Sonication-Assisted Synthesis of Bimetallic Hg/Pd Alloy Nanoparticles for Catalytic Reduction of Nitrophenol and its Derivatives

In this article, we report a facile approach for the synthesis of an inexpensive catalyst of bimetallic Hg/Pd alloys comprising nanoparticles with various structures using a unique ultrasonic reaction that is conducted without the use of any reducing agent. The nanoparticles of Hg/Pd alloys (HgPd and Hg₂Pd₅) were achieved for the first time by sonicating an aqueous solution of Palladium (II) nitrate with metallic liquid mercury, as evidenced by XRD. EDS further confirmed the presence of Pd and Hg elements in the alloy. The surface morphology and structure of the nanoparticles have been systematically investigated by HRSEM, HRTEM and SAED pattern. In order to explore the catalytic activity of the as-synthesized nanoalloys, the catalytic reduction of 4-nitrophenol and a few other nitrophenol derivatives were investigated. Excellent catalytic activity was obtained for Hg/Pd (1:1) alloy, and the rate constant for the reduction of 4-NP with Hg/Pd at room temperature was found to be 58.4 × 10⁻³ s⁻¹, which is possibly the highest ever reported. The catalyst exhibited superior stability and reusability when compared with those reported in the literature for other catalysts based on noble metals.     

Mechanism of Iodine(III)-Promoted Oxidative Dearomatizing Hydroxylation of Phenols: Evidence for a Radical-Chain Pathway

The oxidative dearomatization of phenols with the addition of nucleophiles to the aromatic ring induced by hypervalent iodine(III) reagents and catalysts has emerged as a highly useful synthetic approach. However, experimental mechanistic studies of this important process have been extremely scarce. In this report, we describe systematic investigations of the dearomatizing hydroxylation of phenols using an array of experimental techniques. Kinetics, EPR spectroscopy, and reactions with radical probes demonstrate that the transformation proceeds by a radical-chain mechanism, with a phenoxyl radical being the key chain-carrying intermediate. Moreover, UV and NMR spectroscopy, high-resolution mass spectrometry, and cyclic voltammetry show that before reacting with the phenoxyl radical, the water molecule becomes activated by the interaction with the iodine(III) center, causing the Umpolung of this formally nucleophilic substrate. The radical-chain mechanism allows the rationalization of all existing observations regarding the iodine(III)-promoted oxidative dearomatization of phenols.     

Amphiphilic poly(ionic liquid)/Wells–Dawson-type phosphovanadomolybdate ionic composites as efficient and recyclable catalysts for the direct hydroxylation of benzene with H2O2

Three novel amphiphilic poly(ionic liquid) (PIL)/Wells–Dawson-type phosphovanadomolybdate (V-POM) ionic composites with tunable oxidative catalytic activity and unique nanostructure were synthesized using carboxylic acid-functionalized PIL and H₇[P₂Mo₁₇VO₆₂], H₈[P₂Mo₁₆V₂O₆₂] and H₉[P₂Mo₁₅V₃O₆₂] as synthetic units via self-assembly in water. The results of characterization indicated that V-POM anions were finely dispersed in the PIL cation framework, and their structures were well preserved. The three composites are amorphous V-POM salts of PIL cation with a considerable thermal stability, and an open three-dimensional network structure with hierarchical porosity. The as-synthesized composites were found to be efficient heterogeneous catalysts for the direct hydroxylation of benzene to phenol with H₂O₂ in the liquid phase. Under optimum conditions, a phenol yield of 37.3% was achieved with selectivity of 100%. The high catalytic performance could be attributed to the synergistic catalytic effect between V-POM anion and carboxylic acid-functionalized PIL cation framework, and good benzene adsorption and phenol desorption ability of amphiphilic micropores in the structure of the composites. Additionally, these composites exhibited high stability under the reaction conditions and could be easily recovered and reused at least six times without noticeably loss of activity.     

Improving efficiency for removal of ammoniacal nitrogen from wastewaters using hydrodynamic cavitation

The present study reports significant improvements in the removal of ammoniacal nitrogen from wastewater which is an important problem for many industries such as dyes and pigment, distilleries and fisheries. Pilot plant studies (capacity, 1 m³/h) on synthetic wastewater using 4-amino phenol as model nitrogen containing organic compound and two real industrial effluents of high ammoniacal nitrogen content were carried out using hydrodynamic cavitation. Two reactor geometries were evaluated for increased efficiency in removal-orifice and vortex diode. Effect of initial concentration (100–500 mg/L), effect of pressure drop (0.5–5 bar) and nature of cavitating device (linear and vortex flow for cavitation) were evaluated along with effect of salt content, effect of hydrogen peroxide addition and aeration. Initial concentration was found to have significant impact on the extent of removal: ~ 5 g/m³ removal for initial concentration of 100 mg/L and up to 12 g/m³ removal at high concentration of 500 mg/L. Interestingly, significant improvement of the order of magnitude (up to 8 times) in removal of ammoniacal nitrogen could be obtained by sparging air or oxygen in hydrodynamic cavitation and a very high removal of above 80% could be achieved. The removal of ammoniacal nitrogen by vortex diode was also found to be effective in the industrial wastewaters and results on two different effluent samples of distillery industry indicated up to 75% removal, though with longer time of treatment compared to that of synthetic wastewater. The developed methodology of hydrodynamic cavitation technology with aeration and vortex diode as a cavitating device was found to be highly effective for improving the efficiency of the conventional cavitation methods and hence can be highly useful in industrial wastewater treatment, specifically for the removal of ammoniacal nitrogen.     

浊点萃取-荧光光度法测定水中的苯酚

基于非离子表面活性剂Triton X-100,以浊点萃取结合荧光光度法测定水中的苯酚,考察影响浊点萃取的各种因素。在pH=3.0的磷酸氢二钠-磷酸二氢钾缓冲溶液中,采用2.0mL Triton X-100(5%)、82℃平衡温度、8min平衡时间的条件下,苯酚被萃取到Triton X-100表面活性剂相与水相分开,用于环境水样中苯酚的测定,结果令人满意。     

Dendrimers Functionalized with Palladium Complexes of N-, N,N-, and N,N,N-Ligands

Pyridine, pyridine imine, and bipyridine imine ligands functionalized by a phenol have been synthesized and characterized, in many cases by X-ray diffraction. Several of these N-, N,N-, and N,N,N,-ligands have been grafted onto the surface of phosphorhydrazone dendrimers, from generation 1 to generation 3. The complexation ability of these monomers and dendrimers towards palladium(II) has been assayed. The corresponding complexes have been either isolated or prepared in situ. In both cases, the monomeric and dendritic complexes have been tested as catalysts in Heck couplings and in Sonogashira couplings. In some cases, a positive dendritic effect has been observed, that is, an increase of the catalytic efficiency proportional to the dendrimer generation.     

Proteome profile of salt gland‐rich epidermis extracted from a salt‐tolerant tree species

Preparation of proteins from salt‐gland‐rich tissues of mangrove plant is necessary for a systematic study of proteins involved in the plant's unique desalination mechanism. Extraction of high‐quality proteins from the leaves of mangrove tree species, however, is difficult due to the presence of high levels of endogenous phenolic compounds. In our study, preparation of proteins from only a part of the leaf tissues (i.e. salt gland‐rich epidermal layers) was required, rendering extraction even more challenging. By comparing several extraction methods, we developed a reliable procedure for obtaining proteins from salt gland‐rich tissues of the mangrove species Avicennia officinalis. Protein extraction was markedly improved using a phenol‐based extraction method. Greater resolution 1D protein gel profiles could be obtained. More promising proteome profiles could be obtained through 1D‐LC‐MS/MS. The number of proteins detected was twice as much as compared to TUTS extraction method. Focusing on proteins that were solely present in each extraction method, phenol‐based extracts contained nearly ten times more proteins than those in the extracts without using phenol. The approach could thus be applied for downstream high‐throughput proteomic analyses involving LC‐MS/MS or equivalent. The proteomics data presented herein are available via ProteomeXchange with identifier PXD001691.     

异质结Bi_2WO_6/ZnO复合光催化剂的制备及其光催化降解含酚废水的研究

采用水热法制备了一系列Bi2WO6/Zn O异质结光催化剂,并对其进行X射线衍射(XRD)、紫外-可见光谱(UV-Vis DRS)、扫描电镜(SEM)、光电子能谱(EDS)等手段对其结构性质进行了表征。在含酚废水的液相反应体系中,研究了异质结Bi2WO6/Zn O复合光催化剂光催化降解苯酚的性能。结果表明,Bi2WO6/Zn O异质结的形成可以有效的抑制光生电子和空穴对的结合,使其光催化活性明显优于纯的Zn O和Bi2WO6;另外,异质结型Bi2WO6/Zn O复合光催化剂的表面OH·自由基更有利于光催化活性的提高。当Bi2WO6复合量为4wt%时,异质结Bi2WO6/Zn O复合光催化剂光催化降解苯酚的效果最佳。     

5-甲氧基-2-[(E)-(6-甲基吡啶-2-亚氨基)甲基]苯酚的合成与表征

研究了以2-羟基-4-甲氧基苯甲醛和2-氨基-6-甲基吡啶为原料合成新型席夫碱化合物5-甲氧基-2-[(E)-(6-甲基吡啶-2-亚氨基)甲基]苯酚的方法。当2-羟基-4-甲氧基苯甲醛与2-氨基-6-甲基吡啶摩尔比为1∶1.6,反应时间为6 h,反应温度为75℃时,反应产率最高。采用元素分析、UV-Vis、IR、1H NMR、X-射线单晶衍射等方法进行结构表征。该化合物为单斜晶系,空间群P21/c,a=1.1886(3)nm,b=0.65948(16)nm,c=1.6897(4)nm,β=108.505(3)°,V=1.2560(5)nm3,Dc=1.281 g·cm-3,Z=4,F(000)=512,μ=0.087 mm-1,R1=0.0477,wR2=0.1342。通过π···π堆积和分子内氢键O2-H2···N1、C8-H8A···N2形成较稳定的晶体结构,并具有蓝色荧光。     

近红外光谱结合共识模型快速检测果酒的总酚含量

果酒发酵中的多酚是引起果酒口感、颜色变化的重要因素。为保证果酒品质,有必要开发一种快速监测发酵过程中多酚含量变化的技术。收集不同批次成熟期的蓝莓、桑葚为原料,分别碾压成汁,同时按比例混合二者,于小型发酵罐进行发酵。通过离线收集不同发酵时段的发酵液于离心管,高速离心后取上清液置于棕色瓶保存,共计得到48个果酒发酵样本。将上清液置于三个平行样比色皿,以傅里叶快速变换近红外光谱仪(FT-NIR)采集其透射光谱,取平均值作为该样本的光谱信号。然后将棕色瓶内的发酵液以国标法(即以标准液的吸光度值制定标准曲线)测定各样品的总酚含量,以duplex法计算样本光谱之间的距离且按2∶1的比例划分为训练集和预测集。采用间隔偏最小二乘法(iPLS)将训练集样本的透射光谱与总酚含量之间构建定量模型,间隔数从2依次变化到60个。该研究创新之处是使用共识方法融合多个已构建好的iPLS成员模型,按一定的共识规则分配权系数。通过各成员模型交互验证的残差及其残差之间的相关性来优化各成员模型的线性组合,以拉格朗日乘数法求解各成员模型的权系数,使间隔偏最小二乘-共识模型(consensual iPLS,CiPLS)的交互验证均方根误差最小。相比于全局PLS模型、划分不同间隔数量时的iPLS模型,CiPLS均具有较小的预测误差。当划分39个间隔时由三个iPLS成员模型(即14th,16th,18th)组成的共识模型误差最小为124.2,交互验证相关系数为0.944,对预测集样本的预测均方根误差为163.4,预测相关系数为0.931,预测性能均优于PLS和iPLS模型。另外,作为对比选用连续投影算法与无信息变量剔除法来优化光谱模型,其预测性能均不及本文提出的共识模型。分析各iPLS模型预测残差之间的相关性,发现共识模型主要是融合那些具有较高预测性能且模型间较低相关性的成员模型。结果表明,光谱分析结合共识方法可提高回归模型的预测精度、减少建模所需变量数,能够用于果酒总酚含量的离线快速检测。