宁波市饮用水中重金属铁锌铜健康风险度评价

对宁波市区内36个样点的饮用水中Fe,Zn,Cu的质量浓度进行了调查研究,并应用目前美国环保局推荐的健康风险评价模型对各区饮用水中Fe,Zn,Cu所引起的健康风险度作了初步评价。结果表明,宁波市区Fe,Zn,Cu的平均质量浓度范围分别为Fe 35~809μg/L,Zn51~1 147μg/L,Cu 14~98μg/L;通过饮水途径所引起的非致癌健康风险中Zn在邱隘(样点)的致癌年风险最大(1.7×10-5),但低于国际辐射防护委员会(ICRP)推荐的通过饮水途径最大可接受年风险水平(5×10-5),Cu,Fe的年风险水平(10-8~10-9)均远低于ICRP推荐的最大可接受风险水平。因此与Fe,Cu相比,Zn为主要的风险污染物,应进行优先管理。     

温州横阳支江地表水健康风险评价

对温州市横阳支江水的监测数据,利用风险评价模型进行了风险评价。结果表明,由非致癌物饮水途径健康危害的总风险值处在10^-8～10^-9水平,风险水平均远低于国际辐射防护委员会（ICRP）推荐的通过饮水途径最大可接受风险水平（5×10^-5a^-1）,因此通过饮水途径所引起的慢性非致癌物暴露不会对暴露人群引起健康危害。砷对暴露人群所导致的致癌风险在10^-5a^-1水平,风险水平均接近于国际辐射防护委员会（ICRP）推荐的通过饮水途径最大可接受风险水平,因此,应优先对砷进行管理。最后探讨了生态风险评价中存在的问题和尚需进一步研究的工作。     

黔产市售绿茶重金属的含量特征及健康风险评估

为研究黔产市售绿茶中重金属的含量分布特征及健康风险,以五个生产加工地的黔产市售绿茶为研究对象,分析其9种重金属(Pb、Cr、Cd、Hg、Cu、Zn、Mn、Ni和As)含量,利用美国环境保护署(USEPA)推荐的健康风险评价模型进行人体重金属的健康风险评价。结果表明,五种茶叶中Cr、Cd、Pb、Hg、Cu和As含量均低于国家限量标准。黔产市售绿茶的重金属浸出率大小次序为Zn>Mn>Hg>As>Cd>Pb>Cr>Cu>Ni。健康风险评价结果表明,五个产地的绿茶中重金属通过饮茶途径所产生的健康危害个人年风险大小次序为Cd>As>Mn>Ni>Cr>Hg>Pb>Zn>Cu,茶叶中重金属通过饮茶途径所产生的个人健康危害年风险总和为4.33×10-6~5.73×10-6 a-1,均低于USEPA和ICRP推荐的最大可接受风险水平,表明重金属引起的健康危害极小,其对暴露人群造成的健康危害可忽略不计,绿茶中重金属均处于安全范围内。     

瑞安东山垃圾场地下水污染对人体的健康风险评价

以某垃圾场污染调查为依据,采用污染场地健康风险评价方法综合评价了由地下水污染带来的人群健康风险。综合分析表明,场地目标污染物为NO3^-、甲苯、二甲苯和锰,成年人和儿童两类人群通过饮水暴露途径的健康风险均远远大于洗浴带来的健康风险,儿童的洗浴风险大于成年人;无论饮水还是洗浴途径,4种污染物质中,锰的风险贡献最大,其次为硝酸根;从评价的4个污染因子来看,该垃圾场地下水对人体健康的危害已经相当大,须引起重视。     

云南东川区域重金属环境暴露健康风险评价

以云南省昆明市东川主要河流及附近土壤、植物为研究对象,对其进行采样分析,并根据美国环境保护署(U.S.EPA)推荐健康风险评价方法对东川流域多种环境因素进行了重金属的健康风险评价。结果表明,水环境中致癌物质造成的风险最大,风险值在2.35×10^(-4)~8.27×10^(-4),达到U.S.EPA推荐的最大值10^(-4),植物根部的健康风险值为0.40×10^(-1)~7.00×10^(-1),茎叶部分的风险值为2.42×10^(-2)~15.24×10^(-2),根部存在的重金属对人体的健康风险约为茎叶部分的5倍;土壤中非致癌物质的健康风险影响较大,总健康风险值区间为0.64×10^(-1)~3.83×10^(-1)。评价结果可为该区域地表水、土壤和植物资源的污染治理、保护开发提供依据。     

缅甸进口姜黄无机元素分析研究

目的：通过测定缅甸进口姜黄中26种无机元素,并对进口姜黄中重金属含量进行风险评价,为缅甸进口姜黄的质量控制奠定基础。方法：采用微波消解ICP-MS法对24批来自缅甸地区的姜黄进行26种无机元素的测定,通过靶标危害系数（THQ）和总危害指数（HI）对Pb、Cd、Cu 3种元素进行非致癌风险评价,用终生致癌风险（R）对As进行致癌风险评价。结果：结果表明,缅甸进口姜黄中含有24种无机元素,其中K、Na、Mg、Ca 4种营养元素含量占比24种无机元素的92.39%。缅甸姜黄中均未检出Sn、Hg 2种金属元素,Pb、Cd、As、Cu 、Hg5种重金属元素含量均符合2020版中国药典限定值。经过缅甸姜黄中Cu、Pb、Cd 3种重金属元素健康风险评价,THQ和HI均小于1,表明人体通过缅甸姜黄摄入的Cu、Pb、Cd不会对人体造成非致癌伤害。经过对姜黄中As的致癌健康风险评价,致癌风险R为7.72 x10-6,低于世界卫生组织建议的致癌风险值（1.00 x 10-5）,通过缅甸姜黄摄入的总As不存在致癌风险。结论：总体而言,缅甸进口姜黄重金属元素保持在较好水平。     

2019年泰州市某区PM_(2.5)中多环芳烃的污染特征及健康风险评价

了解泰州市某区大气环境中多环芳烃的浓度水平和人群暴露健康风险水平,可为污染防治提供参考依据。2019年每个月连续采集7天PM_(2.5),称重法计算PM_(2.5)的质量浓度,超声萃取-液相色谱法测定PM_(2.5)中16种多环芳烃,特征比值法判断多环芳烃来源,人群终身致癌超额危险度评估经呼吸途径产生的健康暴露风险。结果显示,全年萘、苊烯、苊都未检出。但是,冬季多环芳烃总浓度较高,夏季浓度最低。依据《环境空气质量标准》(GB3095-2012)二级标准来判断,PM_(2.5)年度质量浓度均值超标率为16.7%(14/84),苯并[a]芘24 h日均浓度超标率为10.7%(9/84)。多环芳烃年均浓度为(7.57±0.72) ng/m~3,略低于周边地区的水平。根据特征比值法判断,该区多环芳烃主要源自汽油燃烧为主的混合源燃烧排放。人群暴露危险度值均小于最大可接受危险度值1.0×10~(-6),PM_(2.5)中多环芳烃的人群健康风险处于可接受水平。     

1,10-邻菲啰啉-5,6-二酮修饰碳糊电极测定水中镉

以1,10-邻菲啰啉-5,6-二酮(phendio)修饰碳糊电极为工作电极,在0.05mol/L HAc-NaAc(pH4.74)电解液中,于-1.30V(vs.SCE)处Cd2 以Cd-1,10-邻菲啰啉-5,6-二酮络合物的形式吸附到电极上,再经过阳极溶出,从而建立了一种测定水样中痕量镉的新方法。本法于-0.69V处产生一个灵敏的溶出峰,其二阶导数峰电流与Cd2 的浓度在2.4×10-7~6.0×10-9mol/L范围内呈良好的线性关系;检出限为3.0×10-10mol/L(S/N=3)。应用本方法测定水样中的Cd2 ,结果令人满意。     

碳纳米管-离子液体-木质素磺酸钠复合物修饰电极同位镀铋膜测定水中铅和镉

采用涂覆法制备多壁碳纳米管(MWCNTs)-离子液体([BMIM]PF6)-木质素磺酸钠(LSS)修饰玻碳电极(GCE),然后在其表面同位镀铋膜,研究Pb(Ⅱ)和Cd(Ⅱ)在该修饰电极上的阳极溶出伏安行为。实验表明,Pb、Cd在该修饰电极上分别于-0.44V、-0.73V产生灵敏的溶出峰,Pb(Ⅱ)和Cd(Ⅱ)分别在3.0×10-8～1.0×10-6mol·L-1和2.0×10-8～8.0×10-7mol·L-1浓度范围内与其溶出峰电流呈良好的线性关系,检出限分别为4.1×10-9mol·L-1、6.9×10-9mol·L-1。该修饰电极制备简单,重现性好,用于河水中铅和镉的测定,效果良好。     

人红细胞摄入Cd~(2 )离子的动力学和机理

不同Cd2 离子浓度引起的人红细胞相对溶血率及临界溶血浓度CH0 已经测定 ,CH0 =2 .5× 10 - 4mol·L- 1。Cd2 跨膜进入人红细胞遵从一级动力学过程 ,其一级速率常数为 1.2× 10 - 2 h- 1。阴离子通道抑制剂DIDS及K ,Na ATPase抑制剂均可部分抑制人红细胞摄入Cd2 ,Cl- 浓度和介质pH也影响Cd2 的细胞摄入 ,细胞摄入镉量随胞外Cd2 浓度增加线性增加。这些实验结果证明 ,人红细胞摄入Cd2 是涉及简单被动扩散、阴离子通道转运及主动传送的复杂过程     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.