On the Nature of Mass Spectrometer Analyzer Contamination

Sample throughput in electrospray ionization mass spectrometry (ESI-MS) is limited by the need for frequent ion path cleaning to remove accumulated debris that can lead to charging and general performance degradation. Contamination of ion optics within the vacuum system is particularly problematic as routine cleaning requires additional time for cycling the vacuum pumps. Differential mobility spectrometry (DMS) can select targeted ion species for transmission, thereby reducing the total number of charged particles entering the vacuum system. In this work, we characterize the nature of instrument contamination, describe efforts to improve mass spectrometer robustness by applying DMS prefiltering to reduce contamination of the vacuum ion optics, and demonstrate the capability of DMS to extend the interval between mass spectrometer cleaning. In addition, we introduce a new approach to effectively detect large charged particles formed during the electrospray ionization (ESI) process.

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Methodology of chemometric modeling of spectrometric signals in the analysis of complex samples

A generalized algorithm of the multivariate simulation of spectrometric data is considered for solving typical analytical problems, like the determination of the concentration of a particular analyte and the assignment of a sample to one of predefined classes. In particular, we considered preliminary data processing, exploratory analysis, optimization of a chemometric model, calculation of performance characteristics, transfer of the model to other spectrometers, and automation of chemometric processing for the routine analysis of samples. To illustrate the potential of the method, we selected a system of bovine and porcine heparin, mixtures of soy and sunflower lecithin, and a set of red and white wine samples as test samples. Partial least squares and discriminant analysis were used as chemometric methods. We used proton nuclear magnetic resonance (1H NMR) to record signals. Using the MATLAB environment, chemometric programs were developed for automated data processing in the context of problems under consideration and for the transfer of multivariate models to other spectrometers. Based on the results obtained, a methodology is proposed for the multivariate analysis of spectrometric data, which can be used in the analysis of various types of matrices and spectrometric signals.     

An electrochemical aptasensor for cytochrome C,based on pillar[5]arene modified with Neutral Red

An electrochemical aptasensor is developed for the highly sensitive determination of cytochrome C, using a change in the redox current of Neutral Red covalently bound to terminal carboxyl groups of decasubstituted pillar[5]arene as a signal. The inclusion of the analyte into the complex with an aptamer reduces peaks of redox current of the dye through the dissociation of electron transfer chain in the surface layer. The aptasensor enables the determination of 1 nM to 1.0 mM of cytochrome C in the presence of 1000-fold excesses of albumin, polyethylene glycol, and lysozyme as models of interfering components in biological fluids.     

Mechanism of reaction of selenium elimination in diacetophenonyl selenide under the action of reduced glutathione

Products of reaction between the organoselenium xenobiotic, diacetophenonyl selenide (1,5-diphenyl-3-selenapenta-1,5-dione), and reduced glutathione at different molar ratios and pH values were studied by HPLC and TLC. Reaction intermediates, S-(acetophenylselenyl)glutathione and glutathione selenodisulfide, and reaction products, acetophenone and hydroselenide anion, were detected. The reaction scheme proposed earlier was confirmed.     

Primary photophysical and photochemical processes for Pt(SCN)<Subscript>6</Subscript><Superscript>2–</Superscript> complex

Photosolvation of a Pt^IV hexathiocyanate complex Pt(SCN)₆ ^2– in water and ethanol was studied by steady-state photolysis, nanosecond laser flash photolysis, and ultrafast kinetic spectroscopy. Complexes Pt(SCN)₅(H₂O)^– and Pt(SCN)₅(C₂H₅OH)^– were found to be the only reaction products. The quantum yields of photosolvation are independent of the excitation wavelength, being equal to 0.25 and 0.5 for the solutions of the complex in water and ethanol, respectively. Photosolvation proceeds by the mechanism of heterolytic metal—ligand bond dissociation without involvement of redox processes. The characteristic time of formation of the end products for both solvents is about 10 ps. Three successive intermediates detected on the picosecond time scale were interpreted as Pt^IV complexes. The nature of the intermediates and possible mechanisms of photosolvation are discussed.     

Conjugation of indole derivatives by copper-catalyzed alkyne-azide cycloaddition

An efficient synthetic procedure to combine biologically active indole derivatives by the triazole-containing spacer in a molecule has been proposed. The procedure was based on a copper-catalyzed alkyne-azide cycloaddition of azide-containing carbazoles and N-propargyl-containing carbazoles, tetrahydrocarbazoles, and tetrahydro-γ-carbolines.     

Heterocyclization of carboxy- and sulfonamides in the course of oxidative addition to unsaturated substrates

Formation of heterocyclic compounds in the course of oxidative addition of carboxamides and sulfonamides to alkenes and dienes is reviewed. Main attention is focused on reactions proceeding in the presence of halo-containing oxidative systems and reagents. Features of behavior of fluorine-substituted sulfonamides and carboxamides are discussed.     

Alkaline Protease Production from <Emphasis Type="Italic">Brevibacterium luteolum</Emphasis> (MTCC 5982) Under Solid-State Fermentation and Its Application for Sulfide-Free Unhairing of Cowhides

Enzyme-based unhairing in replacement of conventional lime sulfide system has been attempted as an alternative for tackling pollution. The exorbitant cost of enzyme and the need for stringent process control need to be addressed yet. This study developed a mechanism for regulated release of protease from cheaper agro-wastes, which overcomes the necessity for stringent process control along with total cost reduction. The maximum protease activity of 1193.77 U/g was obtained after 96 h of incubation with 15% inoculum of the actinomycete strain Brevibacterium luteolum (MTCC 5982) under solid-state fermentation (SSF). The medium after SSF was used for unhairing without the downstream processing to avoid the cost involved in enzyme extraction. This also helped in the regulated release of enzyme from bran to the process liquor for controlled unhairing and avoided the problem of grain-pitting. Unhairing process parameters were standardized as 20% enzyme offer, 40% Hide-Float ratio at 5 ± 1 rpm, and process pH of 9.0. The cost of production of 1000 kU of the protease was calculated as 0.44 USD. The techno-economic feasibility studies for setting up an SSF enzyme production plant showed a high return on investment of 15.58% with a payback period of 6.4 years.     

Effect of heterocyclic ring system on formation of dimeric quinolones under catalyst-free conditions: a green approach

The intermediate-dependent green and efficient synthesis of dimeric quinolones 4a–l and 7a–l by the Knoevenagel condensation followed by Michael-type addition of 4-hydroxy-1-methylquinolin-2(1H)-one 1a, b to indole-3-aldehydes 2a–f and aromatic aldehydes 5a–l in water through the condensed compound 3a–l under catalyst-free conditions is described. This reaction was found to be environmentally friendly, has easy-workup and shorter reaction times giving good yields of the product without the need for its isolation using column chromatography.     

Optical activity of films based on chitosan of various molecular masses and modifications

The effect of chemical (polysalt → polybase reaction) and physicochemical (heat and vapor processing) modifications of the films of chitosan of various molecular masses and prehistories on the optical activity of the polysaccharide is studied. For both of the chitosan chemical modifications, the following dependence that is nontrivial for high-molecular compounds is established: [α] = f(log\({\bar M_\eta }\)); as the degree of polymerization decreases, the modulus of [α] of the films increases. The X-ray diffraction study shows that the differences in the optical activity of the samples with different \({\bar M_\eta }\) are caused by a restriction in the mobility of the macromolecular sections upon formation of the films of high-molecular chitosan and incompleteness of the relaxation processes of the film systems to the state with energetically favorable conformations. The comparison of humidity and optical and biological activities of the initial and dehydrated chitosan films is performed. The chitosan films in the salt modification feature moderate bactericidal activity, which decreases with an increase in \({\bar M_\eta }\) of the polymer. The thermal processing of the salt modification reduces the antibacterial action; a conversion to the base form is accompanied by the loss of bactericidal activity.