彭泽贝母中微量元素的测定及初级形态分析

采用HNO3-H2O2微波消解体系,电感耦合等离子质谱法(ICP-MS)测定彭泽贝母中Pb、Ca、Fe、Mn、Zn、Cd、Ba、Cr等10种微量元素,初步探究微量元素的存在形态.结果表明:彭泽贝母中含有丰富的人体必需微量元素,可能促进其有效成分作用的发挥.其中Ca在彭泽贝母中含量最高,而Mo含量最低;彭泽贝母中微量元素是以无机态为主、多种形态共存的复杂体系.     

Recent trends in carbon nanomaterial-based electrochemical sensors for biomolecules: A review

Carbon nanomaterials are advantageous for electrochemical sensors because they increase the electroactive surface area, enhance electron transfer, and promote adsorption of molecules. Carbon nanotubes (CNTs) have been incorporated into electrochemical sensors for biomolecules and strategies have included the traditional dip coating and drop casting methods, direct growth of CNTs on electrodes and the use of CNT fibers and yarns made exclusively of CNTs. Recent research has also focused on utilizing many new types of carbon nanomaterials beyond CNTs. Forms of graphene are now increasingly popular for sensors including reduced graphene oxide, carbon nanohorns, graphene nanofoams, graphene nanorods, and graphene nanoflowers. In this review, we compare different carbon nanomaterial strategies for creating electrochemical sensors for biomolecules. Analytes covered include neurotransmitters and neurochemicals, such as dopamine, ascorbic acid, and serotonin; hydrogen peroxide; proteins, such as biomarkers; and DNA. The review also addresses enzyme-based electrodes that are used to detect non-electroactive species such as glucose, alcohols, and proteins. Finally, we analyze some of the future directions for the field, pointing out gaps in fundamental understanding of electron transfer to carbon nanomaterials and the need for more practical implementation of sensors.     

Multielemental speciation of trace elements in estuarine waters with automated on-site UV photolysis and resin chelation coupled to inductively coupled plasma mass spectrometry

An integrated approach for the accurate determination of total, labile and organically bound dissolved trace metal concentration in the field is presented. Two independent automated platforms consisting of an ultraviolet (UV) on-line unit and a chelation/preconcentration/matrix elimination module were specifically developed to process samples on-site to avoid sample storage prior to inductively coupled plasma mass spectrometry (ICP-MS) analysis. The speciation scheme allowed simultaneous discrimination between labile and organic stable dissolved species of seven trace elements including Cd, Cu, Mn, Ni, Pb, U and Zn, using only 5 ml of sample with detection limits ranging between 0.6 ng l⁻¹ for Cd and 33 ng l⁻¹ for Ni. The influence of UV photolysis on organic matter and its associated metal complexes was investigated by fluorescence spectroscopy and validated against natural samples spiked with humic substances standards. The chelation/preconcentration/matrix elimination procedure was validated against an artificial seawater spiked sample and two certified reference materials (SLRS-4 and CASS-4) to ensure homogenous performance across freshwater, estuarine and seawater samples. The speciation scheme was applied to two natural freshwater and seawater samples collected in the Adour Estuary (Southwestern, France) and processed in the field. The results indicated that the organic complexation levels were high and unchanged for Cu in both samples, whereas different signatures were observed for Cd, Mn, Ni, Pb, U and Zn, suggesting organic ligands of different origin and/or their transformation/alteration along estuarine water mixing.     

Microfabricated chemical preconcentrators for gas-phase microanalytical detection systems

The gas or vapor preconcentrator is an analytical device that significantly improves the detection limit of a microanalytical system by preconcentrating the analyte. The preconcentrator performs front-end sampling and preconcentration of analyte by collecting and concentrating analyte over a period of time. After the analyte-collection phase is complete, a heat pulse releases the analyte as a concentrated wave into the detector. Desirable features of the preconcentrator device include the capability of operating at high flow rates, thermal heating with short-time constants, and selective collection of the analyte(s) of interest. The preconcentrators presented in this review are used as a generic front-end modification to gas-phase microanalytical detection systems, such as gas chromatographs, mass spectrometers, ion-mobility spectrometers, and microelectromechanical system (MEMS)-based chemical sensors. The advantages of the detector in incorporating a preconcentrator device are enhanced sensitivity and improved selectivity. Target analytes concentrated by the preconcentrators described in this review include various organic compounds in gas or vapor phase, such as explosives 2,4,6-trinitrotouluene (TNT) and 1,3,5 trinitro-1,3,5-triazine (RDX), chemical agent dimethyl methylphosphonate (DMMP), a broad range of organic vapors, such as toluene, benzene, ethylene and acetone, and mixtures of these gas-phase organic compounds. We discuss examples of the current trends in microfabricated preconcentrator technology as well as several applications of microfabricated preconcentrators.     

Recent trends in microdialysis sampling integrated with conventional and microanalytical systems for monitoring biological events: A review

Microdialysis (MD) is a sampling technique that can be employed to monitor biological events both in vivo and in vitro. When it is coupled to an analytical system, microdialysis can provide near real-time information on the time-dependent concentration changes of analytes in the extracellular space or other aqueous environments. Online systems for the analysis of microdialysis samples enable fast, selective and sensitive analysis while preserving the temporal information. Analytical methods employed for online analysis include liquid chromatography (LC), capillary (CE) and microchip electrophoresis and flow-through biosensor devices. This review article provides an overview of microdialysis sampling and online analysis systems with emphasis on in vivo analysis. Factors that affect the frequency of analysis and, hence, the temporal resolution of these systems are also discussed.     

The determination of trace elements in crude oil and its heavy fractions by atomic spectrometry

A literature review on the determination of trace elements in crude oil and heavy molecular mass fractions (saturates, aromatics, resins and asphaltenes) by ICP-MS, ICP OES and AAS is presented. Metal occurrences, forms and distributions are examined as well as their implications in terms of reservoir geochemistry, oil refining and environment. The particular analytical challenges for the determination of metals in these complex matrices by spectrochemical techniques are discussed. Sample preparation based on ashing, microwave-assisted digestion and combustion decomposition procedures is noted as robust and long used. However, the introduction of non-aqueous solvents and micro-emulsions into inductively coupled plasmas is cited as a new trend for achieving rapid and accurate analysis. Separation procedures for operationally defined fractions in crude oil are more systematically applied for the observation of metal distributions and their implications. Chemical speciation is of growing interest, achieved by the coupling of high efficiency separation techniques (e.g., HPLC and GC) to ICP-MS instrumentation, which allows the simultaneous determination of multiple organometallic species of geochemical and environmental importance.     

Recent on-line processing procedures for biological samples for determination of trace elements by atomic spectrometric methods

Few of the elements present in nature play a metabolic role in living organisms. According to their abundance, these elements are classified as macro-, micro- or trace elements, representing 93%, 5% and around 1% respectively, of the total body weight. The remaining percentage could be attributed to those elements with unknown biological functions, to others which are present only because of the exposure to polluted environment or to those intentionally introduced into the body for a special treatment. This review summarizes and discusses the most recent publications related to the on-line processing of biological samples for trace element determination using atomic spectrometry-based detectors. Preconcentration/separation procedures based on solid phase or cloud point extractions, electrochemical deposition, microdialysis, as well as chemical vapor generation are the common practice for improving the sensitivity and selectivity of the available atomic spectrometric techniques. The advantages of using isotope dilution mass spectrometry in speciation studies are also emphasized. Digestion or leaching in oxidizing acidic mixtures aided by heat or by ultrasound or microwave radiation, performed off- or on-line, is necessary to previous steps when processing solid biological samples. The most relevant analytical figures of merit such as detection limits, enrichment factors and sample throughput as well as some aspects related to the on-line system configurations and accuracy assessments are critically presented.     

Alteration of biological samples in speciation analysis of metalloproteins

For investigations of metalloproteins by speciation analysis, the integrity of the protein–metal complexes before and during separation is crucial. Knowledge about potential alterations of the samples is thus essential to avoid misinterpretations of the analytical results. Chromatographic element profiles of different cytosolic samples from animal tissues were measured repeatedly to estimate the sample stability. The dependence of the signals on the dwell time of the sample in an autosampling device at 4 °C for a period of 10 h was observed. Alterations in the element content of different metal-containing fractions were quantified by means of recovery values. Some metalloprotein fractions (e.g. ≈27-kDa arsenic, ≈27-kDa iron and different zinc fractions) were stable or only minor alterations were observed and for their investigation an autosampling device is therefore suitable. However, most of the other metalloprotein fractions, especially nickel-containing proteins, showed major alterations: these samples should therefore be analysed immediately after preparation or directly after thawing. Figure Chromatographic manganese-profiles of 11 repeated SEC-ICP-MS-separations of rat brain cytosol. The first sample at time 0 h was the run immediately started after thawing of the prepared cytosol; the other samples were measured hourly, taken from the same sample vial. In addition to the time axis the estimated molecular mass axis is plotted Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Polystyrene film-coated glassware: a new means of reducing metal losses in trace metal speciation

A recently developed process for coating a glass surface with polystyrene (PS) film, by use of a simple chemical process has been used to reduce trace metal adsorption by cell components. The glass coating is a two-step procedure consisting of covalent attachment of vinyl-terminated PS to Si atoms on the glass surface then adsorption of PS from solution to create a stable PS film. To assess the quality of the coating we used anodic stripping voltammetry to study the adsorption of lead and cadmium ions in coated and untreated glass cells. In both short and long-term (24 h) experiments we observed that the amount of metal adsorbed was considerably less for the PS film-coated glass cell than for the uncoated cell. Further experiments showed that metal desorption is faster and metal contamination after cleaning is significantly lower for the coated cells. The PS film was, moreover, stable over a period of 6 months within the pH range 3.5–9.     

Application of enriched stable isotopes as tracers in biological systems: a critical review

The application of enriched stable isotopes of minerals and trace elements as tracers in biological systems is a rapidly growing research field that benefits from the many new developments in inorganic mass spectrometric instrumentation, primarily within inductively coupled plasma mass spectrometry (ICP-MS) instrumentation, such as reaction/collision cell ICP-MS and multicollector ICP-MS with improved isotope ratio measurement and interference removal capabilities. Adaptation and refinement of radioisotope tracer experiment methodologies for enriched stable isotope experiments, and the development of new methodologies coupled with more advanced compartmental and mathematical models for the distribution of elements in living organisms has enabled a broader use of enriched stable isotope experiments in the biological sciences. This review discusses the current and future uses of enriched stable isotope experiments in biological systems.     

Capillary microextraction (CME) and its application to trace elements analysis and their speciation

As a solvent-free miniaturized sample preparation technique, capillary microextraction (CME) has been hyphenated with different analytical instruments for trace elements analysis of environmental, biological, food and pharmaceutical samples. This review discusses the fundamentals and recent development of CME, including the theoretical basis, extraction modes (packed, open-tubular and monolithic CME) and capillary materials for CME. The emphasis is placed on the application of CME to trace/ultra-trace elements analysis and their speciation. Existing coating/monolithic materials used for CME are summarized together with a detailed overview of their preparation methods.     

ICP-AES法同时测定石英砂中的痕量元素

采用微波溶样,并通过条件试验,建立了微波溶样ICP－AES法同时测定石英砂中13种痕量元素的分析方法并已应用于实际样品的分析,方法的相对标准偏差≤10％,加标回收率为90％－107％。     

原子吸收法对藏草药川木香中12种元素的初级形态分析

用原子吸收分光光度法,测定了产于青藏高原的藏草药川木香的全药材、水提液、醇提液中12种元素(Cr、Cu、Fe、Mn、Ni、Se、Zn、K、Ca、Mg、Cd、Pb)的含量,以及水提液中各元素可溶态、水溶态的含量,同时采取正辛醇-水分配体系模拟藏药水提液中各微量元素在人体胃肠中的分配情况,对藏药中微量元素的初级形态进行了分析,初步探讨了酸度变化(人体胃肠酸度)对微量元素的影响,结合藏药药效讨论其相关性,为进一步研究微量元素与藏药药性、药效的关系提供科学的依据和奠定基础.     

Selenium speciation from food source to metabolites: a critical review

Especially in the last decade, a vast number of papers on Se and its role in health issues have been published. This review gives a brief, critical overview of the main analytical findings reported in these papers. Of particular interest is the Se content in different food sources worldwide and the extent to which their consumption is reflected in the Se content of human tissues and body fluids. Several food sources, both natural (Brazil nuts, garlic, Brassica juncea) and Se-enriched (yeast-based supplements), are discussed as to origin, characteristics, Se metabolism and impact of their consumption on the human body. The continuous development of new and improvement of existing analytical techniques has provided different powerful tools to unravel the Se species and their function. An up-to-date literature study on Se speciation analysis is given, illustrating how analytical chemistry in its different facets aids in the identification of Se compounds and provides insight into the complete metabolic pathway of Se throughout the human body. This review includes a detailed image of the current state-of-the-art of Se speciation analysis in these food sources and in human tissues and body fluids.     

原子吸收法对藏草药水母雪兔子和多刺绿绒蒿中12种元素的初步形态分析

用原子吸收光谱法,对产于青藏高原的藏草药水母雪兔子和多刺绿绒蒿,测定了全药材、水提液、醇提液中12种元素(Cr、Cu、Fe、Mn、Ni、Se、Zn、K、Ca、Mg、Cd、Pb)的含量,以及水提液中各元素可溶态、水溶态的含量,同时采取正辛醇-水分配体系模拟藏药水提液中各微量元素在人体胃肠中的分配情况,对藏药中微量元素的初级形态进行了分析,初步探讨了酸度变化(人体胃肠酸度)对微量元素的影响,结合藏药药效讨论其相关性,为进一步研究微量元素与藏药药性、药效的关系提供科学依据.     

A CRL–IRMM joint proficiency test for trace elements in fish tissue

The Community Reference Laboratory (CRL) for residues and contaminants in food of animal origin at the Istituto Superiore di Sanità (ISS) plans and undertakes on a regular basis Proficiency Tests Schemes (PTSs) focused on the residues under its responsibility, as prescribed by the Council Directive 96/23/EC of April 29, 1996. In consideration of the benefits ensuing from a constant monitoring of the daily activities of the National Reference Laboratories (NRLs) for residues in the Member States, the ISS–CRL frequently prepares test materials to promote comparability of data and support harmonisation of routine analytical procedures. When target values for the analytes are set, the PTSs also provide objective assessment and improvement of the analytical trueness in the daily work.In this context, an interlaboratory comparison for trace elements in tuna fish matrix was organised in cooperation with the Institute for Reference Materials and Measurements (IRMM), Joint Research Centre, European Commission. Freeze-dried tuna fish samples were sent out to the NRLs for chemical elements in the Member States. Participants were requested to carry out at least three independent measurements of the elements As, Cd, Cr, Cu, Fe, Hg, Pb and Zn. The assessment of the proficiency was based on the z-score approach and a relative bias better than or equal to 10% of the target value was deemed to be an acceptable performance for this kind of measurements. On this basis, more than 50% of the laboratories returned accurate results for As, Cu, Fe, Hg and Zn, whereas the analysis of Cd, Cr and Pb appeared to be more problematic.     

火焰原子吸收光谱法分析沉积物中重金属元素的形态

采用原子吸收光谱法研究了金沙江攀枝花段水系沉积物中重金属的形态及分布特征。研究发现,各重金属的形态以残渣态为主,离子交换态含量很少。同时说明原子吸收光谱法完全可以用来研究重金属形态特征,在环境研究中具有重要意义。     

Global status of trace elements in the ocean

Trace elements in seawater can be limiting factors of biological productivity, tracers of ocean circulation and biogeochemical processes, and proxies for paleoceanography. The global status of trace elements and their isotopes (TEIs) in the ocean is being explored this decade through an international study of the global marine biogeochemical cycles of TEIs (GEOTRACES). Such an international study has become possible due to recent methodological developments in sampling, preconcentration, and measurement of TEIs. Here, we present an overview of recent methodological developments and initial GEOTRACES intercalibration activities for obtaining data about TEIs that are accurate, precise, and intercomparable.     

Biopolymer based nanomaterials in drug delivery systems: A review

Drug delivery systems (DDS) are used to achieve a higher therapeutic effects of a pharmaceutical drug or natural compound in a specific diseased site with minimal toxicological effect and these systems consists of liposomes, microspheres, gels, prodrugs and many. Nanotechnology is a rapidly developing multi-disciplinary science that ensures the fabrication of the polymers to nanometer scale for various medical applications. Uses of biopolymers in DDS ensure the biocompatibility, biodegradability and low immunogenicity over the synthetic ones. Biopolymers such as silk fibroins, collagen, gelatin, albumin, starch, cellulose and chitosan can be easily made into suspension that serve as delivery vehicles for both macro and mini drug molecules. There are various methods such as supercritical fluid extraction, desolvation, electrospraying, spray-drying, layer-by-layer self-assembly, freeze-drying and microemulsion introduced to make these DDS. This drug carrier systems enhance the drug delivery actively and can be used in ocular, transdermal, dental or intranasal delivery systems. This review describes the new trends in nanomaterials based drug delivery systems mainly using biopolymers such as proteins (silk fibroin, collagen, gelatin and albumin) and polysaccharides (chitosan, alginate, cellulose and starch).