北江干流沉积物重金属污染生态风险评价

通过北江干流水体沉积物重金属含量,研究其典型污染物的潜在生态风险。采集了北江干流韶关至清远段7份沉积物样品,经混酸消解后,以电感耦合等离子体质谱仪测定沉积物中重金属含量,并对沉积物重金属分布特征进行了分析。同时利用Hakanson的潜在生态危害指数（RI）评价模式,对北江干流沉积物重金属生态风险进行了评价。评价结果表明,北江干流沉积物中重金属综合生态危害程度均表现为很高级别,其生态危害因子Pb、Cd已成为北江干流突发性水污染事故潜在预警因子。     

高效液相色谱-电喷雾串联质谱法测定畜禽粪便中四环素类抗生素

建立了高效液相色谱-电喷雾串联质谱法(HPLC-MS/MS)测定畜禽粪便中四环素类抗生素的分析方法。样品经甲醇-乙酸-水(体积比6∶3∶1)溶液提取,OASIS HLB小柱净化后,采用Waters Symmetry C18色谱柱(150×3.9mm,5μm)进行分离,以0.3%甲酸水溶液-0.3%甲酸乙腈溶液梯度洗脱,电喷雾正离子模式多反应监测(MRM)模式定量分析。在优化的色谱条件下,四环素、土霉素和金霉素在0.05~1.0mg/L范围内具有良好的线性,其检出限分别为0.025、0.084、0.098mg/kg;样品回收率为80%~103%。实验结果表明,该方法较液相色谱法具有更高的准确性和灵敏度,可满足畜禽粪便中四环素类抗生素残留的检测要求。     

Mechanistic Study of Unprecedented Highly Regioselective Hydrocyanation of Terminal Alkynes: Insight into the Origins of the Regioselectivity and Ligand Effects

Density functional theory (DFT) calculations were performed to gain insight into the mechanism of the nickel-catalyzed hydrocyanation of terminal alkynes with Zn(CN)₂ and water to exclusively generate the branched nitrile with excellent Markovnikov selectivity. After precatalyst activation to give the LNi(0) active species, the transformation proceeds via the following steps: (1) oxidative addition of H₂O to the LNi(0) provides the intermediate LNi(II)H(OH); (2) ligand exchange of LNi(II)H(OH) with Zn(CN)₂ gives the intermediate LNi(II)H(CN); (3) alkyne insertion to the LNi(II)H(CN) forms the alkenyl nickel complex, followed by the reductive elimination step reaching the final product. This mechanism is kinetically and thermodynamically more favorable than that of the experimental proposed ones. On the basis of the experimental observations, more water molecules cannot further improve the reaction as it has also been rationalized. Furthermore, the origin of the high regioselectivity of the product, the variable effectiveness of the metal mediator as function of ligands, as well as the high yield of the alkyl-substituted alkynes substrates, is analyzed in detail. © 2019 Wiley Periodicals, Inc.     

Switchable Polymerization Triggered by Fast and Quantitative Insertion of Carbon Monoxide into Cobalt–Oxygen Bonds

A strategy that uses carbon monoxide (CO) as a molecular trigger to switch the polymerization mechanism of a cobalt Salen complex [salen=(R,R)-N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine] from ring-opening copolymerization (ROCOP) of epoxides/anhydrides to organometallic mediated controlled radical polymerization (OMRP) of acrylates is described. The key phenomenon is a rapid and quantitative insertion of CO into the Co−O bond, allowing for in situ transformation of the ROCOP active species (Salen)Co^III-OR into the OMRP photoinitiator (Salen)Co^III-CO₂R. The proposed mechanism, which involves CO coordination to (Salen)Co^III-OR and subsequent intramolecular rearrangement via migratory insertion has been rationalized by DFT calculations. Regulated by both CO and visible light, on-demand sequence control can be achieved for the one-pot synthesis of polyester-b-polyacrylate diblock copolymers (Đ<1.15).     

山梨酸钾与Zn2+在NaCl溶液中对Q235钢的缓蚀协同作用

采用失重法、电化学法、X射线光电子能谱(XPS)和扫描电子显微镜(SEM)研究了0.5 mol/L NaCl溶液中,山梨酸钾(PS)与Zn²⁺对Q235钢的缓蚀协同效应。 失重实验结果表明,在0.5 mol/L NaCl溶液中,PS对Q235钢具有一定的缓蚀效果,缓蚀效率随PS质量浓度的增加而增大,当添加PS的质量浓度为25.0 g/L时,最大缓蚀效率仅为38.37%,而PS与Zn²⁺复配后存在显著的缓蚀协同作用,缓蚀效率高达91.03%。 动电势极化结果表明,PS与Zn²⁺混合物可同时抑制Q235钢的阴、阳极反应,属于阳极型缓蚀剂。 阻抗谱表明,该混合物可在电极表面形成致密的保护膜。 XPS分析证明保护膜是由PS、铁的氧化物/氢氧化物和Zn(OH)₂沉淀组成。     

聚对氨基苯磺酸/石墨烯电化学修饰电极检测药物中氧氟沙星

基于石墨烯纳米材料和循环伏安法技术制备了聚对氨基苯磺酸/石墨烯修饰电极并研究了氧氟沙星(OFL)在该修饰电极上的电化学行为,建立了一种简单快速灵敏测定氧氟沙星的电化学分析方法。 结果表明,与玻碳电极相比,对氨基苯磺酸/石墨烯电化学修饰电极能显著提高氧氟沙星的峰电流。 在优化条件下,其检测线性范围为1~600 μmol/L,最低检测限为(S/N=3)0.33μmol/L。 该修饰电极具有较好的重现性和稳定性,用于实际样品氧氟沙星滴眼液的测定,效果良好。     

铝与碱溶液反应的实验研究

铝与氢氧化钠溶液反应一直以来都是教学的难点,从定量角度证明了该反应的氧化剂,并解释了氢氧根离子在反应中的作用。在此基础上,结合实验表现出的铝与不同碱溶液反应的差异,进一步探讨了几种阳离子对铝与碱溶液反应的影响。     

高效液相色谱-荧光检测法测定塑料儿童玩具中苯并■唑类荧光增白剂

建立了高效液相色谱-荧光检测法同时测定塑料儿童玩具中4种苯并■唑类荧光增白剂(FWA 135、FWA 367、FWA 368、FWA 184)的方法。样品经粉碎后,采用20 mL乙腈-三氯甲烷(6∶4,体积比)混合溶液一步溶剂提取法对样品进行前处理,40℃下超声提取30 min后,进行高效液相色谱分析。以乙腈和水作为流动相,Waters SunFire C_(18)色谱柱梯度洗脱,荧光激发波长(Ex)为360 nm,发射波长(Em)为430 nm。结果显示,FWA 135在1～100μg/L质量浓度范围内具有良好的线性关系,其他3种荧光增白剂在2～200μg/L质量浓度范围内线性关系良好,相关系数(r~2)均不小于0.999 3,检出限分别为0.5、1、1、1μg/L。加标水平为0.1、0.4、2.0 mg/kg时,4种荧光增白剂的回收率为84.2%～106%,相对标准偏差均小于10%。对市售10种儿童玩具进行检测,部分样品中4种苯并■唑类荧光增白剂均有检出。该方法操作简单,回收率好,精密度高,适用于各种类型塑料儿童玩具中上述荧光增白剂的测定。     

One-pot synthesis of VO x /Al 2 O 3 as efficient catalysts for propane dehydrogenation

Vanadium oxides, as highly efficiently catalysts, are widely applied in various catalytic reactions, such as the dehydrogenation of light alkanes and epoxidation of alkenes. In this paper, a series of VO _x /Al ₂ O ₃ catalysts were fabricated by the 1-pot method for catalytic propane dehydrogenation. The results indicated that the VO _x /Al ₂ O ₃ catalysts with loading of 10 wt.% vanadium exhibited optimized catalytic performance. The as-prepared catalysts were characterized by N ₂ adsorption-desorption, XRD, TEM, H ₂ -TPR, and XPS to explore the texture properties, morphology, and electronic environment of vanadium. In addition, several vanadium catalysts were also prepared by the incipient wetness impregnation (IWI) method to compare their catalytic performance with the 1-pot synthesized catalysts. The catalysts synthesized by the 1-pot method exhibited higher selectivity of propylene and longer catalyst lifetime at high propane conversion when compared to the counterpart synthesized by the IWI method.     

Switchable Polymerization Triggered by Fast and Quantitative Insertion of Carbon Monoxide into Cobalt–Oxygen Bonds

A strategy that uses carbon monoxide (CO) as a molecular trigger to switch the polymerization mechanism of a cobalt Salen complex [salen=(R,R)‐N,N′‐bis(3,5‐di‐tert‐butylsalicylidene)‐1,2‐cyclohexanediamine] from ring‐opening copolymerization (ROCOP) of epoxides/anhydrides to organometallic mediated controlled radical polymerization (OMRP) of acrylates is described. The key phenomenon is a rapid and quantitative insertion of CO into the Co?O bond, allowing for in situ transformation of the ROCOP active species (Salen)Co^III‐OR into the OMRP photoinitiator (Salen)Co^III‐CO₂R. The proposed mechanism, which involves CO coordination to (Salen)Co^III‐OR and subsequent intramolecular rearrangement via migratory insertion has been rationalized by DFT calculations. Regulated by both CO and visible light, on‐demand sequence control can be achieved for the one‐pot synthesis of polyester‐b‐polyacrylate diblock copolymers (?<1.15).