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. 相似文献
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 (Asi). In order to document the methylation process in humans, the kinetics of Asi, MMA and DMA elimination were studied in volunteers given a single dose of one of these three arsenicals or repeated doses of Asi. 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 Asi 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 Asi 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. 相似文献
Electrochemistry is one of the most advanced techniques for monitoring neurochemical activities in the living brain because electrochemical approaches bear the advantageous features of high spatial and temporal resolutions, which facilitate its tremendous potential in investigating the highly spatially heterogeneous brain system and the fast dynamics of neurochemical activities. On the other hand, since brain is the most complicated organ in the sense of its numerous kinds of neurochemical species, high selectivity is always required for any analytical methods that approach the brain. In this review, we will discuss various electrochemical methodologies to achieve selective detection of neurochemicals in mammalian brain and the strategies developed mainly by our group towards selective monitoring of both electrochemically active and inactive neurochemicals. At the end, we will discuss possible solutions towards brain mapping of neurochemical species and combination of neurochemical detection strategy with electrophysiology as the direction of future development of electroanalysis in living brain. 相似文献
Summary At the session of the WPAC of Fechem on education in analytical chemistry it was concluded that it is now essential to include chemometrics and basic knowledge of computers in all courses on analytical chemistry.
Tendenzen in der analytisch-chemischen Ausbildung
Zusammenfassung Bei einer Tagung der WPAC über die Lehre auf dem Gebiet der analytischen Chemie wurde bei der Betrachtung neuer Aspekte festgestellt, daß vor allem Chemometrie und Grundkenntnisse in Computertechnik in die Ausbildung aufgenommen werden sollten.
Summary: The recently developed initiation system, activators generated by electron transfer (AGET), is used in atom transfer radical polymerization (ATRP) in the presence of a limited amount of air. Ascorbic acid and tin(II ) 2‐ethylhexanoate are used as reducing agents in miniemulsion and bulk, respectively. An excess of reducing agent consumes the oxygen present in the system and, therefore, provides a deoxygenated environment for ATRP. ATRP of butyl acrylate is successfully carried out in miniemulsion and in the presence of air. During polymerization the radical concentration remains constant. The polymerization reaches over 60% monomer conversion after 6 h, which results in polymers with a predetermined molecular weight = 14 000 g · mol−1 and a low polydispersity ( = 1.23). AGET ATRP of styrene is also successful in bulk in the presence of air, as evidenced by linear semi‐logarithmic kinetics, which leads to polystyrene with an of 13 400 g · mol−1 and a low polydispersity index ( = 1.14).
Appearance of miniemulsion before and after the reducing agent ascorbic acid was added (left); and GPC traces representing molecular weights during the AGET ATRP of BA in miniemulsion in the presence of air (right). 相似文献
Recent developments in nitroxide-mediated polymerizations conducted in emulsion and miniemulsion have advanced the field across a range of both experimental and theoretical fronts. This article reviews progress in bicomponent initiating systems (including use of camphorsulfonic acid to enhance rate), unimolecular initiating systems, miniemulsions not requiring the use of volatile costabilizers, polymerization of acrylates, mathematical modeling and simulation, and theoretical understanding with regards to issues such as compartmentalization, preservation of polymer chain livingness, the role of aqueous phase kinetics and phase partitioning. These topics are discussed and analyzed to present an integrated portrait of the current status of nitroxide-mediated polymerizations in emulsion/miniemulsion and to identify the most pressing concerns, issues, and opportunities. To cite this article: M.F. Cunningham, C. R. Chimie 6 (2003).相似文献
The aim of this study was to explore the protective effects of Trichosanthes kirilowii ethanol extract (TKE) against cisplatin-induced acute renal failure (ARF). In the in vitro study, TKE-pretreated porcine kidney cells (PK15) exhibited enhanced cell viability after cisplatin (15 μg mL? 1) treatment in both MTT and crystal violet assays. PK15 cells pretreated with TKE (50 μg mL? 1) exhibited increased glutathione content, decreased reactive oxygen species production and ameliorated p53 expression. In vivo study, rats were administered with TKE for 4 weeks before cisplatin (5 mg kg? 1) injection. TKE (100 mg kg? 1) decreased blood urea nitrogen and creatinine levels by 24% and 47%, respectively, in comparison with cisplatin-alone group. In addition, TKE pretreatment ameliorated cisplatin-induced oxidative stress, as evidenced by increased antioxidative enzyme levels and decreased lipid peroxidation levels. Moreover, TKE pretreatment reduced histopathological alterations in the kidney with decreased apoptotic cells. Taken together, TKE might be beneficial in treating cisplatin-induced ARF. 相似文献
Intein-mediated protein splicing is a self-catalytic process in which the intervening intein sequence is removed from a precursor protein and the flanking extein segments are ligated with a native peptide bond. Splice junction proximal residues and internal residues within the intein direct these reactions. The identity of these residues varies in each intein, as groups of related residues populate conserved motifs. Although the basics of the four-step protein splicing pathway are known, mechanistic details are still unknown. Structural and kinetic analyses are beginning to shed some light. Several structures were reported for precursor proteins with mutations in catalytic residues, which stabilize the precursors for crystallographic study. Progress is being made despite limitations inherent in using mutated precursors. However, no uniform mechanism has emerged. Kinetic parameters were determined using conditional trans-splicing (splicing of split precursor fragments after intein reassembly). Several groups concluded that the rate of the initial acyl rearrangement step is rapid and Asn cyclization (step 3) is slow, suggesting that this latter step is rate limiting. Understanding the protein splicing pathway has allowed scientists to harness inteins for numerous applications. 相似文献
Two bands make light work: since the isomerization of azobenzenes is usually induced by UV light, its application is limited in living systems. A new azobenzene switch now operates entirely in the visible range. The new design is based on the introduction of OMe groups in the ortho positions, which splits the n-π* transition into two absorption bands. The two isomeric forms can be obtained with more than 80 % enrichment from the respective photostationary state. 相似文献
In a recent derivation of relaxation effects in the Debye-Hückel-Onsager theory of electrolyte conductance, with a length parameter a, terms are included which have been omitted in earlier treatments (see Appendix). The new expression was applied earlier in a reanalysis of conductance data for aqueous solutions and is applied here to solutions in acetonitrile and in formamide, representing respectively dielectric constants considerably lower and higher than water. As in aqueous solutions, a minimum standard deviation is found over a wide range of (KA,a) pairs without much effect on A0, so that only approximate determinations ofKA are possible. On the whole, the most appropriate length parametera is the physical contact distance between counterions, not a fixed radius, independent of ionic size, such as the Bjerrum value, nor a much larger radiusR serving as a boudary between free and associated ions in the ionic atmosphere about a central ion. Relaxation effects calculated by the new analysis are smaller than those from previous expressions for equal values ofa, and this leads to considerably larger values ofKA than in the original papers. As a consequence, specific short-range ion-ion and ion-solvent forces in most solutions predominate over electrostatic attraction between counterions in their contribution toKA. A table of limiting equivalent conductance based on the A0 values obtained is presented; this differs little from previous tables since A0 values obtained by the new analysis are similar to those obtained originally. 相似文献
Biocatalytic electrodes made of buckypaper were modified with PQQ‐dependent glucose dehydrogenase on the anode and with laccase on the cathode. The enzyme modified electrodes were assembled in a biofuel cell which was first characterized in human serum solution and then the electrodes were placed onto exposed rat cremaster tissue. Glucose and oxygen dissolved in blood were used as the fuel and oxidizer, respectively, for the implanted biofuel cell operation. The steady‐state open circuitry voltage of 140±30 mV and short circuitry current of 10±3 µA (current density ca. 5 µA cm?2 based on the geometrical electrode area of 2 cm2) were achieved in the in vivo operating biofuel cell. Future applications of implanted biofuel cells for powering of biomedical and sensor devices are discussed. 相似文献