In-channel indirect amperometric detection of nonelectroactive anions for electrophoresis on a poly(dimethylsiloxane) microchip

In the present paper, we describe a microfluidics-based sensing system for nonelectroactive anions under negative separation electric field by mounting a single carbon fiber disk working electrode (WE) in the end part of a poly(dimethylsiloxane) microchannel. In contrast to work in a positive separation electric field described in our previous paper (Anal. Chem. 2004, 76, 6902-6907), here the electrochemical reduction reaction at the WE is not coupled with the separation high-voltage (HV) system, whereas the electrochemical oxidation reaction at the WE is coupled with the separation HV system. The electroactive indicator is the carbon fiber WE itself but not dissolved oxygen. This provides a convenient and sensitive means for the determination of nonelectroactive anions by amperometry. The influences of separation voltage, detection potential, and the distance between the WE and the separation channel outlet on the response of the detector have been investigated. The present detection mode is successfully used to electrochemically detect F-, Cl-, SO4(2-), CH3COO-, H2PO4-. Based on the preliminary results, a detection limit of 2 microM and a dynamic range up to three orders of magnitude for Cl- could be achieved.     

A new piezoelectric response model for population growth of bacteria

A piezoelectric response model on the population growth of microorganism is proposed. This model is based on a novel population growth model, which has a more obvious ecological meaning and the fact that the series piezoelectric quartz crystal (SPQC) sensor responses to conductivity changes of the medium during the growth of the microorganism. From the response model four parameters can be obtained including the maximum specific growth rate mu(m), saturated population size N(m), and two constants C and K(1). The influence of the parameters on the response curve is discussed in which the influences of mu(m) and N(m) are more obvious. With the proposed model the quantitative determination of bacteria may be more accurate than the frequency detection time (FDT) method. Then the growth of Escherichia coliform (E. coli) monitored with a SPQC sensor is compared with the simulated growth curve obtained by the proposed model and a good agreement is obtained.     

Gap exponents for percolation processes with triangle condition

A study is made of the gap exponents for percolation processes with the triangle condition in the subcritical region. It is show that the gaps are given by _t =2 fort=2, 3,. Scaling theory predicts thatP _p (¦C ₀¦S(p))–(p _c –p) andE _p (1/¦C ₀¦; ¦C ₀¦S(p))–(p _c –p)³, whereS(p) is the typical cluster size. It is found that (p _c –p)P _p (|C ₀S(p) ^1–)(p _c –p)^1–2 and (p _c –p)³E _p (1/|C ₀|;|C ₀|S(p) ^1–))(p _c –p)^3–4.     

Alkylation of benzene with 1-hexene in acidic ionic liquid systems: Et3NHCl-FeCl3and Et3NHCl-AlCl3ionic liquids

Summary The alkylation of benzene with 1-hexene has been investigated in different triethylamine hydrochloride-ferric chloride (Et₃NHCl-FeCl₃) and triethylamine hydrochloride-aluminium chloride (Et₃NHCl-AlCl₃) ionic liquids. Both high catalyst activity and monoalkylation selectivity were observed for these two type of ionic liquids. Systems prepared by modification with HCl in Et₃NHCl-FeCl₃ionic liquids prove to be very suitable solvents and catalysts for the reaction. When employing Et₃NHCl-AlCl₃ionic liquids as catalysts, the reaction takes place in biphasic mode with facile catalyst separation and catalyst recycling.     

X射线衍射仪新功能的开发及其应用

根据Ｘ射线衍射仪的结构特点,通过巧妙而简易的改装,增添了“同步照相”新功能。文中分析了开发新功能的可行性;列举了新功能在某些场合下,能使传统的照相法和现代的衍射仪法结合起来,取长补短的例子;指出新功能有助于提高分析测试水平,并可收到一机多用、节能高效的综合效果。     

The determination of calcium in yttrium oxide by alpha-particle activation analysis

The determination of calcium in yttrium oxide through the⁴⁰Ca(α, p)⁴³Sc reaction was studied, using a post-irradiation radiochemical separation procedure. The half-life of⁴³Sc was determined to be 3.87 hr. The chemical recovery was about 70%. The detection limit was about 10 ppb, for a 30 min irradiation at an alpha-particle beam current of 1 μA (E_α=13.4 MeV) and γ−γ coincidence counting (background counts being<1, cpm), with counting starting at 4 hours after the end of irradiation. Four samples of a batch of yttrium oxide (A.R.) were analyzed, and found to contain 13.9±1.0 ppm of calcium.     

Characterization of N-terminal processing of group VIA phospholipase A<Subscript>2</Subscript> and of potential cleavage sites of amyloid precursor protein constructs by automated identification of signature peptides in LC/MS/MS analyses of proteolytic digests

Dysregulation of proteolytic processing of the amyloid precursor protein (APP) contributes to the pathogenesis of Alzheimer's Disease, and the Group VIA phospholipase A(2) (iPLA(2)beta) is the dominant PLA(2) enzyme in the central nervous system and is subject to regulatory proteolytic processing. We have identified novel N-terminal variants of iPLA(2)beta and previously unrecognized proteolysis sites in APP constructs with a C-terminal 6-myc tag by automated identification of signature peptides in LC/MS/MS analyses of proteolytic digests. We have developed a Signature-Discovery (SD) program to characterize protein isoforms by identifying signature peptides that arise from proteolytic processing in vivo. This program analyzes MS/MS data from LC analyses of proteolytic digests of protein mixtures that can include incompletely resolved components in biological samples. This reduces requirements for purification and thereby minimizes artifactual modifications during sample processing. A new algorithm to generate the theoretical signature peptide set and to calculate similarity scores between predicted and observed mass spectra has been tested and optimized with model proteins. The program has been applied to the identification of variants of proteins of biological interest, including APP cleavage products and iPLA(2)beta, and such applications demonstrate the utility of this approach.     

Fast atom bombardment induced ring rupture of silatranes

During a comparison study of the fast atom bombardment (FAB) and electron impact mass spectra of 1-organyl-2,9,10-trioxa-6-aza-1-silatricyclo[4.3.3.0^1,6]dodecanes, an unusual ion peak at m/z 164 was noticed in the FAB spectra. Accurate mass measurement indicated that m/z 164 corresponds to protonated 1-[N,N-bis(2-hydroxyethyl)amino]-1-propanol (BHAP), which is produced by a ring-rupture reaction. Further experiment showed that the intensity of the [BHAP + H]⁺ ion peak increased markedly as the 7keV Ar⁰ bombardment proceeded, suggesting a FAB-induced reaction. The possible mechanism is also discussed.     

Mechanism and kinetics of the 2,2′-bipyridyl catalysis of the chromium(VI) oxidation of malic acid

A spectrophotometric study of the kinetics and mechanism of the oxidation of malic acid (Mal) by chromium(VI) catalyzed by 2,2′-bipyridyl (bpy) in aqueous acidic medium was conducted in a temperature range of ～298 to 313 K. This reaction was found to be pseudo-first order with respect to Cr(VI) and first order with respect to malic acid. Under the conditions of the pseudo-first order ([Mal]_o ? [Cr(VI)]_o), the observed rate constant (k _obs) increased with the increase in [H⁺] and [bpy]. There was a weak negative salt effect. Based on the experimental results, a possible reaction mechanism for this oxidation catalyzed by bpy is proposed. The rate equation derived from this mechanism can explain all the experimental phenomena.