THE 31P NMR INVESTIGATION OF PHOSPHORUS BURNS

为了明确磷烧伤创面及吸收毒性物质的化学形式及分布.作者采用\+\{31\}P NMR波谱,研究皮下注射黄磷、磷酸及磷烧伤后创面残留、肝脏及脑组织吸收的元素磷及其化合物含量.其结果皮下注射非致死与致死剂量的黄磷后,肝脏可测到元素磷的吸收,磷燃烧后创面磷绝大部分转化为磷酸及其结合物,极少部分以元素磷形式存在.致死面积的磷酸烫伤与磷烧伤后肝脏区域磷酸增加4～5倍,未检测到元素磷的波谱,各组脑组织均未检测到元素磷峰,而磷酸峰只有微小的增加.结论为磷烧烧后吸收的主要中毒物质与创面残留的主要化学物质一致,磷烧伤中毒的致死性主要是创面磷酸吸收所致.     

我国几种地带性土壤中磷素形态的研究

探明土壤磷素的存在形态,有助于揭示其在环境中的累积、迁移和转化过程及生物有效性。目前,在大尺度样带上开展土壤磷素形态空间变异规律的研究较少。本研究中,沿纬度方向采集了我国东部不同气候带分布的7种地带性林地土壤（包括寒温带的棕色针叶林土、中温带的暗棕壤、暖温带的棕壤、北亚热带的黄棕壤、中亚热带的黄壤、南亚热带的赤红壤和热带的砖红壤）,将化学浸提法与溶液磷-31核磁共振（31P NMR）波谱法相结合,分析了土壤中磷素形态以及与其他土壤性质之间的关系,以期为阐明土壤磷素形态的空间变异性及其驱动因素提供基础资料。结果表明：供试土壤中,全磷、有效磷、无机磷和有机磷的含量范围分别为179.8～825.2,2.41～15.3,92.6～351.2和14.7～474.4 mg·kg-1,其中活性、中等活性、中等稳定性和高稳定性有机磷组分的含量范围分别为1.38～30.9,8.63～213.7,3.01～32.2和1.73～199.2 mg·kg-1。根据溶液31P NMR波谱,鉴定出供试土壤中含有无机形态的磷素即正磷酸盐和焦磷酸盐,同时也鉴定出了磷酸单酯、磷酸二酯和膦酸盐等有机形态磷素的存在,其中磷酸单酯中又鉴定出了新-肌醇六磷酸、D-手性-肌醇六磷酸、RNA单核苷酸、α-磷酸甘油、肌-肌醇六磷酸、β-磷酸甘油和鲨-肌醇六磷酸,磷酸二酯中又鉴定出了DNA的存在;所有土壤中均未检测出多聚磷酸盐的存在,除棕色针叶林土和暗棕壤外的其他土壤中未检测出膦酸盐的存在,而赤红壤中未检测出DNA的存在;无机形态的磷素以正磷酸盐为主,而有机形态的磷素则以磷酸单酯为主。总体来看,无论化学浸提法还是溶液31P NMR波谱法,从寒温带的棕色针叶林土到热带的砖红壤,全磷、有效磷、无机磷、有机磷及其组分的含量均呈现下降趋势。溶液31P NMR波谱与化学浸提法鉴定的磷素形态之间存在相关关系,其中正磷酸盐与活性有机磷的关系最为密切,磷酸单酯和膦酸盐与中等活性有机磷的关系最为密切,而焦磷酸盐和磷酸二酯与中等稳定性有机磷的关系最为密切。与化学浸提法相比,溶液31P NMR波谱法能从详细的分子水平上揭示土壤磷素形态的空间变异规律。     

一种脑代谢研究的有效方法——高分辨率磁共振波谱分析

介绍了一种脑代谢研究的有效方法.成年大鼠脑经漏斗法液氮冷冻,制备脑组织高氯酸提取物并冷冻干燥,所得固体溶于D2O后用¹H和³¹P磁共振波谱(MRS)检测.结果表明：脑高氯酸提取物的磁共振波谱有着极好的分辨率,³¹P MRS可以分辨出ATP、ADP、磷酸肌酸(PCr)、无机磷以及多种磷酯和糖磷;¹H MRS可以分辨出乳酸(Lac)、N-乙酰天冬氨酸(NAA)、胆碱(Cho)、肌酸(Cr)、GABA、肌醇(Ino)、琥珀酸(Suc)以及多种氨基酸.各波峰积分后得到各种物质的相对含量,而这些代谢中间产物的相对含量变化可以反应脑内的代谢状况和脑受损伤情况.     

原子吸收法测定有机化合物中的磷和硫

共振线处于远紫外区的磷和硫元素,不能用一般的原子吸收法直接进行测定。我们在Christian和Feldman及El-Shaarawy提出的间接测定正磷酸根、硫酸根的原子吸收法的基础上进行了改进,结合采用W.Schniger氧瓶燃烧方法破坏有机试样,使有机磷和硫化合物分别转化成磷酸根和硫酸根。对若干有机磷和硫测定与容量法结果相符。磷和硫分析绝对误差为±0.3%。当磷和硫共存时不宜直接使用本法。     

不同浓度稀土溶液的反射波谱特征研究

波谱吸收特征一般和物质成分具有密切联系,其中描述波谱吸收特征的参数——波谱吸收深度可以作为一种定量评估样品化学组成的参数。 波谱吸收特征及化学特征之间的相关性研究已经在土壤学、 矿物学及植被科学等领域得到了证实,但是针对稀土元素及其化学特征之间的相关性研究目前还未开展相关工作。 为开展此方面的研究,针对赣南稀土矿区采集的10个不同浓度的稀土溶液样品,运用便携式地物波谱仪和等离子质谱仪分别获取了其波谱特征和稀土总浓度,研究结果表明稀土溶液呈现出水体和稀土氧化物的混合波谱特性,在可见光-近红外波段有6个明显的稀土特征吸收谷。 针对这6个特征吸收谷,运用原始波谱与纯水波谱比值的方法计算得出的波谱吸收深度和稀土总浓度进行线性回归分析,表明两者高度线性相关,由此建立了稀土浓度定量评估模型。 这一研究提供了一种间接评估溶液中稀土浓度的新方法,并且为稀土元素高光谱信息提取研究提供了理论基础。     

激光诱导击穿光谱对污染鱼体内重金属元素分布与含量的分析

环境污染可造成生物体的中毒、病变及死亡。生物体各组织对污染物质的吸收、积累情况是不同的。生物体各组织对污染物质重金属元素的吸收是生物医学中的一项重要研究。采用激光诱导击穿光谱(LIBS)方法对受污染的鱼体各组织进行了重金属元素定量分析。实验中得到了一组探测鱼类组织元素成份的LIBS最佳条件,拟合了Pb和Ba元素的定标曲线并通过外标法测定了重金属含量。实验结果表明,鱼体中肝脏及口腮等部位有重金属积累,而在鱼肉中重金属含量极低。所提出的方法可用于生物体受污染影响的评估研究, 在生物医学领域有重要推广价值。     

急性低氧大鼠脑31P核磁共振波谱研究

³¹P磁共振波谱是目前唯一可以用作在体无损伤的检测细胞水平能量代谢变化的非侵入性技术,可测得脑内多种能量代谢产物.目的：急性低氧大鼠脑组织的³¹P MRS检测.方法：(1)20只成年SD大鼠分为4组：低氧0min(对照),5min,10min,15min后,迅速液氮冷冻;(2)将脑组织研碎后,加入高氯酸(PCA),冷冻干燥;(3)将提取物用0.5mL D\-2O溶解后进行MRS检测.结果：(1)急性低氧早期即引起³¹P MRS中PCr和ATP峰降低,ADP和Pi峰增高,PCr/Pi和ATP/Pi降低,而ADP/ATP增高.可交换磷池(EPP)中PCr的正常值为42.4%,低氧5min后降到28.9%, ATP从33.8%降到19.2%,Pi从17.7%升到42.0%.(2)急性低氧时³¹P MRS中脑内磷酯分解代谢产物GPC、GPE含量增加,说明低氧早期脑内即有膜磷酯的分解增加.结论：³¹P磁共振波谱可用于脑低氧性疾病的诊断,我们波谱中最敏感的指标是PCr/Pi和ATP/Pi,尤其早期降低更为显著.     

波谱学发展近况

一、引 言 广义来说,物质与电磁波相互作用,产生各种频率的吸收线、散射线或发射线,称为物质的谱线,研究谱线的特征及其与物质结构和运动状态关系的科学称为波谱学.图1列出物质与电磁波相互作用的一般特征[1]. 从图中看出,波谱学涉及到电磁波各个波段,联系到物质各个层次和运动状态,范围相当广泛.但历史上波谱研究是从可见光开始的,习惯上人们把光频段的称为光谱学,涉及微波及射频波段的称为波谱学.然而近代科学技术的发展已经把光频段和微波射频段的波谱现象结合起来研究(光学—微波、射频双共振),特别是激光出现以后,射频波谱的一些概念,…     

肝脏肿瘤高分辨魔角旋转质子波谱分析

应用高分辨魔角旋转质子核磁共振波谱分析了正常肝脏（9例）、良性肿瘤（7例）及肝细胞癌（9例）代谢物变化. 半定量分析表明,肝细胞癌组织的甘氨酸、牛黄酸、胆碱、谷氨酸盐、丙氨酸、缬氨酸及乳酸明显高于正常对照和良性肝脏肿瘤组织. 实验结果表明肝细胞癌的代谢特征不同于正常肝脏和良性肝脏肿瘤. 不同肝脏组织的代谢改变可以通过高分辨魔角旋转质子核磁共振波谱检测.     

胶磷矿中杂质赋存形式及酸解过程变化

我国中低品位胶磷矿量大、分布广,磷矿中杂质种类及含量对于磷石膏结晶及磷酸品质均有较大影响。以湖北某地区的典型低品位胶磷矿为原料,采用X射线光电子能谱仪、扫描电镜、能谱等方法,分析了磷矿及反应后磷石膏中的主要杂质种类及含量变化,并以此推测湿法磷酸过程中杂质的主要变化。结果表明磷矿中的主要成分是氟磷灰石和石英,杂质组分占比最高的分别是硅、铝、氟、镁,其中硅主要以石英和硅酸钙存在,氟主要存在于氟磷酸钙中,铝是以不同形式的铝硅酸盐存在的,而镁则是以MgF₂和部分硅酸盐存在。通过酸解反应,钙与硫酸根生成磷石膏,硅元素主要存在于固相石膏中,而铝、氟、镁则大部分进入到液相磷酸中,其中存在于固相中的硅则基本以石英形式存在,硅酸钙溶解于酸液中,铝主要以铝硅磷的化合物存在,氟则以氟硅化物形式存在,大部分的MgF₂溶解进入液相,磷石膏中镁主要以镁硅酸盐形式存在。通过磷矿中杂质存在形式及反应过程的变化研究,可以更好的明晰酸解过程中的体系变化,从而为磷石膏结晶过程的考察和控制提供理论基础。     

TOF-SIMS analysis of polystyrene/polybutadiene blend using chemical derivatization and multivariate analysis

Chemical imaging with high spatial resolution is one of the features of TOF-SIMS. However, degradation of the sample due to primary ion bombardment becomes problematic when the analysis area is small. Although polystyrene (PS) and polybutadiene (PB) separately show relatively distinct spectra, observation of their phase separation in PS/PB blends is difficult when the analysis area is small because degradation of both polymers and especially PS leads to disappearance of their characteristic peaks, resulting in low chemical image contrast. We therefore investigated the application of various forms of multivariate analysis (MVA) to the TOF-SIMS image data to improve the chemical image contrast. PCA, MCR, and the other forms of MVA provided improvement in contrast, but the images were still obscure and observation of phase separation remained difficult. Chemical derivatization using osmium tetroxide was also investigated, and found to give clear images of phase separation in the PS/PB blend. In quantitative determinations with MVA and chemical derivatization, PLS demonstrated the best predictive capability and chemical derivatization resulted in large deviations from both the bulk chemical composition and the determinations with MVA, particularly in regions of low PB content.     

以新型原子距边矢量ν估计和预测烷烃核磁共振碳谱(13C NMR)化学位移(CSC)

系统研究了核磁共振碳谱与化学位移和规律,以及分子拓扑指数在定量[结]构[波]谱关系（QSSR）中的应用. 本文基于分子路径长度矢量p=（P\-1, P\-2, P\-3,\:, P\-m）与分子中原子相互作用, 提出了一种新型原子距边矢量并发现它与烷烃13C NMR 化学位移有良好线性相关性, 回归方程及其统计参数为: CSC=aν+ap\-3=∑m\-j=0a\-jν\-j+a\-10p\-3=a\-0(ν\-0=1)+a\-1ν\-1+a\-2ν\-2+a\-3ν\-3+a\-4ν\-4+bP\-3, R>0.990, EV=94.5%, RMS<0.772, F=49.069-3513.18,结果良好.     

A quantitative assessment of liver metabolites during jaundice using three dimensional phosphorus chemical shift imaging

Phosphorus metabolites in the jaundiced rat liver were studied by three-dimensional phosphorus chemical shift imaging (CSI). Animals were studied at 1, 2, and 3 weeks post-ligation of the common bile duct. Quantitation of metabolites was performed using an external standard. Metabolite T(1) values were assessed in CSI experiments on normal untreated animals. High-performance liquid chromatography (HPLC) was used to measure adenine nucleotides in a separate group of jaundiced rats. 3D-CSI did not detect significant changes in NTP in jaundiced animals relative to baseline controls. At two and three weeks post bile duct ligation, pH was significantly elevated. HPLC data comparing ATP levels to baseline controls also detected no change except for elevated ATP detected on Day 21. (31)P NMR chemical shift imaging may be used to assess liver metabolites under conditions of stress such as jaundice. However, absolute quantitation requires careful attention to many factors including point spread function, correct T(1) values, and adequate signal-to-noise ratio.     

Structural changes during phase transitions and the critical and noncritical order parameters in the (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>Nb(O<Subscript>2</Subscript>)<Subscript>2</Subscript>F<Subscript>4</Subscript> crystal

The structures of two phases of the (NH₄)₃Nb(O₂)₂F₄ crystal, namely, the parent cubic phase and the most distorted low-temperature phase, have been determined from data of an X-ray diffraction experiment performed for a powder sample. The profile and structural parameters have been refined according to the procedure implemented in the DDM program. The results obtained have been discussed with invoking the group-theoretical analysis of the complete order parameter condensate, which takes into account the critical and noncritical atomic displacements and allows the interpretation of the obtained experimental data. It has been found that the most probable sequence of structural transformations occurring in the crystal can be schematically represented in the following form:

Development of Fiber Optic Sensing System for Analyzing Isozymes Reaction of Cytochrome P450-1A Doubted as Carcinogen Activator

This paper presents a high performance fiber-optic sensing system for analyzing the isozymes reaction of cytochrome P450 (CYP). In the inherent biological system of lifeguard against chemical toxicants, the enzymes metabolize such chemical species to safer formulae. As is well known, some particular types of CYP, such as CYP-1A, however, often trigger the cancer development process by selective activation of carcinogen. A new technique for medical diagnosis of cancer development at very early or even predictive stage may be achievable based on the evaluation of the activity of the enzymes related to the cancer development by using the present system. In order to demonstrate the potential of the system, CYP-1A induced in liver of living rats by medication using 2,3,7,8-tetrachloro-dibenzofuran (2,3,7,8-TCDF) is measured and curves revealing the fluorescent power transition for each concentration of toxicants are successfully observed with good sensitivity.     

Polarization-optical and X-ray diffraction investigations on the symmetry of distorted phases of ammonium cryolite (NH4)3 ScF6

Single-crystal plates of different sections of the (NH₄)₃ScF₆ crystal have been investigated by polarization-optical microscopy and X-ray diffraction over a wide temperature range, including the temperatures of two known phase transitions and the third transition found recently. It is established that the symmetry of 5 phases changes in the following sequence: $\begin{gathered} O_h^5 - Fm3m(Z = 4) \leftrightarrow C_{2h}^5 - {{P12_1 } \mathord{\left/ {\vphantom {{P12_1 } {n1}}} \right. \kern-0em} {n1}}(Z = 2) \leftrightarrow C_{2h}^3 - {{I12} \mathord{\left/ {\vphantom {{I12} {m1}}} \right. \kern-0em} {m1}} \\ (Z = 16) \leftrightarrow C_i^1 - I\bar 1(Z = 16) \\ \end{gathered} $ .     

Creating room temperature Ohmic contacts to 4H-SiC: studied by specific contact resistance measurements and X-ray photoelectron spectroscopy

The use of a silicon interface pre-treatment to produce low resistance Ohmic nickel contacts to 4H-SiC, circumventing the need for contact post annealing, is reported. The effects of two different SiC pre-metal deposition surface preparation techniques: RCA cleaning (control sample) and a silicon interlayer pre-treatment (SIP), are discussed. Electrical characterization of contacts on treated surfaces, using circular transfer length measurements (CTLM), revealed that contacts to RCA cleaned samples were Schottky in nature, unless annealed at temperatures greater than 700 °C. In contrast, contacts formed on SIP SiC surfaces exhibited Ohmic behaviour directly after fabrication, without the need for post metallisation annealing. Average contact resistances as low as 1.3E−05 Ω cm² have been recorded for SIP samples. This fabrication process has distinct technological advantages compared to standard techniques for forming Ohmic contacts to SiC. To consolidate our findings the chemical and electrical nature of the SIP nickel-SiC interface, as it was sequentially formed and annealed, was examined using X-ray photoelectron spectroscopy (XPS). Based on these results, a model is proposed to explain the as-deposited Ohmic contact nature of the SIP sample.     

Measurement of the Λ→p μ− ¯v branching ratio

A sample of 1.2× 10⁶ Λ-hyperons was analyzed in order to detect the rare decay mode: Λ →pμ^?¯v. The Λ-hyperons were produced by stoppingK ^?-mesons in the 81 cm Saclay hydrogen bubble chamber at the CERN PS. We obtained for the branching ratio: $$\frac{{\Gamma {\text{(}}\Lambda \to p\mu ^ - \bar \nu )}}{{\Gamma {\text{(}}\Lambda \to {\text{all)}}}} = (1.4 \pm 0.5) \times 10^{ - 4} ,$$ based on 20 events, of which 6 have to be attributed to the background from the reaction $$\Lambda \to p\pi ^ - , \pi ^ - \to \mu ^ - \bar v.$$ The background was determined by a Monte Carlo calculation.     

原子吸收法间接测定水中可溶性PO4^3—的研究

研究并建立了测定水中PO4^3-的方法,用草酸钙将PO4^3-转化为磷酸钙,加醋酸溶解磷酸钙,离心沉降未反应的试剂,用AAS法测定清液中的Ca^2 ,即可间接测定PO4^3-的含量。