

农药关键中间体4,4'-联吡啶的合成研究

4,4'-联吡啶不仅是金属催化反应中的重要有机配体,更是高效除草剂百草枯的原料和中间体。以吡啶为原料,使用Cu/Beta催化剂氧化偶联生成4,4'-联吡啶,并考察了不同的催化剂载体、金属铜负载量、溶剂和反应温度对反应的影响。实验结果表明:选择吡啶作为原料、6%Cu/Beta作为催化剂、二甲基亚砜作为反应溶剂、100℃、12 h是合成4,4'-联吡啶最佳反应条件,转化率为94.3%,选择性是96.7%。

3,3’,4,4’-联苯四甲酸合成用Pd/C催化剂制备工艺研究

采用浸渍沉淀法制备3,3’,4,4’-联苯四甲酸合成用Pd/C催化剂,考察不同沉淀剂、还原剂对Pd/C催化剂性能的影响,发现使用不同沉淀剂和还原剂时,催化剂活性及3,3’,4,4’-联苯四甲酸收率存在明显差异,硼氢化钠还原的Pd/C催化剂活性及3,3’,4,4’-联苯四甲酸收率最高。进一步考察助金属协同催化作用对Pd/C性能的影响,结果表明,Pd/C中添加质量分数1.0%Mn后催化剂活性及3,3’,4,4’-联苯四甲酸收率均有所提高。

超高效液相色谱-串联质谱法测定牛奶中4,4'-硫代二苯酚残留量

建立牛奶中4,4'-硫代二苯酚残留量的超高效液相色谱-串联质谱检测方法。用乙腈将牛奶中4,4'-硫代二苯酚全部提取,加入氯化钠去除脂类物质,用固相萃取柱去除杂质,采用超高效液相色谱-串联质谱仪检测4,4'-硫代二苯酚,以外标的方式进行定量。结果显示,4,4'-硫代二苯酚标准品的质量浓度在1.0~20.0 ng/mL范围内线性关系良好,相关系数r大于0.99。样品中4,4'-硫代二苯酚的检出限为0.5μg/kg,定量限为1.0μg/kg。在空白牛奶中添加4,4'-硫代二苯酚,质量浓度在1.0~5.0μg/kg范围内,回收率均在60%~90%之间,计算得出相对标准偏差(RSD)均小于10%。该方法具有检测限低、回收率高、定性准确等优点,适用于牛奶中4,4'-硫代二苯酚残留量的检测。

Synthesis and Crystal Structure of a Cu(Ⅱ) Complex with Reduced Schiff-base N-(2-Hydroxybenzyl)-D,L-alanine and 4,4'-Bipyridine

A new complex [Cu2（sala）2（H20）2（4,4＇-bipy）]＇H20 （sala = N-（2-hydroxybenzyl）- D,L-alaninate, 4,4＇-bipy = 4,4＇-bipyridine） has been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. The complex crystallizes in monoclinic system, space group C2/c with a = 42.44（3）, b = 10.416（8）, c = 15.487（13） ./k, fl = 97.455（14）°, C30H36Cu2N4O9, Mr = 723.71, V = 6789（9） A3, Dc = 1.416 g/cm3, Z = 8, F（000） = 2992, μ（MoKa） = 1.308 mm-1, R = 0.0493 and wR = 0.1004 for 4878 observed reflections （I 〉 2σ（I））. Structural analysis shows that each copper（II） atom displays a distorted square-based pyramidal coordination geometry with two oxygen atoms and one nitrogen atom from one N-（2-hydroxybenzyl）-D,L-alaninate, one nitrogen atom from 4,4＇-bipyridine ligand and one water molecule. 4,4＇-Bipyridine ligand bridges two Cu（II） ions to form a dinuclear compound. The molecular structure is extended into a one-dimensional wavy chain through hydrogen bonds. These 1D chains are further expanded into 2D networks through hydrogen bonds.

Synthesis, Structure and Luminescent Property of a New Zn(Ⅱ) Coordination Polymer Based on 1,3,5-Benzenetricarboxylate and 4,4'-Bipyridine Ligands

A new Zn（II） coordination polymer [Zn3（BTC）2（4,4＇-bpy）（CO）2]n （1, H3BTC = 1,3,5-benzenetricarboxylic acid, 4,4＇-bpy = 4,4＇-bipyridine） has been prepared through urothermal reaction of zinc nitrate hexahydrate with 1,3,5-benzenetricarboxylic acid and 4,4＇-bipyridine, and characterized by elemental analysis, IR spectroscopy, TGA and powder XRD, and its crystal structure was determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in the monoclinic system, space group C2/c, with a = 10.262（3）, b = 18.838（5）, c = 15.083（4）/k, fl = 99.203（4）°, V = 2878.3（14） A3, C30H14Zn3N2O14, Mr= 822.54, Z = 4, Dc = 1.898 g/cm3,μ = 2.561 mm-1,F（000） = 1640, R = 0.0363 and wR = 0.0932 for 2828 observed reflections （I 〉 2σ（I））. X-ray analysis shows that the asymmetric unit of the title compound contains two crystallographically unique Zn（lI） atoms which are connected by BTC3- ligands and 4,4＇-bpy coligands to form a 3D framework with 1D channels. The solid luminescence of ligand and the title complex was also studied at room temperature.

超高效液相色谱法测定食品接触材料制品中1,1′-磺酰基二(4-氯苯)和4,4′-联苯二酚的迁移量

参考GB 5009.156-2016和GB 31604.1-2015,以水、4%(体积分数)乙酸溶液、10%(体积分数)乙醇溶液、20%(体积分数)乙醇溶液、50%(体积分数)乙醇溶液、95%(体积分数,下同)乙醇溶液、异辛烷等食品模拟物浸泡聚苯砜材质的水杯、奶瓶、螺纹口和涂层罐,前5种食品模拟物的浸泡液直接过0.22μm滤膜,滤液采用超高效液相色谱法(UHPLC)分析。分取95%乙醇溶液和异辛烷浸泡液各10mL,于50℃,5 000Pa条件下旋转蒸发至近干,用70%(体积分数)甲醇溶液溶解、定容至10mL,过0.22μm滤膜,滤液采用UHPLC分析。以ACQUITY UPLC BEH C18色谱柱作固定相,以不同体积比甲醇和水的混合溶液作流动相进行梯度洗脱,在检测波长247nm下进行检测。结果显示,7种食品模拟物中的两种目标物可在6.500min以内实现完全分离,其中1,1′-磺酰基二(4-氯苯)和4,4′-联苯二酚的质量浓度分别在0.03~0.40mg·L^(-1)和0.3~4.0mg·L^(-1)内与峰面积呈线性关系,测定下限(10S/N)分别为0.015~0.030 mg·kg^(-1)和0.023~0.030mg·kg^(-1);3个浓度水平下的加标回收率为89.0%~110%,测定值的相对标准偏差(n=6)为1.9%~6.7%;方法用于10批实际样品的分析,两种目标物的测定值均小于测定下限,符合GB4806.6-2016和GB 9685-2016的特定迁移限量要求。

In situ Alkylation of 4,4'-Bipyridine in Hydrothermal Synthesis of an Iodoplumbate Inorganic-organic Hybrid with Fluorescence

A novel 1-D iodoplumbate hybrid, 2（Pb3I9）^3＊·3（C14H18N2）^2＋ 1, has been hydrothermally synthesized and characterized by IR spectra, TGA and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic, space group P21/c, with a = 12.057（2）, b = 14.024（3）, c = 24.742（5） A, β = 90.48（3）°, V = 4183.6（14） A^3, Z = 4, R= 0.0477 and wR = 0.0800. The title compound consists of 1-D chains （Pb3I9）n^3n＊ parallel to the [100] direction and stacks of alkylated 4,4＇-bipyridium cations running along the [011] direction. Each anionic chain is surrounded by six arrays of alkylated 4,4＇-bipyridium cations through extensive C-H…I atypical hydrogen-bonding interactions to afford an interesting 3-D supramolecular network. Significant fluorescent property of the compound was observed at room temperature.

Synthesis and Crystal Structure of a One-dimensional Silver(I) Coordination Polymer with 4,4'-Bipyridine

The title compound, { [Ag2（bipy）2（H2O）2]·pydc·2H2O}n （bipy = 4,4＇-bipyridine, pydc = pyridine-3,5-dicarboxylate）, has been synthesized by the reaction of Ag2O with pydc and bipy in CH3OH solution. It crystallizes in the monoclinic system, space group C2/c with a = 21.419（8）, b = 7.515（3）, c = 18.070（7） A,β = 108.273（6）°, Mr = 765.27, V = 2761.9（17） A^3, Z = 4, Dc = 1.840 g/cm^3, F（000） = 1528,μ = 1.478 mm^-1, the final R = 0.0307 and wR = 0.0681. The structure determined demonstrated that the Ag（I） is three-coordinated by two nitrogen atoms from bipy and one water molecule, forming a one-dimensional coordination polymer [Ag2（bipy）2（H2O）2]n^2n＋, which is further linked to generate a two-dimensional layer structure via Ag---Ag attractions.

4,4'-二氨基二苯醚合成技术研究进展

4,4’-二氨基二苯醚是重要的高分子单体,用于制备正处于成长期的聚酰亚胺等树脂。综述了4,4’-二氨基二苯醚的合成路线,分析了各种方法的利弊,首选的工业方法是4,4’-二硝基二苯醚催化加氢。重点介绍镍基催化剂、连续催化加氢和ODA精制的新进展。今后的开发重点是优化精制工艺,提升产品品质,开发非贵金属加氢催化剂,实现连续催化加氢,降低生成成本。

4,4′-二(羟甲基)联苯的合成、表征与机理探究

4,4′-二(羟甲基)联苯是一种重要的化工原料,可用于合成高附加值的有机化合物或新型功能性材料。由于其特殊的结构和性质,4,4′-二(羟甲基)联苯在许多领域都具有广泛的应用和重要性。以4,4′-二(氯甲基)联苯为原料,经水解生成苄醇类化合物4,4′-二(羟甲基)联苯。采用1 H NMR,IR和HPLC对产物进行了表征,讨论了溶剂、水解剂、配料比、反应温度、反应时间和催化剂种类对产物含量和收率的影响。优化了4,4′-二(羟甲基)联苯的合成工艺,提出了可能的催化合成反应机理。结果表明:聚乙二醇作为催化剂,可与溶液中的阳离子发生络合,增强了亲核试剂的反应活性,提高了反应速率。在以PEG-600为催化剂,乙腈为溶剂,KOH为水解剂,配料比n(BCMBP)∶n(KOH)=1.0∶3.0,V(乙腈)∶V(H 2 O)=10∶1,78℃反应12 h的优化工艺下,粗产品HPLC含量可达97.2%(质量分数,下同),收率为93.9%。

THE STUDY OF ADSORPTION MODEL FOR 4,4'-BIPYRIDINE ADSORBED AT THE CHEMICALLY DEPOSITED SILVER FILM BY SERS

This paper presents the SERS spectru spectrum of 4,4′-bipyridine adsorbed at the chemically deposited silver filem.Comparing with the normal Raman spectra of 4,4′-bipyridine in the solid state and in 0.5 mol/L methanol solution ,we have studied the SERS spectrum and further discussed the adsorption model for 4,4′-bipyridine adsorbed at the chemically deposited silver film,and also explained the experimental results with image field mode,Experimental results show that 4,4′-bipyridine adsorbed at the chemically deposiled silver ilm via N-atom of pyridinering (Upright).

A Cadmium(II) Coordination Polymer: Crystal Structure and Fluorescent Property of [CdCl_2(4,4'-bipyridine)]_ ∞

The reaction of L-histidine, CdCl22.5H2O and 4,4-bipyridine in methane/water gave rise to a two-dimensional coordination polymer [CdCl2(4,4-bipyridine)] which has been characterized by single-crystal X-ray diffraction. The polymer crystallizes in the orthorhombic sys- tem, space group Cmmm with a = 12.083(7), b = 11.771(7), c = 3.781(2) ? V = 537.8(6) ?, Z = 2, C10H8N2CdCl2, Mr = 339.48, Dc = 2.097 g/cm3, F(000) = 328 and (MoK? = 2.490 mm-1. The final R = 0.0658 and wR = 0.1398 for 257 observed reflections with I≥2(I).

基于4,4’-偶氮苯二甲酸的金属-有机框架合成及其荧光性质

分别以吡嗪和4,4’-联吡啶为共配体,Cd^(2+)、Zn^(2+)与4,4’-偶氮苯二甲酸(H 2(4,4’-azo))配位反应得到了两个金属-有机框架(MOFs)。X射线单晶衍射研究结果表明,其结构中均不含共配体,与之前报道的[Cd(4,4’-azo)(H 2 O)]n(1)和[Zn(4,4’-azo)(H 2 O)2]n(2)的晶体结构一致。将共配体变为几何尺寸更长的1,3-二(四吡啶基)丙烷(bpp),金属离子变为Co^(2+),合成了一个共晶[H 2(4,4’-azo)(bpp)]n(3),其为单斜晶系,C2/c空间群,晶胞参数:a=3.2168(19)nm,b=0.4755(3)nm,c=1.8732(14)nm。用热重分析仪和荧光分光光度计分别研究了三个化合物的热稳定性和两个MOFs的发光性质。1和2都具有优异的热稳定性,尤其是2的初始失重温度高达247℃。由于1是由4,4’-azo双齿配位两个Cd^(2+)形成双核3D网络结构,而2是4,4’-azo单齿配位Zn^(2+)形成的1D“zig-zag”链,两者的紫外光谱和荧光光谱不同。2除具有配体固有的荧光发射(359 nm)外,由于Zn^(2+)与4,4’-azo配位后产生的配体到金属的电荷跃迁(LMCT),还在420 nm处新增一个增强的荧光发射峰。