锑矿石化学物相分析方法精密度的确定与评估

长期以来化学物相分析方法的精密度一直没有得到科学的量化控制,实验室间的精密度更是缺少控制限要求。实验在建立我国具有代表性锑矿石化学物相分析方法的过程中,按照标准GB/T6379.2—2004《测量方法与结果的准确度(正确度与精密度)第2部分:确定标准测量方法重复性与再现性的基本方法》,通过配制6个水平的协作试验样品,选择Al_2O_3、TFe(以Fe_2O_3形式表示)、CaO、MgO、Sb、S等主量组分或元素进行均匀性检验,检验结果 F值均小于临界值4.39,表明试验样品是均匀的。组织8家实验室进行协作试验,获得锑总量和3个锑矿物相中的锑随质量分数(m)变化的重复性限(r)和再限性限(R),结果表明,在确定的矿石中总锑和各矿物相中锑的重复性限和再现性限中,总锑的重复性限和再现性限最小,均小于锑矿石各相态分析的重复性限和再现性限,化学物相分析方法重复性限和再现性限参数验证了化学物相分析误差主要来源于串相误差的基本特性。锑矿石化学物相的精密度为锑矿石化学物相分析标准方法的建立和质量控制提供了依据。     

Partition distribution of insecticides as a critical factor affecting their rates of absorption from water and relative toxicities to fish

Loaches, Misgurnus anguillicaudatus (Cantor), a common fish in Taiwan, were treated with DDT, dieldrin, and monocrotophos by continuous exposure in aqueous solutions (or suspensions) and by injection. DDT and dieldrin were 150 and 220 times more toxic, respectively, than monocrotophos, to the fish exposed in aqueous solutions (24-hr LC50), but only 1/9 and 1/4 as toxic as monocrotophos by injection (24-hr LD50). Results of GLC analyses indicate that, at the end of 24-hr exposure, 96.5% of DDT, 92.7% of dieldrin, and 14.3% of monocrotophos were absorbed by loaches from aqueous solutions. The initial rates of absorption for DDT and dieldrin were about 10 to 20 times faster than that for monocrotophos. The large differences in relative toxicity may be due to partition distribution which in turn caused differences in absorption, as DDT and dieldrin are lipophilic and monocrotophos is hydrophilic. Statistical analysis of the relationship between fish toxicities and partition coefficients supports the present finding. The coefficient of correlation is 0.70 between parition coefficients (benzene/water) and toxicities to fish (rainbow trout) of 12 organophosphorus insecticides, 0.74 between coefficients and corrected fish toxicities, and 0.96 between partition coefficients and corrected fish toxicities for organophosphates only. Results of analyses are significant at less than 1% probability level. Similar correlation was also obtained between partition coefficients for hexane/water and toxicities of 8 organophosphorus and 5 organochlorine insecticides to rainbow trout.     

Coupled Environmental-Mechanical Damage Model of RC Structures

The evaluation of strength reduction of RC structures subjected to mechanical damage process and chemical attack is carried out, with regard to concrete deterioration and steel corrosion. A coupled environmental-mechanical damage model, developed as an extension of that previously published is presented. Two independent scalar mechanical damage parameters are introduced, each of them representing the degradation mechanisms occurring under tensile and compressive stress conditions. The stiffness recovery upon loading reversal, which is manifest when passing from tension into compression, is fully captured by the proposed model. The environmental damage is strongly related to the diffusion process, as well as to the evolution of the chemical reaction between pollutant and cementitious constituents. An enhanced local method is proposed to regularize the problem of nonobjectivity of the finite-element solution due to the strong strain softening behavior of concrete material. The splitting test of a concrete specimen and a static analysis of an RC frame subjected to mechanical loads and chemical attacks are carried out, and the damage evolution is analyzed in detail.     

The persistence of leptospiral agglutinins titers in human sera diagnosed by the microscopic agglutination test

Human serum albumin (HSA) is used in large amounts as an excipient in many biopharmaceutical formulation to prevent loss of the active ingredient through adsorption and/or degradation. Traditionally, iso-electric focusing has been used to demonstrate charge heterogeneity in HSA preparations. In an effort to develop new methods for the analysis of formulation components, a capillary zone electrophoresis method was developed for the analysis of HSA. Under initial separation conditions using untreated silica capillaries and 20 mM sodium phosphate, pH 6.0 as electrophoretic buffer, HSA migrated as a single peak. Addition of 1,4-diaminobutane allowed separation of several components which could be further resolved by varying the buffer pH. Optimal separation conditions were attained at 5 mM 1,4-diaminobutane and pH 8.5. The reproducibility of the separation conditions was verified by using capillaries from a different manufacturer. A comparative analysis of HSA preparations from different manufacturers provided evidence that the method may be used to qualitatively differentiate individual preparations. The analysis of rhEPO formulations, composed largely of HSA, showed levels of heterogeneity comparable to that of HSA preparations. Electrospray ionisation mass spectrometry (ESA-MS) was used as an independent method to confirm the heterogeneous nature of HSA.     

Analyses of Heated Concrete Spalling due to Restrained Thermal Dilation: Application to the “Chunnel” Fire

Two spalling mechanisms are generally quoted in the literature. The first one is due to pore pressure buildup. The second one, which is analyzed in this paper, is generated by restrained thermal dilation. We seek to model the channel tunnel fire by a thermochemoplastic constitutive model. A simplified analytical approach allows us to express mechanical variables as stresses and strains near the heated surface (the concrete wall). This study leads to introducing a “plastification” temperature and to deduce a plastification depth that can be useful for determining the spalling localization. A comparison between different cases (with and without chemical softening or decohesion) shows that thermal spalling is due to chemical decohesion (strength degradation) and not to chemical softening (rigidity reduction).     

Older persons'' preferences for site of treatment in acute illness

OBJECTIVES: The objective of this pooled analysis was to examine whether exposure to DDT was associated with the risk of non-Hodgkin's lymphoma among male farmers. METHODS: Data from three case-control studies from four midwestern states in the United States (Nebraska, Iowa, Minnesota, Kansas) were pooled to carry out analyses of 993 cases and 2918 controls. Information on use of agricultural pesticides and other risk factors was based on interviews. Non-farmers (people who had never lived or worked on a farm) were used as a reference category. RESULTS: There were 161 cases and 340 controls who reported use of DDT on animals or crops, or on both, yielding an odds ratio (OR) of 1.2 (95% confidence intervals (95% CI) 1.0 to 1.6). Farmers who had used DDT for > or = 15 years had an OR of 1.5 (95% CI 1.0 to 2.3). Adjustment for respondent status and use of other pesticides resulted in slightly reduced ORs. Analyses by the number of days of use a year was limited to the Nebraska data. The most notable increase was found among farmers who used DDT for > or = 5 days a year (OR 2.6, 95% CI 1.1 to 5.9); however, additional adjustment for use of organophosphates, phenoxyacetic acids, and the individual pesticides lindane, malathion, and atrazine reduced the ORs to 1.0, 0.9, 1.1, 1.6, and 1.9 respectively. CONCLUSIONS: No strong consistent evidence was found for an association between exposure to DDT and risk of non-Hodgkin's lymphoma. It seems that the excess risk initially found may be explained by use of other pesticides.     

Interactions of chlorinated hydrocarbons with steroid hormones

Effects of chlorinated hydrocarbons of the DDT class in mammals were examined. Two effects were considered: a) induction of hepatic mixed function oxidase (MFO), and b) estrogenic activities. The induction of MFO was discussed primarily with reference to the enhancement of steroid hydroxylation. In turn, the increase in steroid hydroxylation by chlorinated hydrocarbons was usually accompanied by a decrease in the biological activity of endogenous and administered steroid hormones. The estrogenic activity of chlorinated hydrocarbons was found to reside primarily in the o,p'-DDT (a major contaminant of technical grade DDT). The mechanism of the estrogenic activity by DDT homologs was explored. It appears that o,p'-DDT acts like estradiol (E2). Similarly to E2, o,p'-DDT binds to the uterine cytosolic receptor. Furthermore, like E2, o,p'-DDT is a potent inducer of certain uterine enzymes. For instance induction of ornithine decarboxylase of about 200-fold was observed with a high dose (250 mg/kg body wt); however as little as 5 mg/kg of o,p'-DDT exhibited marked induction of this enzyme--about threefold. The above activities of the chlorinated hydrocarbons were considered with respect to the potential long-term toxic effects which these compounds might elicit.     

The effect of a low energy diet on the concentration of DDT in the adipose tissue of turkeys

Turkey hens which had completed a breeding season and contained DDT in their fat were divided into 2 groups of 20 hens each. One group was fed a high wheat control diet throughout a 6 week period while another group was fed a low energy diet for 3 weeks and then the control diet for 3 weeks. Biopsy samples of adipose tissue taken initially and at 3 weeks and carcass adipose tissue samples of 6 weeks were analyzed for DDT and DDE. Total DDT concentration in adipose tissue increased when the hens were fed the low energy diet but decreased again when fed the control diet so that the overall change in DDT concentration over the 6 week period was not different for the two groups. The biopsy technique used in this study was successful in greatly reducing variability and improving precision.     

A saponin from the roots of Gypsophila bermejoi

A new saponin was isolated from the methanol extract of the roots of Gypsophila bermejoi and identified by a combination of chemical degradation and spectral methods, which included negative FABMS and extensive 1D and 2D-NMR analysis (DQCOSY, TOCSY, ROESY, HMQC and HMBC), as gypsogenin 28-O-beta-D-glucopyranosyl(1-->2)-[beta-D-glucopyranosyl (1-->6)]-beta-D-glucopyranoside.     

Factors affecting the biodegradation of toluene in soil

The biodegradation of toluene in soil microcosms was examined in order to identify the physical, chemical, and biological factors which determine the fate and lifetime of organic chemicals in soils. Toluene degradation rates were proportional to the initial substrate concentration and these rates reached a maximum at a concentration of 200 micrograms/g. No degradation occurred above this concentration presumably due to the toxicity of the hydrocarbon to the soil microorganisms. Small differences were observed in the degradation rates in soils at different moisture content. However, the availability of water in soil appeared to limit toluene degradation only at a very low water content. The lifetime of toluene in soil was also related to the initial level and activity of the soil microorganisms. Toluene was metabolized rapidly in those soils which initially contained high levels of degrading microorganisms. Furthermore, exposure of the soil to toluene resulted in an increase in the number of degrading organisms. The lack of inorganic nutrients such as nitrogen prevented complete degradation of toluene in a clay soil which contained high levels of degrading microorganisms. The biodegradation of organic chemicals in soil is not an intrinsic property of the molecule and cannot be predicted without first delineating the environment in which it is found. The biodegradation of a compound is defined by the biological, physical, and chemical characteristics of the soil environment. The lifetime of a chemical in soil results from a combination of all three of these parameters.     

Stabilization of pericardial tissue by dye-mediated photooxidation

Bovine pericardial tissue was stabilized through a dye-mediated photooxidation reaction. Shrink temperature analysis of the stabilized tissue indicated a material with similar properties to untreated pericardial tissue and unlike identical tissue treated with glutaraldehyde. Photooxidized tissue was resistant to extraction when compared with untreated tissue or control tissues treated in the absence of light or dye. Photooxidized tissue was also resistant to enzymatic digestion by pepsin and to chemical digestion by cyanogen bromide (CNBr). In contrast, untreated or control treated tissues were readily digested by these reagents. Reduction of photooxidized tissue with beta-mercaptoethanol prior to CNBr digestion partially restored susceptibility of the tissue to CNBr digestion, indicating the photooxidation of methionine residues. Soluble collagen derived from bovine pericardium was used as a model compound for the photooxidation reaction. Polyacrylamide gel electrophoresis analysis indicated the photooxidative conversion of collagen into higher molecular weight aggregates consistent with intermolecular crosslink formation. Photooxidized tissue was stable to in vivo degradation when compared with control tissue. Results presented here indicate a crosslinked pericardial tissue produced by dye-mediated photooxidation possessing properties of chemical stability, enzymatic stability, in vivo stability, and biomechanical integrity suitable for use as a biomaterial.     

Chemoporoplasticity of Calcium Leaching in Concrete

This paper presents a macroscopic material model for calcium leaching in concrete, for the quantitative assessment, in time and space, of the aging kinetics and load bearing capacity of concrete structures subjected to severe chemical degradation (such as radioactive waste disposal applications). Set within the framework of chemically reactive porous continua, the model accounts explicitly for the leaching of calcium of portlandite crystals and C-S-H, and its cross-effects with the elastic deformation (chemical damage) and irreversible skeleton deformations (chemical softening) treated within the theory of chemoplasticity. In the first part of this paper the governing equations are derived focusing on the chemomechanical couplings between calcium dissolution, increase in porosity, and deformation and (micro-) cracking of concrete. Without any a priori assumption concerning local equilibrium between the solid calcium concentration s and the interstitial calcium concentration c the well-known calcium leaching state function s = s(c) is then derived using combined thermodynamic equilibrium and dimensional arguments relating to the structural dimension of containment structures. In the second part, this paper addresses the experimental determination of chemical damage and chemical softening of the calcium leaching. For chemical damage, a simple mixture rule involving different skeleton constituents suffices to capture the main chemoelastic features of leaching; in turn, microhardness measurements allow access to the chemical softening state function capturing chemoplastic cross-effects. The intrinsic nature of these functions, and of the proposed procedure, is validated by means of finite-element analysis of experimental compression tests of a degraded specimen with nonhomogeneous chemical degradation states.     

MSA在钢的化学成分分析中的应用

介绍了测量系统和测量系统分析(MSA)的概念及意义,重点阐述了开展测量系统的重复性和再现性分析的步骤和方法,以钢中磷元素成分分析的测量系统的重复性和再现性分析为例,介绍了运用Minitab软件对钢中化学成分分析系统进行测量系统分析的新方法及应用。     

Conserved gene structure and genomic linkage for D-dopachrome tautomerase (DDT) and MIF

Macrophage migration inhibitory factor (MIF) and D-dopachrome tautomerase (DDT) are small proteins, which are related both by sequence and by in vitro enzyme activity. Here we show that the gene for DDT in human and mouse is identical in exon structure to MIF. Both genes have two introns that are located at equivalent positions, relative to a twofold repeat in protein structure. Although in similar positions, the introns are in different phases relative to the open reading frame. Other members of this superfamily exist in nematodes and a plant, and a related gene in C. elegans shares an intron position with MIF and DDT. In addition to similarities in structure, the genes for DDT and MIF are closely linked on human Chromosome (Chr) 22 and mouse Chr 10.     

Predicting Fenton-Driven Degradation Using Contaminant Analog

The reaction of hydrogen peroxide (H2O2) and Fe(II) (Fenton's reaction) generates hydroxyl radicals (?OH) that can be used to oxidize contaminants in soils and aquifers. In such environments, several factors can limit the effectiveness of chemical oxidation, including reactions involving H2O2 that do not yield ?OH, ?OH reactions with nontargeted chemicals, and insufficient iron in the soil or aquifer. Consequently, site-specific studies may be necessary to evaluate the feasibility of chemical oxidation using H2O2. Here, the degradation of a contaminant analog, α-(4-pyridyl-1-oxide) N-tert-butylnitrone (4POBN), was used to estimate ?OH concentration and simplify testing procedures. A kinetic model was developed, calibrated using 4POBN degradation kinetics, and used to predict the disappearance of 2-chlorophenol (2CP), a representative target. Good agreement between predicted (Y) and measured (X) values for 2CP (Y = 0.95X) suggests that the kinetics of analog degradation can be used to predict the degradation rate of compounds for which the rate constant for reaction with ?OH is known.     

Age peculiarities of changes in the contractile function of isolated rat hearts during prolonged perfusion

A selective and sensitive assay for the determination of TNP-470 and two of its metabolites, AGM-1883 and M-II, in human plasma was developed. The assay involved liquid-liquid extraction followed by analysis using high-performance liquid chromatography-atmospheric pressure chemical ionization tandem mass spectrometry. Because TNP-470 is most stable in a pH of 4-5, an acidification procedure was utilized to prevent degradation of TNP-470 during sample collection which involved acidifying the whole blood sample collected with 5 mg of citric acid per ml of blood. Liquid-liquid extraction using an organic solvent mixture was chosen over solid-phase extraction to minimize the degradation of TNP-470 during solvent evaporation.     

辉光放电原子发射光谱法测定钢铁表面纳米尺度薄膜厚度的重复性和再现性

以辉光放电原子发射光谱法测定钢铁表面纳米尺度薄膜的厚度为例进行了膜厚测定的多家实验室共同试验。对共同试验的结果进行了计算,得到相应的重复性和再现性数据,得出膜厚与重复性之间的关系为:lgr=0.018 3+0.459 6 lgm;膜厚与再现性之间的关系为:lgR=0.140 9+0.485 lgm。并对共同试验中出现的准确度问题——薄膜的密度和最小光源稳定时间进行了讨论。     

Change in stiffness and effect of orientation in degrading polylactide films

The degradation pattern of the synthetic absorbable polyester is thought to occur from the center of the material outward, and the bulk degradation is therefore attributed largely to the chemical composition of the material. It was hypothesized that this pattern might be altered by changing the morphology of the material, i.e., by introducing molecular orientation into the system. A new solid state uniaxial orientation (SS-UO) process was used to orient two types of lactide polymer films. The films were exposed to a phosphate buffered solution, then chemically, mechanically, and visually analyzed after predetermined times. This paper explores the results of flexural testing which will be later correlated with microscopic degradation events, as part of the larger degradation study. The results show that, while orientation does not have an overall significant effect on the flexural modulus, there is a significant material/orientation interaction.     

Comparative pharmacodynamics of CYP2B induction by DDT, DDE, and DDD in male rat liver and cultured rat hepatocytes

In this study the pharmacodynamics were characterized of rat hepatic cytochrome P-450 2B (CYP2B) induction by the pesticide DDT [1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane] and its metabolites DDE [1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene], which is bioretained, and DDD [1,1-dichloro-2,2-bis(p-chlorophenyl)ethane], which is metabolized further and therefore less prone to bioaccumulate. DDT, DDE, and DDD were each found to be pure phenobarbital-type cytochrome P-450 inducers in the male F344/NCr rat, causing induction of hepatic CYP2B and CYP3A, but not CYP1A. The ED50 values for CYP2B induction (benzyloxyresorufin O-dealkylation) by DDT, DDE, and DDD were, respectively, 103, 88, and > or = 620 ppm in diet (14 d of exposure). The efficacies (Emax values) for induction of benzyloxyresorufin O-dealkylation by DDT, DDE, and DDD were 24-, 22-, and > or = 1-fold, respectively, compared to control values. The potencies of the three congeners for CYP2B induction appeared also to be similar, with EC50 values (based on total serum DDT equivalents) of 1.5, 1.8, and > or = 0.51 microM, respectively. The EC50 values based on DDT equivalents in hepatic tissue were 15, 16, and > or = 5.9 micromol/kg liver tissue, respectively. In primary cultures of adult rat hepatocytes, DDT, DDE, and DDD each displayed ability to induce total cellular RNA coding for CYP2B (ED50 values of 0.98, 0.83, and > or = 2.7 microM, respectively). These results suggest that DDT, DDE, and DDD each possess a high degree of intrinsic CYP2B-inducing ability for rat liver, despite marked differences in bioretention among the congeners.