硝酸银自动电位滴定法测定铜电解液中氯离子时稳定剂的影响

针对电位滴定法测定氯电位较不稳定的特点,建立了小剂量异丙醇作为稳定剂,自动电位滴定法测定铜电解液中氯离子含量的方法。确定的实验方法如下:准确移取10.00 mL铜电解液样品于50 mL烧杯中,控制反应温度为20～30 ℃,加入2 mL异丙醇,加水至50 mL左右,将银复合电极和滴头冲洗干净插入待测液中,选择搅拌器转速为625 r/min,用0.010 0 moL/L硝酸银标准溶液进行滴定。干扰试验表明,铜电解液样品中的硫酸和铜基体及其他共存元素对氯离子测定的影响可忽略。将实验方法用于铜电解液实际样品中氯的测定,测得结果与比浊法基本一致,相对标准偏差(RSD,n=5)不小于0.74%,回收率为98%～102%。     

沉淀分离-铅试金富集-氯化钠电位滴定法测定贵铋中银

对贵铋中银采用铅试金法富集后再测定时,存在铋干扰银的富集从而使得银的测定结果偏低的问题。实验采取硝酸、氟化铵和高氯酸分解样品后,加入EDTA溶液以络合铋,加入氯化钠使银以氯化银沉淀的形式析出,而铋仍留在溶液中,过滤,实现了铋与银的分离,从而消除了铋对银富集的干扰。分离铋后,用铅试金法使沉淀中银富集于合粒中,用硝酸溶解合粒,最后用氯化钠电位滴定法测定,据此建立了沉淀分离-铅试金富集-氯化钠电位滴定法测定贵铋中银的分析方法。探讨了贵铋样品中共存组分(铋、钙、铅、铁、锌、锡、锑、砷、铜和金)对银测定结果的影响,结果表明,样品中共存组分对银的测定无影响。按照实验方法对4个贵铋实际样品中银进行测定,测定结果的相对标准偏差(RSD, n=10)为0.26%~0.68%,加标回收率在99%~101%之间,所得结果与重量法的测定值相吻合。     

硝酸银比浊法测定硫酸氧钒中氯离子

采用氢氧化钠-过氧化氢处理硫酸氧钒样品,冰乙酸调整试样溶液酸度后沸水浴加热沉淀分离钒,用硝酸银比浊法测定了滤液中氯离子的含量。讨论了硝酸用量、硝酸银加入量、测量时间等对溶液浊度的影响,确定了最佳测定条件。结果表明,将硝酸银溶液与氯离子形成的氯化银悬浊液,暗置15 min后,其在420 nm波长下的吸光度保持稳定,且氯离子质量浓度在0.5～3 μg/mL范围内符合比尔定律,方法的测定下限为0.002%。将方法应用于硫酸氧钒中氯的测定,结果与离子色谱法相符,相对标准偏差(RSD,n=8)小于5.0%,加标回收率在99%～102%之间。     

灰吹富集-氯化钠电位滴定法测定贵铅中银

采取样品加铅块灰吹法于900℃灰吹炉中对贵铅中银进行富集,灰吹后得到合粒。用硝酸溶解合粒得到硝酸银溶液,最后用氯化钠电位滴定法分析硝酸银溶液中银含量,建立了灰吹富集-氯化钠电位滴定法测定贵铅中银的分析方法。对灰吹富集的实验条件进行了考察,确定灰吹方式为样品加铅块灰吹法、样品量为0.65g、铅块用量为25g。实验称取与样品中银含量相当的金属银,采用与样品相同的实验方法进行灰吹,以银的加入量与回收量的比值作为补正因子对样品中银在灰吹过程的损失进行了补正。探讨了贵铅样品中共存杂质元素(铅、锑、铋、铜、砷、碲、铁、镍、钯)对测定的干扰,结果表明,贵铅样品中共存杂质元素不干扰银的测定。将实验方法应用于贵铅实际样品中银的测定,测定结果的相对标准偏差(RSD,n=8)为0.38%~0.94%,加标回收率在99%~101%之间,所得结果与硫氰酸钾电位滴定法测定值相吻合。     

Solvation of ions. Some applications. IV A novel process for the recovery of pure silver from impure silver chloride

Silver chloride is exceptionally soluble in dimethylsulfoxide saturated with calcium chloride at 25°C. Solutions containing up to 196 gl^?1 silver as Ca(AgCl₂)₂ have been prepared. If 30–40% by volume of water is added to such solutions, then pure silver chloride is precipitated almost quantitatively. The silver chloride can be easily converted to pure (99.99%) silver metal either by melting at 1100°C with excess sodium carbonate as flux, or by reducing with hydrogen at 300–400°C, or by reducing an aqueous suspension with zinc dust. The water added to the DMSO solution can be recovered by distillation and both it and the CaCl₂-DMSO bottoms are recycled for further leaching. This leads to a fast and cheap process for obtaining silver from crude silver chloride, or from materials containing silver in a form that can be converted to silver chloride. Applications to an anode slimes leach residue, a silver halide teaching laboratory residue, and the silver chloride cake from a gold refinery are demonstrated.     

火焰原子吸收光谱法间接测定氧化锌烟尘中氯

以稀硝酸溶解样品,然后向样品溶液中加入过量Ag⁺标准溶液,溶液中的微量Cl^-会与定量的Ag⁺形成氯化银胶体,加热煮沸溶液使氯化银胶体迅速凝聚并完全沉淀,采用火焰原子吸收光谱法测定滤液中剩余的Ag⁺量,通过换算间接得出氧化锌烟尘中的氯含量。讨论了共存离子的干扰、试样溶解条件、沉淀反应时间和测定介质,确定了最佳实验条件。采用实验方法测定烟化炉氧化锌烟尘和回转窑氧化锌烟尘中氯的含量,测得结果与氯化银比浊法基本一致,相对标准偏差(n=5)为0.65%～0.89%,回收率为99%～101%。     

氢氧化钠熔融-氯化银比浊法测定铅锌矿中氯

采用氢氧化钠熔融分解试样, 熔渣用水煮沸浸出, 冷却定容后分取上层清液, 用氯化银比浊法测定氯。考察了试样与熔剂氢氧化钠的比例、试样熔解温度与时间、氯化银悬浊液中硝酸和硝酸银加入量及试样中共存的银和硫化物对测定的影响。结果表明:试样与氢氧化钠以1∶4的质量比于650 ℃熔融15 min即可彻底分解, 同时共存的S^2－被氧化而不干扰测定;常见共存元素及试样含银量小于21.4%对测定不产生干扰。校准曲线线性范围为 0～10 μg/mL, 相关系数为0.999, 表观摩尔吸光系数为1.21×10³ L·mol^－1·cm^－1。对铅锌矿实际样品进行分析, 结果的相对标准偏差(n=7)在1.4%~2.2%范围内, 测定值与硫氰酸汞分光光度法基本一致。     

铅试金重量法结合原子吸收光谱法测定银钯精矿中银

采用硝酸、盐酸、高氯酸分解样品,加入盐酸与银反应形成氯化银沉淀后过滤,采用铅试金重量法对沉淀中银量进行了测定,并扣除了钯产生的干扰,同时采用原子吸收光谱法(AAS)对滤液中的银量进行了测定,将沉淀与滤液中的银量相加后除以样品量得到样品中银的含量,实现了铅试金重量法联合原子吸收光谱法对银钯精矿中银的测定。考虑到在沉淀形成的过程中,氯化银沉淀对铂和钯有严重的吸附作用,因此考察了铂和钯对沉淀中银量测定的影响。试验表明,采用铅试金法对沉淀中贵金属进行捕集后,贵金属合粒中的铂对银测定的干扰可忽略不计,但钯的干扰不可忽略。实验采取用10mL硝酸(1+1)低温溶解贵金属合粒,以原子吸收光谱法测定合粒溶液中钯量,从铅试金重量法所得结果中扣除合粒中钯量的方法消除了沉淀中钯对测定的干扰。干扰试验表明,滤液中的主要共存元素钯、铜、铋、金、铂对样品中银测定的干扰可忽略不计。按照实验方法,对钯银精矿样品中银平行测定11次,相对标准偏差(RSD)为0.028%~0.059%,同时加入高纯硝酸银进行加标回收试验,回收率为98%~102%。将实验方法应用于银钯精矿样品中银的测定,其测定结果与碘化钾电位滴定法基本一致。     

元素分析仪测定土壤和水系沉积物中氯

氯元素是土地质量调查和评价的重要指标,在地质行业中,分析氯的行业标准方法为X射线荧光光谱法(DZ/T 0279.10—2016),其难点在于氯容易污染,测量值极易受测量时间、测量次数、样片保存条件等因素影响。实验将样品在高温条件下分解,生成的氯化物经过硫酸干燥后进入元素分析仪的电解池吸收池,吸收产生的Cl^—与电极产生的Ag⁺发生反应生成氯化银沉淀,元素分析仪可根据滴定平衡电位自动判断滴定终点,自动计算出样品中氯的含量。试验发现,电解液中加入过量乙酸,可以有效抑制水电解,避免因水电解产生的分析误差。方法的检出限为10.4 μg/g。采用实验方法测定土壤和水系沉积物国家标准物质中氯,结果的相对标准偏差(RSD,n=12)小于7%,相对误差(RE)小于6%。实际样品的分析结果与X射线荧光光谱法测定结果的双差(RD)满足规范要求。实验方法采用固体进样,样品使用量少(0.050 0~0.150 0 g),无需曲线校准,适合于大批量样品检测。     

火焰原子吸收光谱法间接测定石灰石中氯含量

提出了用硝酸溶解样品,以火焰原子吸收光谱间接测定石灰石中氯含量的分析方法。采用先往样品与校准曲线溶液中加入等量的氯离子,然后再往样品溶液中加入过量银离子使样品溶液及校准曲线溶液形成氯化银饱和溶液的方法,解决了火焰原子吸收间接法测定氯含量时微量悬浮氯化银及氯化银溶解性对测定的影响问题。在溶样过程中加入过硫酸铵氧化除去S2-、I-及大部分Br-等干扰离子,避开了过滤、蒸馏等繁琐且易受污染的操作步骤。方法相对标准偏差(RSD,n=9)为0.3 %～7.0 %。经国家标准物质验证,测定值与认定值基本符合。     

Reproductive hormone profile among pesticide factory workers

Serum follicle-stimulating hormone (FSH), luteinizing hormone (LH), and testosterone levels, as well as urinary levels of FSH, LH, and E1C, a metabolite of testosterone, were measured to investigate the adverse reproductive effects of organophosphate pesticides among Chinese factory workers who were occupationally exposed to ethylparathion and methamidophos. Thirty-four exposed workers were randomly chosen and recruited from a large pesticide factory, and 44 unexposed workers were selected from a nearby textile factory. A quantitative pesticide exposure assessment was performed among a subset of the exposed and unexposed workers. Information on potential confounders was collected in an interview. A single blood sample was collected at the end of a work shift, when each subject also donated a semen sample. Three first-voided urine samples were collected from each worker on 3 consecutive days. Urinary p-nitrophenol level at 1 hour after the work shift correlated with serum (r = 0.71, P < 0.01) and urinary (r = 0.51, P = 0.04) FSH levels. Stratifying by the subjects' exposure status, we found a significant negative correlation among the exposed group between urinary FSH level and sperm count (r = -0.61, P < 0.01) and between urinary FSH level and sperm concentration (r = -0.53, P = 0.03). Pesticide exposure alone was significantly associated with serum LH level (beta [coefficient of exposure effect] = 0.79; 95% confidence interval [CI] = 0.42, 1.16) but not with serum FSH or testosterone or with any urinary hormone levels. With adjustment for age, rotating shift work, current cigarette smoking, and current alcohol consumption, exposure significantly increased the serum LH level by 1.1 mIU/mL (95% CI = 0.34, 1.82). Meanwhile, the serum FSH level was slightly elevated (beta [coefficient of exposure effect] = 1.38; 95% CI = -0.09, 2.85) and the serum testosterone level was decreased (beta = -55.13; 95% CI = -147.24, 37) with increased pesticide exposure. Age and rotating shift work appeared to act as confounders. We conclude that organophosphate pesticides have a small effect on male reproductive hormones, suggestive of a secondary hormonal disturbance after testicular damage.     

超声波加速溶解-硝酸银比浊法测定海绵钛中氯

采用氢氟酸超声溶解样品,加入硝酸氧化低价钛,加入硼酸络合过量的氟离子,以丙三醇作为分散剂,利用超声的方式提高氯化银胶体的稳定性,以硝酸(1+19)定容,于420nm处进行测定,实现了硝酸银比浊法对海绵钛中氯的测定。实验表明:用20mL氢氟酸(1+5)于80kHz的超声波下震荡5min可消解1g左右的样品。分取适量体积的样品消解液,依次加入30mL硝酸(1+19)、2.5mL丙三醇和3.0mL硝酸银溶液,用硝酸(1+19)定容,超声波震荡40s,避光静置10min后测定,氯离子的质量浓度在0.05~2.4μg/mL范围内与其对应的吸光度呈线性关系,线性相关系数为0.999 7,方法中氯的检出限为0.05μg/mL。采用实验方法测定2个海绵钛样品中的氯,结果与国标方法 GB/T 4698.25—1996基本一致,相对标准偏差(RSD,n=11)小于5%,加标回收率在96%~103%之间。     

An enzymeimmunoassay for total thyroxine using avidin-biotin separation system and thyroxine-peroxidase conjugate

An avidin-biotin enzymeimmunoassay for total thyroxine in serum is described. Avidin was adsorbed to biotinylated bovine serum albumin coated tubes prepared with glutaraldehyde as coupling agent. In the enzymeimmunoassay, affinity purified biotinylated anti-thyroxine IgG, sample or standards, and thyroxine-horseradish peroxidase were simultaneously added to the avidin coated tubes. The bound enzymatic activity was then measured with o-phenylenediamine and H2O2. Results showed that the assay has good precision (within-assay CV% less than 10% and between assay 11.7% in hypo- and 6.9% in hyperthyroid range), good assay range (0-800 nmol/L), good sensitivity (4 nmol/L), and can be performed in 2.5 hours. The results obtained correlate well (r = 0.93) with those of an RIA.     

电位滴定法测定银钨合金中银

银钨合金是制备微电子元件和耐高温元件的关键材料,准确测定其中银的含量对于把控产品质量、银钨合金废料回收利用具有重要意义。采用硫酸-硫酸铵溶解样品,可以有效提高消解体系的温度,同时铵根离子的存在可以络合溶液中的钨离子,促进样品的消解,在酸性条件下,用氯化钠标准滴定溶液滴定至电位突跃,记为终点,建立了电位滴定法测定银钨合金中银含量的分析方法。研究表明,产品中存在的其他元素钨、铝、钴、铬、铜、铁、锰、镁、镍、锡对银量的测定无干扰。按照实验方法测定4个银钨合金样品中银,测定结果的相对标准偏差(RSD,n=11)为0.14%~0.53%,加标回收率为99%~102%。选取Ag20W和Ag80W两个样品,按照实验方法对其中银含量进行测定,并采用标准方法JB/T 4107.4—2014进行验证,经F检验和t检验分析,证明两种方法具有较好的一致性。     

A ferric chloride hydrometallurgical process for recovery of silver from electronic scrap materials

A hydrometallurgical method for the recovery of silver from electronic scrap materials is suggested. Electronic scrap materials, containing silver with the accompanying brass and beryllium bronze, are leached at 80°C with ferric chloride. The leaching should be carried out with the concentration of ferric chloride and phase ratio chosen so that in the final phase of leaching the concentration ratio of Fe(III) to Fe(II) is not lower than 1. Under such conditions silver is found to be only slightly solubilized. This was confirmed by electrochemical studies.Potentiodynamic studies of the behaviour of silver in hydrochloric acid demonstrated that at the electrode potential value of 0.77 V, corresponding to the redox potential at 25°C of the solution where the concentration ratio [Fe(III)]/[Fe(II)] = 1, the silver surface is passivated not only by silver chloride but also by silver oxide. This prevents solubilization of silver in chloride solutions owing to the formation of AgCl₂^? and AgCl₃^2? complexes. The lowering of the solution oxidation potential resulting from consumption of Fe³⁺ ions during the leaching process causes a sudden increase in silver concentration in solution.     

Combinations of three immunological assays for detecting anti-Toxoplasma IgG in the sera of patients infected with Toxoplasma gondii

Enzyme-linked immunosorbent assay (ELISA), Dot-ELISA and Dot-immunogold silver staining (Dot-IGSS) were simultaneously used to detect the specific IgG against Toxoplasma gondii in 65 patients infected with the protozoa. The positive rates were 86.51%, 92.51% and 98.64%, respectively. When ELISA and Dot-ELISA results were put together, the positive rate increased to 95.38%. When Dot-IGSS results were combined with those of ELISA or Dot-ELISA, the positive rate was raised to 100%. The difference in positive rate between ELISA and Dot-IGSS was significant (x2 = 6.93, p < 0.01), but no statistically significant differences were found between ELISA and Dot-ELISA or between Dot-ELISA and Dot-IGSS. Paired comparison of the reacting intensities of the sera in the 3 assays showed the correlations were highly significant (p < 0.001), with r = 0.608 between Dot-IGSS and Dot-ELISA, r = 0.8194 between Dot-IGSS and ELISA and r = 0.517 between Dot-ELISA and ELISA. Hence combination of different serological assays may increase their sensitivity and specificity for detecting the anti-Toxoplasma antibodies.     

超声浸取-离子选择电极法测定银精矿中水溶性氯

以水为溶剂超声浸取样品,加入适量0.25mol/L柠檬酸三钠-1mol/L硝酸钾溶液作为总离子强度调节剂,控制响应时间为5min,建立了离子选择电极法测定银精矿中水溶性氯的测定方法。对超声浸取的条件进行了优化,确定浸取条件如下:采用20mL水在水浴温度为50℃时对0.5g样品超声浸取15min。对测定条件进行了考察,结果表明,为减少电位的波动,保证测定结果的准确性,电极响应斜率S值的测定与样品测试均应在同一恒温体系下进行。在优化的实验条件下,氯离子在2~12μg/mL范围内其质量浓度的自然对数与电位值呈良好的线性关系,相关系数为0.9998,检出限为0.863μg/mL。选取两个银精矿样品,按实验方法分别平行测定6次,测定值与离子色谱法的测定值基本一致,相对标准偏差(RSD)为2.1%~2.8%。     

火试金法测定银阳极泥中的金和银

运用火试金法分离并捕集银阳极泥中的金和银,灰吹所得金银合粒称重后,加入一定量纯银标准并进行二次灰吹,使金银合粒能被稀硝酸溶解。利用金不溶于硝酸的性质使金、银分离,用重量法测定金量和银量。应用于实际试料的分析,方法的精密度(RSD,n=5)分别为Au<0.1%,Ag<0.2%。加标回收率分别为Au:99.88%~100.67%,Ag:98.81%~100.06%。     

Impact of family history on the risk of breast cancer among the Japanese

OBJECTIVE: The serum concentration of the high-affinity growth hormone-binding protein (GHBP) is increased in obesity but the mechanisms are poorly understood. This study assessed the physiological mechanisms involved in the regulation of GHBP in adiposity. SUBJECTS AND MEASUREMENTS: We tested a number of obesity specific parameters for their association with GHBP. In this study, 199 normal or overweight children and adolescents (101 boys, 98 girls, aged (mean +/- s.d.): 13.7 +/- 2.3 y) underwent an anthropometric evaluation (circumference measurements and bioimpedance analysis) combined with blood withdrawal for the measurement of insulin-like growth factor-I (IGF-I), insulin, leptin and GHBP (by specific RIA), uric acid, triglycerides and cholesterol. RESULTS: By linear regression analysis GHBP correlated significantly (P < 0.001) with percent body fat mass (r = 0.71), waist (r = 0.73) and hip (r = 0.69) circumference, weight (r = 0.61) waist hip ratio (WHR) (r = 0.54), as well as with the serum concentrations of leptin (r = 0.64), uric acid (r = 0.54), insulin (r = 0.45), LDL-cholesterol (r = 0.43), cholesterol (r =0.33), LDL/HDL ratio (r = 0.47), triglycerides (r = 0.30) and with height standard deviations scores (SDS) (r = 0.23). Age, gender and pubertal stage had no impact on GHBP. In a multiple regression analysis containing age and gender, as well as the anthropometric variables, percent fat mass and waist circumference, as independent variables, associations between GHBP and leptin (P < 0.001), cholesterol (P < 0.01), LDL-cholesterol (P = 0.01), LDL/HDL ratio (P = 0.02), triglycerides (P = 0.01) remained significant. In a final model using the stepwise analysis involving age, gender and all the independent predictors of GHBP, waist circumference (P < 0.001), accounted for 49.5% of the 60.0% total variability in GHBP, while the implication of leptin (P < 0.001), age (P < 0.01) and cholesterol (P < 0.05) increased the predicted variability for 7.5%, 1.9%, and 1.0%, respectively. Serum GHBP was significantly reduced in a subgroup of 104 overweight or obese patients during a diet-induced weight loss programme, the coefficient of correlation between GHBP and leptin after (r = 0.45, P < 0.001) and before weight reduction (r = 0.41, P < 0.001) were comparable. CONCLUSION: Waist circumference, an indicator of abdominal body fat mass, is a major determinant of GHBP levels during childhood, while leptin may be one candidate for a signal linking adipocytes to the growth hormone receptor related GHBP release. Additionally, elevated serum levels of GHBP may reflect metabolic disturbances of adiposity.     

Serum N-terminal osteocalcin is a good indicator for estimating responders to hormone replacement therapy in postmenopausal women

To estimate the response to hormone replacement therapy (HRT) by bone metabolic markers, 36 patients with postmenopausal osteoporosis or osteopenia were studied to assess the correlation between percent baseline changes in lumbar bone mineral density (BMD) after 12 months and those in various bone metabolic markers after 3, 6, and 12 months of HRT. All the patients were treated with 0.625 mg of conjugated estrogen and 2.5 mg of medroxyprogesterone per day and continued for 12 months. BMD was significantly increased up to 4.19 +/- 0.87% after 6 months and 4.93 +/- 1.27% after 12 months of HRT (p = 0.0001 by analysis of variance). In accordance with this, changes in the levels of osteocalcin (p = 0.041), alkaline phosphatase (p = 0.0001), N-terminal osteocalcin (p = 0.0001), urinary excretion of pyridinoline/Cr (p = 0.0001), and deoxypyridinoline/Cr (p = 0.0001) were significantly decreased, respectively. Among these bone metabolic markers, only the change in the serum N-terminal osteocalcin at 3 months (r = 0.557, p = 0.0022), at 6 months (r = 0.470, p = 0.0184), and at 12 months (r = 0.545, p = 0.0061) significantly correlated with the change in BMD 12 months after HRT. The elution profiles of immunoreactive osteocalcin-related molecules in serum fractionated by reverse-phase high performance liquid chromatography revealed that the N-terminal fragment as well as the intact osteocalcin molecule decreased after 3 months of HRT. These results demonstrate that N-terminal osteocalcin is a suitable predictor for estimating good responders to HRT in postmenopausal women.