On the electrochemical reduction of some Cr(III) complexes inDMSO investigated by cyclic voltammetry

The compounds investigated were: [Cr(en)₃]³⁺, [Cr(ur)₆]³⁺, [Cr(DMSO)₆]³⁺, [Cr(dien)₂]³⁺, [Cr(en)₂(acac)]²⁺, [Cr(en) (acac)₂]⁺ and Cr(acac)₃.A distinctly different behaviour is caused by the introduction of one or moreacac ligands into the molecule. The first step is much more cathodic and quite irreversible, while it is reversible or quasi reversible for the first group of ions. This is due to a -type interaction between theacac ligand and the central ion. This interaction is responsible for a third peak occurring for the second group of compounds and may be attributed to the reduction of the Cr(I) ion.Some correlations were found e.g. between the extinction of thed-d band of the first group of ions and the potential of the first peak, and the number ofacac groups introduced in the second group of compounds and the shift of the potential of the first peak.The determined electrochemical data are tabulated.

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Untersuchungen zur elektrochemischen Reduktion einiger Cr(III)-Komplexe in DMSO mittels zyklischer Voltammetrie

Zusammenfassung Die elektrochemischen Daten einer Reihe von Cr(III)-Komplexen miten-, ur-, DMSO-, dien- undacac-Liganden werden präsentiert und einige Möglichkeiten der Korrelation der physikalischen Eigenschaften der Komplexe werden aufgezeigt.Die erste Stufe bei der Einführung vonacac-Liganden ist auf Grund einer -Wechselwirkung zwischen Ligand und Zentralion irreversibel.

     

Differentiation between o- and p-quinol/quinone functionality with a simple test using cyclic voltammetry

Complexation with boric acid combined with cyclic voltammetry serves to prove theo-quinol/quinone functionality in emmotin H (1) and I (2). Supported by similar investigation of four reference compounds the method is suggested as a quick and reliable test ofo-quinol/quinone functionality and for differentiation fromp-quinol/quinone functionality. Voluminous groups such as 2-isopropanolyl ino-position do not interfere with the complex formation. The test requires quantities of materials in the order of 10 to 100g.     

HPLC-fluorescence detection and MEKC-LIF detection for the study of amino acids and catecholamines labelled with naphthalene-2,3-dicarboxyaldehyde

Naphthalene-2,3-dicarboxyaldehyde (NDA) is commonly used for detection of primary amines in conjunction with their separation with HPLC and CE. The fluorescence of the derivatives can be measured by a conventional fluorometer or via LIF. NDA is a reactive dye, which can replace o-phthaldehyde (OPA) and provides for derivatives which are considerably more stable than OPA derivatives. In addition, NDA can be used to derivatize primary amines at concentrations as low as 100 pM. In this work, HPLC/fluorescence and MEKC/LIF experiments were performed to separate/detect six neuroactive compounds, the amino acids, Gly, Glu, Asp, gamma-aminobutyric acid (GABA) and the catecholamines, dopamine and noradrenaline. The two methods were compared in terms of performance of separation. The amino acids can be separated in HPLC in less than 30 min and an identical separation is obtained in CE using MEKC and lithium salts with greater resolution (the number of theoretical plates was approximately 5000 for HPLC and 200 000 for MEKC). The lowest detected concentration was in the range of 0.1 nM for CE/LIF. The presence of a high salt concentration does not affect the separation of the samples. Examples of the analysis of microdialysate samples as well as amino acids in Ringer's solution are presented.     

The synthesis and the structure elucidation of <Emphasis Type="Italic">N,O</Emphasis>-diacetyl derivative of cyclic 3-hydroxymelatonin

Melatonin was subjected to an oxidation to give 3-hydroxymelatonin. All spectroscopic data for this compound were collected. Ab initio calculations for both possible configurations were performed. X-ray data on N,O-diacetyl derivative of 3-hydroxymelatonin allowed the unambigous structure determination.     

Micellar capillary electrophoresis – Electrochemical detection of neurochemicals from Drosophila

The fruit fly is one of the most heavily studied model organisms for genetics research and has significantly contributed to the molecular, cellular, and evolutionary understandings of human behavior. Recent research in the analytical chemistry of the fruit fly has focused on developing methods to obtain highly sensitive chemical quantification information of Drosophila melanogaster, especially looking at the nervous system. We provide a brief overview of work in the area of CE of the fly head and brain.     

Liposome-based immunostrip for the rapid detection of Salmonella

Salmonellae are ubiquitous human pathogens, which pose a danger to the elderly and children. Due to the increased number of outbreaks of human illness associated with the consumption of contaminated products in the USA and many other countries, there is an urgent need to develop rapid assays to detect common food-borne pathogens. This study demonstrates the feasibility of using a detectable label comprising methyl blue (MB), a visible dye, entrapped inside liposomes. Immunoliposomes tagged with anti-Salmonella common structural antigens (CSA) antibody encapsulating MB dye were prepared and used as the signal amplifier for the development of a field-portable colorimetric immunoassay to detect Salmonellae. Tapping mode atomic force microscopy (TMAFM), a scanning probe technique, was utilized to demonstrate the presence of anti-Salmonella antibody at the thus-prepared liposome. A plastic-backed nitrocellulose strip with two immobilized zones formed the basis of a sandwich assay. The first zone was the antigen capture zone (AC zone), used in a sandwich (noncompetitive) assay format; the other was the biotin capture zone (BC zone), used as a quality control index for the strip assay. During the capillary migration of the wicking reagent containing 80 μL of immunoliposomes and 40 μL of the test sample (heat-killed S. typhimurium), sample pathogens with surface-bound immunoliposomes were captured at the AC zone, while the unbound immunoliposomes continued to migrate and bind to the anti-biotin antibodies coated on the BC zone. The color density of the AC zone was directly proportional to the number of Salmonella typhimurium in the test sample. The detection limit of the current assay with heat-killed Salmonella typhimurium was 1,680 cells. The cross-reactivity of the proposed immunoassay was also investigated, and pathogens including E. coli O157:H7 and Listeria genus specific caused no interference with the detection of Salmonella typhimurium. Shi-Chin Zeng and Wei-Hsiang Tseng contributed equally to this publication.     

Hydrogen bond formation to cyclic and acyclic polyethers

Equilibrium constants and enthalpies of hydrogen-bond formation of mcresol to various cyclic (crown) and acyclic polyethers have been determined in benzene solvent. Equilibrium constants indicated no evidence for an operative macrocyclic effect; the relationship between the increasing size of the equilibrium constant and the number of ether oxygens was rationalized with a simple statistical thermodynamic model. Enthalpies of interactions ranged between –19 and –23 kJ-mol^–1. In agreement with PCILO calculations, enthalpies of interaction were essentially independent of the number of oxygen atoms in the ether; no significant difference in enthalpies of interaction between cyclic and acyclic ethers was found.     

Capacitive biosensor for detection of endotoxin

A capacitive biosensor for the detection of bacterial endotoxin has been developed. Endotoxin-neutralizing protein derived from American horseshoe crab was immobilized to a self-assembled thiol layer on a biosensor transducer (Au). Upon injection of a sample containing endotoxin, a decrease in the observed capacitive signal was registered. Endotoxin could be determined under optimum conditions with a detection limit of 1.0 × 10⁻¹³ M and linearity ranging from 1.0 × 10⁻¹³ to 1.0 × 10⁻¹⁰ M. Good agreement was achieved when applying endotoxin preparations purified from an Escherichia coli cultivation to the capacitive biosensor system, utilizing the conventional method for quantitative endotoxin determination, the Limulus amebocyte lysate test as a reference. The capacitive biosensor method was statistically tested with the Wilcoxon signed rank test, which proved the system is acceptable for the quantitative analysis of bacterial endotoxin (P < 0.05). Figure The flow-injection capacitive biosensor system and the capacitive properties of the transducer surface, where C_SAM is the capacitance change of the self-assembled thiol monolayer, C_P is the capacitance change of the protein layer, C_a is the capacitance change of the analyte layer and C_Total is the total capacitance change measured at the working electrode/solution interface (modified from Limbut et al., 2006. Biosens Bioelectron 22: 233-240)     

Feasibility studies for the detection of volatile organic compounds in the gas phase using microelectrode sensors

The use of microelectrode sensors to detect volatile organic compounds (VOCs) in air is demonstrated. In general, VOCs that oxidize easily to form protons gave a larger electrochemical response. The use of voltammetry for speciation and the effect of electrode size on the electrochemical response are discussed. We demonstrate that surface enhanced Raman spectroscopy (SERS) can be used to monitor the electrochemical reactions in situ and discuss its applicability in identifying the electroactive species.     

Comparison of electrode materials for the detection of rapid hydrogen peroxide fluctuations using background-subtracted fast scan cyclic voltammetry

Hydrogen peroxide (H(2)O(2)) is a critically important signaling molecule. Endogenous H(2)O(2) mediates diverse physiological processes both intra- and intercellularly; and enzymatically generated H(2)O(2) is a widely used reporter molecule at biosensors that rely on enzymes to detect non-electroactive species. However, the development and application of electroanalytical methods for the direct detection of this molecule has been challenging because the electron transfer kinetics for the irreversible oxidation of H(2)O(2) are slow. We comparatively characterize the electrochemical oxidation of H(2)O(2) on bare and Nafion(?)-coated platinum and carbon-fiber microdisc electrodes using fast-scan cyclic voltammetry (FSCV). Using a waveform ranging from +0.2 to +1.3 V at 400 V s(-1), the electrocatalytic properties of the platinum surface were not readily apparent, and the carbon-fiber microelectrode demonstrated greater sensitivity and selectivity toward H(2)O(2). Nafion(?)-coating further enhanced detection on carbon electrodes. These results confirm that platinum electrodes, with or without Nafion(?), will not work acceptably with this approach, and confirm the value of carbon-fiber microelectrodes relative to more traditionally used platinum electrodes in the direct detection of rapid H(2)O(2) fluctuations using FSCV.     

Simultaneous detection of A and B trichothecenes by gas chromatography with flame ionization or mass selective detection

A clean-up cartridge consisting of ammonium sulfate, celite, alumina, charcoal and C18 was developed for the simultaneous detection of A and B type trichothecenes, namely 4,15-diacetoxy-scirpenol, T2-toxin, deoxynivalenol (DON) and nivalenol (NIV). After derivatization with N,N-dimethyl-trimethylsilyl-carbamate, the purified extracts were analyzed by gas chromatography with flame ionization (GC-FID) or mass selective detection (GC-MSD). Using this cartridge, no further sample clean-up steps are required that makes the developed method time and cost effective. The method is easy to implement; no special experience or instrumentation is required. The limits of detection in semolina and corn grits ranged from 0.30 to 0.47 mg kg⁻¹ for GC-FID and from 0.05 to 0.35 mg kg⁻¹ for GC-MSD. Corn gluten feed (CGF) samples were analyzed as well, for 4,15-diacetoxy-scirpenol and T2 toxin, with a limit of detection of 0.23 and 0.14 mg kg⁻¹, respectively.     

Investigation of the products of interaction of cyclic diketones with nitrogen-containing 1,4-binucleophiles

The interaction of arylbis(5,5-dimethylcyclohexane-1,3-dion-2-yl)methanes with o-phenylenediamine and o-aminophenol leads to the preparation of 3,3-dimethyl-11-aryl-2,3,4,5,10,11-hexahydrobenzo[b,e]-1,4-diazepin-1-ones and 3,3,6,6-tetramethyl-9-aryl-10-(2-hydroxyphenyl)-2,4,5,7,9-decahydroacridine-1,8-diones respectively. A one-pot method is proposed for the synthesis of derivatives of hexahydrodibenzo[b,e]-1,4-diazepin-1-ones. The structure of the first member of this series was confirmed by X-ray diffraction analysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1798–1808, December, 2004.     

Surfactin-like structures of five cyclic depsipeptides from the marine isolate ofBacillus pumilus

Five cyclic depsipeptides with molecular masses of 1007, 1021, 1021, 1035, and 1035 were obtained fromBacillus pumilus KMM 150 associated with Australian marine spongeIrcinia sp. Their structures were assigned by mass spectrometric techniques (high-resolution fast atom bombardment and electron impact mass spectrometry), chemical modification, and extensive spectroscopic analysis, including several types of two-dimensional NMR.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 979–983, May, 1995.The authors are grateful to Dr. V. V. Mikhailov, the Head of the Laboratory of marine microbiology of PIBC of the Far-Eastern Branch of the RAS, and to Dr. E. P. Ivanova for isolation, systematic determination, and cultivation of the strain KMM 150. The authors are also thankful to T. I. Zykova for carrying out the fermentative hydrolysis of peptide4c.     

On the possibilities of ICP-AES for analysis of archaeological bones

The possibility of using inductively coupled plasma atomic emission spectrometry (ICP-AES) to determine the elemental composition of archaeological bones elements was evaluated and discussed. The interferences of the major elements (Ca, P, K, Na, Al and Fe) on the microelements (Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr, Zn) were investigated and the appropriate analytical lines were selected. The role of different nebulizers (cross-flow, Babington and Meinhard) on detection limits were investigated. The applicability of the proposed procedure was demonstrated analyzing IAEA-SRM-H-5 (Animal bone); and authentic bone sample dating back to the 4^th century BC. These results were compared to ETAAS and ICP-MS.     

Statistical Determination of Optimal Baculovirus Infection Condition for Recombinant Protein Production in <Emphasis Type="Italic">Drosophila</Emphasis> S2 Cells

Insect Drosophila melanogaster S2 cell was developed as plasmid-based and, therefore, a nonlytic expression system for functional foreign proteins. To achieve multiple protein expressions, it was suggested that baculovirus be used on S2 cell system because baculovirus can infect S2 cells but cannot replicate inside the cells. Therefore, establishment of baculovirus infection conditions is the first important step and this should be properly optimized for production yield. We used statistical methodology to optimize the baculovirus infection conditions using green fluorescent protein (GFP) as a reporter protein. Consequently, we arrived at optimal infection conditions through a statistical regression method. The secreted GFP yield from vMT-GFP baculovirus-infected wild-type S2 cells under optimal infection conditions was >15-fold higher than that under nonoptimal conditions and comparable to that from stably transfected recombinant S2 cells.     

等离激元增强上转换发光及其分子检测应用

针对荧光分子检测普遍灵敏度低和检测范围窄的问题,制备了具有等离子激元共振特性的重掺杂半导体纳米结构Cu_2-xS和典型的稀土掺杂上转换发光纳米颗粒NaYF₄∶Yb,Er,通过三相界面自组装方法获得了Cu_2-xS/NaYF₄∶Yb,Er薄膜基底。结合有限元模拟,计算了不同摆放情况下Cu_2-xS周围的局域电场分布,研究了在实际薄膜中Cu_2-xS纳米盘之间产生的等离激元耦合对上转换发光性能以及对拉曼信号增强的影响。结果表明,Cu_2-xS等离激元层与NaYF₄∶Yb,Er发光层的耦合,不仅得到了上转换 3个数量级的提高,还实现了分子检测 10^-7 mol·L^-1的检测极限,并且获得了 10^-3~10^-7 mol·L^-1的宽线性响应,从而达到高灵敏度的定性和定量双功能的精确检测。     

Development of bacteria-based bioassays for arsenic detection in natural waters

Arsenic contamination of natural waters is a worldwide concern, as the drinking water supplies for large populations can have high concentrations of arsenic. Traditional techniques to detect arsenic in natural water samples can be costly and time-consuming; therefore, robust and inexpensive methods to detect arsenic in water are highly desirable. Additionally, methods for detecting arsenic in the field have been greatly sought after. This article focuses on the use of bacteria-based assays as an emerging method that is both robust and inexpensive for the detection of arsenic in groundwater both in the field and in the laboratory. The arsenic detection elements in bacteria-based bioassays are biosensor–reporter strains; genetically modified strains of, e.g., Escherichia coli, Bacillus subtilis, Staphylococcus aureus, and Rhodopseudomonas palustris. In response to the presence of arsenic, such bacteria produce a reporter protein, the amount or activity of which is measured in the bioassay. Some of these bacterial biosensor–reporters have been successfully utilized for comparative in-field analyses through the use of simple solution-based assays, but future methods may concentrate on miniaturization using fiberoptics or microfluidics platforms. Additionally, there are other potential emerging bioassays for the detection of arsenic in natural waters including nematodes and clams.     

Prepatellamide A, a new cyclic peptide from the ascidian Lissoclinum patella

A new cyclic peptide, prepatellamide A (1), along with three known cyclic peptides (2)— (4), was isolated from the ascidianLissoclinum patella. The structure of prepatellamide A was determined from one- and two-dimensional¹H and¹³C NMR spectra. The known cyclic peptides were identified as patellamides A (2), B (3) and C (4).     

Determination of zinc(II) in biological samples by anodic stripping voltammetry

The use ofN-benzyltrimethylammonium methoxide as a digesting solvent, for the determination of zinc(II) in biological samples using anodic-stripping voltammetry is reported. It was found possible to determine zinc directly in biological samples containing such metals as copper(II), lead(II), iron(III), arsenic(III) and selenium(IV). The results for zinc in bovine liver and oyster tissue are reported.