Reactions in droplets in microfluidic channels

Fundamental and applied research in chemistry and biology benefits from opportunities provided by droplet-based microfluidic systems. These systems enable the miniaturization of reactions by compartmentalizing reactions in droplets of femoliter to microliter volumes. Compartmentalization in droplets provides rapid mixing of reagents, control of the timing of reactions on timescales from milliseconds to months, control of interfacial properties, and the ability to synthesize and transport solid reagents and products. Droplet-based microfluidics can help to enhance and accelerate chemical and biochemical screening, protein crystallization, enzymatic kinetics, and assays. Moreover, the control provided by droplets in microfluidic devices can lead to new scientific methods and insights.     

Interpretation of inorganic arsenic metabolism in humans in the light of observations made in vitro and in vivo in the rat

The toxicity of inorganic trivalent arsenic for living organisms is reduced by in vivo methylation of the element. In man, this biotransformation leads to the synthesis of monomethylarsonic (MMA) and dimethylarsinic (DMA) acids, which are efficiently eliminated in urine along with the unchanged form (As_i). In order to document the methylation process in humans, the kinetics of As_i, MMA and DMA elimination were studied in volunteers given a single dose of one of these three arsenicals or repeated doses of As_i. The arsenic methylation efficiency was also assessed in subjects acutely intoxicated with arsenic trioxide (As₂O₃) and in patients with liver diseases. Several observations in humans can be explained by the properties of the enzymic systems involved in the methylation process which we have characterized in vitro and in vivo in rats as follows: (1) production of As_i metabolites is catalyzed by an enzymic system whose activity is highest in liver cytosol; (2) different enzymic activities, using the same methyl group donor (S-adenosylmethionine), lead to the production of mono- and di-methylated derivatives which are excreted in urine as MMA and DMA; (3) dimethylating activity is highly sensitive to inhibition by excess of inorganic arsenic; (4) reduced glutathione concentration in liver moderates the arsenic methylation process through several mechanisms, e.g. stimulation of the first methylation reaction leading to MMA, facilitation of As_i uptake by hepatocytes, stimulation of the biliary excretion of the element, reduction of pentavalent forms before methylation, and protection of a reducing environment in the cells necessary to maintain the activity of the enzymic systems.     

Probe measurements in argon plasma jets operated in ambient argon

Measurements of local enthalpies and velocities have been performed in plasma jets generated by a DC plasma spray torch, using an enthalpy probe. The torch has been operated in an argon confined atmosphere at different currents and argon flow rates.⁽¹⁾ The validity of the measured enthalpy and velocity profiles has been checked by performing energy flux and mass flux balances, which show reasonable agreement between the input quantities, measured independently, and those obtained by integrating over the experimental profiles. The data are compared with those obtained by operating the same torch in ambient air. The results show that temperatures and velocities measured in pure argon are substantially higher than those in air, and consequently, the jets in argon appear wider and substantially longer.     

Radiation-Induced Polymerization of Vinylidene Chloride in Bulk and Included in Thiourea Crystals

Vinylidene chloride (VDC) or 1,1-dichloroethylene was polymerized with γ radiation in bulk or as inclusion complex in thiourea crystals (inclusion polymerization). The resulting poly(vinylidenechloride) (PVDC) samples obtained from the two different polymerization techniques were characterized by FT-IR and electronic absorption spectroscopies, by ozonolysis and by thermal analysis (TGA, DTG and DTA). It was found that two selective secondary reactions occur in the two PVDC samples, respectively obtained from bulk polymerization or from inclusion polymerization. In the former case, the main reaction is only a crosslinking reaction, while in the latter case, with the PVDC included into the thiourea channels, the crosslinking reaction is fully inhibited and instead a dehydrohalogenation reaction takes place producing the polyene structures. The presence of polyene structures in the PVDC synthesized by the inclusion polymerization was demonstrated by electronic absorption spectroscopy and by ozonolysis experiments. The presence of polyene segments in the PVDC causes a reduction in the thermal stability of the polymer, lowers its melting point and reduces its crystallinity.     

HPLC-ICP-MS联用技术在富硒金针菇硒的形态分析中的应用

从富硒培养的金针菇中分离得到含硒化合物, 并采用SE-HPLC-ICP-MS联机技术对浸提液中的含硒化合物进行分离分析; 同时对样品中的硒蛋白在特定条件下水解, 采用RP-HPLC-ICP-MS联机技术对水解液中硒代氨基酸进行确认, 并测定其中硒的含量. 结果表明, 可溶态硒是富硒金针菇中硒的主要存在形式, 其中小分子含硒有机化合物中的含硒量占浸提液中硒的71.87%; 而含硒蛋白所占比例为4.88%; 进一步确定富硒金针菇中含有硒代胱氨酸、硒代蛋氨酸和由二者组成的含硒多肽等, 各形态硒的含量为总硒量的12.3%, 17.6%和36.8%. 本方法将具有高效分离能力的色谱技术与高灵敏度的元素检测技术成功结合, 用于含硒生物分子中硒的在线分析, 具有快速、灵敏及准确等特点.     

气相色谱-质谱法测定水中有机含磷农药前处理方法比较

用气相色谱-质谱法测定了水中6种有机含磷农药残留量,并比较了全自动固相萃取(方法1#)和全自动液-液萃取(方法2#)两种样品前处理方法。结果表明:从准确度方面,方法1#优于方法2#,所测得的方法1#的回收率在73.5%～92.0%之间,而方法2#的回收率在63.7%～89.7%之间;但方法2#耗时较方法1#少。     

合成Exendin-4的体外人血浆稳定性研究

为了解决Ⅱ型糖尿病患者注射用药频繁的问题, 需要比Exendin-4更加稳定的GLP-1的激动剂, 本文的研究目的是找到Exendin-4较易水解的氨基酸位点, 为设计新的长效的Exendin-4模拟肽提供相关信息.     

Symmetry Effects in Photoinduced Electron Transfer in Chlorin-Quinone Dyads: Adiabatic Suppression in the Marcus Inverted Region

In donor–acceptor dyads undergoing photoinduced electron transfer (PET), a direction or pathway for electron movement is usually dictated by the redox properties and the separation distance between the donor and acceptor subunits, while the effect of symmetry is less recognized. We have designed and synthesized two isomeric donor–acceptor assemblies in which electronic coupling between donor and acceptor is altered by the orbital symmetry control with the reorganization energy and charge transfer exothermicity being kept unchanged. Analysis of the optical absorption and luminescence spectra, supported by the DFT and TD-DFT calculations, showed that PET in these assemblies corresponds to the Marcus inverted region (MIR) and has larger rate for isomer with weaker electronic coupling. This surprising observation provides the first experimental evidence for theoretically predicted adiabatic suppression of PET in MIR, which unambiguously controlled solely by symmetry.     

Determination of impurities in illicit methamphetamine seized in Korea and Japan

Impurities produced during synthesis of methamphetamine (MA) show different patterns under various synthetic conditions. Valuable information on the origins and smuggling routes can be obtained by using impurities as chemical fingerprints. We have detected more than 100 compounds from 436 MA samples seized in Korea by gas chromatography-flame ionization detector and gas chromatography-mass spectrometer, among which 31 impurities and three additives were identified. Twenty-six impurity peaks including unknowns were selected as the indicators of similarity, and were used as variables for cluster analysis. Cluster analysis result showed that part of the MA samples seized in Japan might have the same origin as those seized in Korea. It means that broad-based cooperation is necessary for efficient regulation of MA. Synthetic trends of the MA seizures of Korea were monitored by cluster analysis with 16 MA samples synthesized by three different methods in the previous work. We could find comparable changes of synthetic trends, which might have been influenced by domestic regulations and international situations.     

城市工业区土壤重金属元素影响评价

选择成都某热电厂,利用X荧光分析法对其表层土、深层土四种重金属元素进行了定量分析,并与成都郊区北湖周边土壤和2004年同点采集土壤对比。研究表明,热电厂表层土存在重金属污染,且某些重金属含量有逐年增加的趋势;另外,土壤中Pb、Zn含量明显受工业活动影响,高于郊区土壤。     

Bimodal proton transfer in acid-base reactions in water

We investigate one of the fundamental reactions in solutions, the neutralization of an acid by a base. We use a photoacid, 8-hydroxy-1,3,6-trisulfonate-pyrene (HPTS; pyranine), which upon photoexcitation reacts with acetate under transfer of a deuteron (solvent: deuterated water). We analyze in detail the resulting bimodal reaction dynamics between the photoacid and the base, the first report on which was recently published. We have ascribed the bimodal proton-transfer dynamics to contributions from preformed hydrogen bonding complexes and from initially uncomplexed acid and base. We report on the observation of an additional (6 ps)(-1) contribution to the reaction rate constant. As before, we analyze the slower part of the reaction within the framework of the diffusion model and the fastest part by a static, sub-150 fs reaction rate. Adding the second static term considerably improves the overall modeling of the experimental results. It also allows to connect experimentally the diffusion controlled bimolecular reaction models as defined by Eigen-Weller and by Collins-Kimball. Our findings are in agreement with a three-stage mechanism for liquid phase intermolecular proton transfer: mutual diffusion of acid and base to form a "loose" encounter complex, followed by reorganization of the solvent shells and by "tightening" of the acid-base encounter complex. These rearrangements last a few picoseconds and enable a prompt proton transfer along the reaction coordinate, which occurs faster than our time resolution of 150 fs. Alternative models for the explanation of the slower "on-contact" reaction time of the loose encounter complex in terms of proton transmission through a von Grotthuss mechanism are also discussed.     

Use of NAA in marine environment and in archaeology in Greece

Neutron activation analysis (NAA) is a very sensitive and accurate multielement analytical method that is widely applied to the investigation of environmental and archaeological problems. The first part of this paper is a review of pollution studies of toxic trace elements in sediments, seawater and marine organisms of Saronikos Gulf, Greece by NAA. The second part of this paper is a review of provenance studies based on minor and trace element research in ancient ceramics, obsidian, flint, limestone, marble and lead by Instrumental NAA, performed at the NCSR Demokritos.     

Trace elements in Taiwanese diet in different seasons

The trace element contents of Taiwanese diet were determined using conventional neutron activation analysis. Sample were prepared with duplicate portion technique by collecting food items ate and drank during a 3 day period in winter. Samples were homogenized, freeze-dried, and elemental concentration of trace elements were determined by instrumental neutron activation analysis. The interference from fast neutron induced reactions were corrected. Concentrations and daily dietary intake of the elements were compared with those collected in the summer, resulting less daily intake of K, Ca, Mn, Fe, and Zn among Taiwanese than the values recommended by WHO and RDA. Alarming low intake of Fe for females and Zn among Taiwanese were indicated.     

Two Distinct Photoprocesses in Cyanobacterial Bilin Pigments: Energy Migration in Light-Harvesting Phycobiliproteins versus Photoisomerization in Phytochromes

The evolution of oxygenic photosynthesis, respiration and photoperception are connected with the appearance of cyanobacteria. The key compounds, which are involved in these processes, are tetrapyrroles: open chain — bilins and cyclic — chlorophylls and heme. The latter are characterized by their covalent bond with the apoprotein resulting in the formation of biliproteins. This type of photoreceptors is unique in that it can perform important and opposite functions—light-harvesting in photosynthesis with the participation of phycobiliproteins and photoperception mediated by phycochromes and phytochromes. In this review, cyanobacterial phycobiliproteins and phytochrome Cph1 are considered from a comparative point of view. Structural features of these pigments, which provide their contrasting photophysical and photochemical characteristics, are analyzed. The determining factor in the case of energy migration with the participation of phycobiliproteins is blocking the torsional relaxations of the chromophore, its D-ring, in the excited state and their freedom, in the case of phytochrome photoisomerization. From the energetics point of view, this distinction is preconditioned by the height of the activation barrier for the photoreaction and relaxation in the excited state, which depends on the degree of the chromophore fixation by its protein surroundings.     

Diffusive gradients in thin films technique for uranium measurements in river water

The diffusive gradients in thin films technique (DGT) was used for uranium measurements in water. DGT devices with Dowex resin binding phase (Dow DGT) were tested in synthetic river water, which gave 84% response to total uranium concentration. The devices were also deployed in natural river water and compared to devices with other types of binding phases, Chelex 100 resin beads imbedded in polyacrylamide hydrogel (Chelex DGT) and DE 81 anion exchange membrane (DE DGT), deployed in the same location at the same time. The measurement by Dow DGT was the lowest among the different types of the DGT devices, 45% of total uranium, while measurement by DE DGT was the highest, 98% of total uranium. The results achieved by the three types of DGT devices were explained by three DGT working mechanisms, equilibrium between complexes of resin/uranyl carbonates and complexes of resin/competitive ligands in water, effective reduction of uranyl carbonate concentration by the binding phase and dissociation of UO₂(CO₃)₂²⁻ and UO₂(CO₃)₃⁴⁻ within the diffusive layer in a DGT device. It is hoped that by deploying the DGT devices with different binding phases in natural waters, additional information on uranium speciation could be obtained.     

Chemistry in Court

Chromatographic separation techniques are now widely used to examine the material evidence associated with a crime. Four areas are considered. Analysis of drugs of abuse by GC, GC-MS and GC-FTIR; HPLC; chiral chromatography; capillary electrophoresis (CE) and capillary electrochromatography (CEC); solid-phase microextraction (SPME). The quantitative detection of adulterants and trace pesticides in foods using supercritical fluid extraction (SFE). DNA profiling by separation of fragments by gel and capillary electrophoresis and fluorescence detection. Future developments in automation and miniaturisation and the design of microchips and micro-electrode devices allowing complete analysis in 8 μL cells.     

From planar defect in opal to planar defect in inverse opal

We demonstrate a facile method of fabricating opal and inverse opal structures with a planar defect. A single layer of silica beads was embedded into polystyrene opals by combining an inward-growing self-assembly method with spin-coating technique. After the infiltration of silica followed by the removal of the polystyrene beads by calcination, an inverted structure was obtained. The silica beads were connected together by the infiltrated silica, thus a solid silica phase with the silica beads as a planar defect embedded in the inverse silica opal was obtained. The thickness of the defect layer can be adjusted by changing the size of the silica beads. Scanning electron microscope images showed the good quality of the crystal and the uniformity of the defect layer. Optical transmission spectra indicated the existence of a defect state induced by the defect layer in both the opal and inverse opal structures. High-cost techniques such as lithography and chemical vapor deposition are not involved in the fabrication of inverse opals with planar defects.     

Redox-triggered molecular movement in a multicomponent metal complex in solution and in the solid state

The Cu(I) and Cu(II) complexes of the new 1,8-diferro-cenylmethyl-4,11-dimethyl-1,4,8,11-tetraazacyclotetra-decane ligand (denoted L) have been isolated and characterized by X-ray structure determination and electrochemical studies. The Cu(I) complex presents an unprecedented stability toward dioxygen. The two complexes adopt two energetically distinct and stable geometries, which differ mainly by the relative positioning of the substituents above or below the cyclam plane. Triggered by a copper-centered electron transfer, a fast and reversible motion of the noncoordinating subunits is obtained in homogeneous solution and in the solid state.     

The Pictet-Spengler reaction in nature and in organic chemistry

Alkaloids are an important class of natural products that are widely distributed in nature and produced by a large variety of organisms. They have a wide spectrum of biological activity and for many years were used in folk medicine. These days, alkaloids also have numerous applications in medicine as therapeutic agents. The importance of these natural products in inspiring drug discovery programs is proven and, therefore, their continued synthesis is of significant interest. The condensation discovered by Pictet and Spengler is the most important method for the synthesis of alkaloid scaffolds. The power of this synthesis method has been convincingly proven in the construction of stereochemicaly and structurally complex alkaloids.