Fast Monitoring of Nano‐Molar Level of Gentamycin by Fast Fourier Transform Continuous Cyclic Voltammetry in Flowing Solution

Abstract

A novel method for the determination of gentamycin in flow‐injection systems has been developed in this work. The principal advantages of this method are that it is rapid, simple, and possesses low detection limit. Some investigations were also done to find the effects of various parameters on the sensitivity of the proposed method. The conditions producing the performance were the pH value of 2, the scan rate value of 350 V/s, accumulation potential of (100 mV), and accumulation time of 0.9 s. Some of the advantages of the proposed method are: the removal of oxygen from the test solution is not required anymore, the detection limit of the method is sub‐nanomolar, and finally, the method is fast enough for determination of such compounds, in a wide variety of chromatographic methods. We also introduce a special computer‐based numerical method for calculation of the analyte signal and noise reduction. After subtracting the background current from noise, the electrode response was calculated, based on partial and total charge exchanges at the electrode surface. The integration range of currents was set for all the potential scan ranges, including oxidation and reduction of the Au surface electrode, to obtain a sensitive determination. The waveform potential was continuously applied on an Au disk microelectrode (12.5 µm in radius). Detention limit of the method for gentamycin was found to be 1.0×10^?9 M. For 10 runs, the relative standard deviation of the method at 1.0×10^?7 M was 2.1%.     

Fast GC–MS Pesticide Multiresidue Analysis of Apples

A fast gas chromatographic–mass spectrometric (GC–MS) method is proposed for pesticide multiresidue analysis of apples. The QuEChERS method was used for sample preparation. GC–MS analysis was performed with a PTV, an autoinjector, and a quadrupole benchtop MS detector. Electron-impact ionization (70 eV) was used with two modes of selected ion monitoring. Compounds were separated under temperature-programmed conditions on a narrow-bore diphenyldimethylsiloxane column. In one chromatographic run 61 pesticides of different chemical classes, and triphenyl phosphate as internal standard, were determined in 11 min. Calibration was performed with matrix-matched standard solutions and response to the pesticides was a linear function of concentration in the range 1–500 ng mL⁻¹ (equivalent to 1–500 μg kg⁻¹ in real samples). High values of the determination coefficients (R ²; 0.9900–1.0000) were obtained for most of the pesticides. Limits of detection and quantification were determined. When the method was used for analysis of pesticide residues in real samples, five pesticides were detected at concentrations in the range 1.00–21.47 μg kg⁻¹. Repeatability of measurements, expressed as relative standard deviations of absolute peak areas, normalized relative to TPP, and of the concentrations determined, met the EU criterion of RSD ≤ 20%. Use of the internal standard moderately improved quantitative results.

     

Real-Time NMR. How Fast Can We Do It?

Network structure development during cross-linking photopolymerization of polyethylene glycol di-acrylate and its mixture with a mono-functional 2-ethylhexyl acrylate was studied using real-time proton NMR T₂ relaxation analysis. The time resolution of the method is typically in the order of seconds. The results reveal largely heterogeneous origin of network build up at the intermediate stages of photocuring. Domains of nano-gel are already formed on initial stages of UV-curing where hardly any change in viscosity is observed. Upon increasing curing time the fraction of gel increases at the expence of sol, the molar mass of network chains decreases and the molar mass of sol increases. The presence of mono-acrylate slows down the curing rate. The curing continues after UV-illumination causing a significant increase in the amount of gel and cross-link density in the gel. Thus, the NMR method is a valuable tool for characterization of the kinetics of photopolymerization, the development of molecular structure and the resultant molecular scale heterogeneity during photocuring.     

Fast sol–gel technology: from fabrication to applications

A novel method to prepare crack-free sol–gel materials without shrinkage is reviewed. The method allows fabrication of a viscous sol–gel resin in a few minutes followed by either thermal-curing or UV-curing requiring several hours or several minutes, respectively. The method is distinguished by the short time required to achieve a solid monolith. The fast sol–gel method uses a combination of organically modified alkoxides with traditional alkoxides as precursors, to produce a final product which is an organic-inorganic hybrid with properties that vary from silicone rubbers to silica glass. Optical and physical properties, such as refractive index and thermal expansion, can be engineered by controlling the ratio between the precursors. This class of materials is a promising candidate for preparation of optical elements such as waveguides and submicron structured replicas and can also be used as an optical bonding material. This paper reviews the fast sol–gel technology, as well as methods to characterize the process and its final products. Various applications of fast sol–gel materials are presented.     

Fast and protecting-group-free synthesis of (±)-subincanadine C

The first total synthesis of (±)-subincanadine C has been accomplished in a protecting-group-free fashion. This pentacyclic indole alkaloid was synthesized in six steps from the known intermediate 4, featuring Ni(COD)(2)-mediated intramolecular Michael addition as a key transformation.     

Fast quantification of amino acids by microchip electrophoresis–mass spectrometry

A fast microchip electrophoresis–nano-electrospray ionization-mass spectrometric method (MCE-nanoESI-MS) was developed for analysis of amino acids in biological samples. A glass/poly(dimethylsiloxane) hybrid microchip with a monolithic nanoESI emitter was used in the platform. The proposed MCE-nanoESI-MS analytical method showed high separation efficiency for amino acids. Baseline separation of an amino acid mixture containing Lys, Arg, Val, Tyr, and Glu was completed within 120 s with theoretical plate numbers of >7,500. The method was applied to study cellular release of excitatory amino acids (i.e., aspartic acid (Asp) and glutamic acid (Glu)) under chemical stimulations. Linear calibration curves were obtained for both Asp and Glu in a concentration range from 1.00 to 150.0 μM. Limits of detection were found to be 0.37 μM for Asp and 0.33 μM for Glu (S/N?=?3). Assay repeatability (relative standard deviation, n?=?6) was 4.2 and 4.5 %, for Asp and Glu at 5.0 μM, respectively. In the study of cellular release, PC-12 nerve cells were incubated with alcohol at various concentrations for 1 h. Both extra- and intracellular levels of Asp and Glu were measured by the proposed method. The results clearly indicated that ethanol promoted the release of both Asp and Glu from the cells.     

Recent Results on Fast Flow Gas-Phase Partial Oxidation of Lower Alkanes

Recent experimental results and kinetic modeling of fast flow gas-phase oxidation of methane and other lower alkanes to methanol and other oxygenates are discussed,alongside with prospects and possible areas for applications of the processes.     

Fast counter-electroosmotic capillary electrophoresis–time-of-flight mass spectrometry of hyaluronan oligosaccharides

Fast capillary electrophoresis–mass spectrometry measurements under counter-electroosmotic analyte migration conditions are presented. Efficient separations of a homologous series of six hyaluronan oligosaccharides (comprising 1–6 hyalobiuronic acid moieties) could be completed in 65 s. Separations were achieved in short-length fused silica capillaries under high electric field strengths of up to 1.25 kV·cm⁻¹. Capillary inner diameters ranging from 5 to 50 μm were investigated, resulting in an optimal value of 15 μm. The influence of capillary dimensions and buffer composition on separation efficiency and sensitivity are discussed. Optimal separations were achieved using a 28 cm × 15 μm capillary, a separation high voltage of 35 kV, a background electrolyte of 25 mM ammonium acetate adjusted to pH 8.5, and negative ionization mode. The optimized method was successfully applied to a bovine testicular hyaluronidase digest of hyaluronan. Only minimal sample pretreatment for protein-containing samples is required. The simple manual injection procedure and fast separations allow for a sample throughput of 35 samples per hour.     

Fast responsive poly(N-sopropylacrylamide) hydrogels prepared by γ-ray irradiation

γ-ray irradiation of N-isopropylacrylamide (NIPAAm) monomer. solution resulted in the formation of the opaque poly (N-isopropylacrylamide) (PNIPAAm) gel having a microporous structure. The thermo-responsive properties of the microporous gel were the same as that of a homogeneous gel prepared by conventional methods. The gel swelled below and shrunk above the lower critical solution temperature (LCST) (33 °C). The rapid and reversible volume change was observed by changing temperature.     

Elastic Polymer Coated Nanoparticles with Fast Clearance for 19F MR Imaging

¹⁹F magnetic resonance imaging (MRI) is a powerful molecular imaging technique that enables high-resolution imaging of deep tissues without background signal interference. However, the use of nanoparticles (NPs) as ¹⁹F MRI probes has been limited by the immediate trapping and accumulation of stiff NPs, typically of around 100 nm in size, in the mononuclear phagocyte system, particularly in the liver. To address this issue, elastic nanomaterials have emerged as promising candidates for improving delivery efficacy in vivo. Nevertheless, the impact of elasticity on NP elimination has remained unclear due to the lack of suitable probes for real-time and long-term monitoring. In this study, we present the development of perfluorocarbon-encapsulated polymer NPs as a novel ¹⁹F MRI contrast agent, with the aim of suppressing long-term accumulation. The polymer NPs have high elasticity and exhibit robust sensitivity in ¹⁹F MRI imaging. Importantly, our ¹⁹F MRI data demonstrate a gradual decline in the signal intensity of the polymer NPs after administration, which contrasts starkly with the behavior observed for stiff silica NPs. This innovative polymer-coated NP system represents a groundbreaking nanomaterial that successfully overcomes the challenges associated with long-term accumulation, while enabling tracking of biodistribution over extended periods.     

Fast gel permeation chromatography–mass spectrometry method for polymer and additive analysis

This study presents gel permeation chromatography (GPC) coupled with mass spectrometry (MS) as a suitable method to evaluate molecular weight distribution, oligomeric structure, and additives of commercial polystyrene resins in just 4?min. The chromatogram recorded by ultraviolet (UV) detection gives information on the high molecular mass fractions, while the mass detector provides knowledge on the chemical structure and concentration of oligomers and additives. A good agreement for the average molecular weights of the broad polystyrene reference SRM 706 and an excellent correlation with the expected isotope distributions for oligomers and additives were obtained using this fast GPC–UV–MS method.     

Fast Detection of Entacapone by a Lanthanide–Organic Framework with Rhombic Channels

Entacapone (ENT) is a powerful catechol-O-methyl transferase inhibitor that is used for the diagnosis and treatment of Parkinson's syndrome, but the amount used must be well controlled to avoid overtreatment and side effect. Fast and selective detection of ENT needs well-matched energy levels and well-designed sensor-ENT interaction which is highly challenging. In this work, a water stable europium-based metal-organic framework ( Eu-TDA ) was synthesized to detect ENT by luminescence with excellent reusability and selectivity in the presence of main coexisting and interference species of plasma with a limit of detection of 5.01 μM. The experimental results showed that the luminescence of Eu-TDA can be effectively quenched by ENT via well-designed photoinduced electron transfer mechanism and internal filtration effect mechanism in the system.     

Fast electron transfer repair of oxidizing OH adduct of dGMP by chlorogenic acid

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Monitoring of Methyldopa by Fast Fourier Transform Continuous Cyclic Voltammetry at Gold Microelectrode

A continuous cyclic voltammetric study of methyldopa at gold micro electrode was carried out. The drug in phosphate buffer (pH 2.0) is adsorpted at 400 mV, giving rise to change in the current of well-defined oxidation peak of gold in the flow injection system. The proposed detection method has some of advantages, the greatest one of which are as follows: first, it is no more necessary to remove oxygen from the analyte solution and second, this is a very fast and appropriate technique for determination of the drug compound in a wide variety of chromatographic analysis methods. Signal-to-noise ratio has significantly increased by application of discrete Fast Fourier transform (FFT) method, background subtraction and two-dimensional integration of the electrode response over a selected potential range and time window. Also in this work some parameters such as sweep rate, eluent pH, and accumulation time and potential were optimized. The linear concentration range was of 1.0×10－7—1.0×10－11 mol•L－1 (r＝0.9975) with a limit of detection and quantitation 0.004 nmol•L－1 and 0.03 nmol•L－1, respectively. The method has the requisite accuracy, sensitivity, precision and selectivity to assay methyldopa in tablets. The influences of pH of eluent, accumulation potential, sweep rate, and accumulation time on the determination of the methyldopa were considered.     

Fast electron density methods in the life sciences--a routine application in the future?

The understanding of mutual recognition of biologically interacting systems on an atomic scale is of paramount importance in the life sciences. Electron density distributions that can be obtained from a high resolution X-ray diffraction experiment can provide--in addition to steric information--electronic properties of the species involved in these interactions. In recent years experimental ED methods have seen several favourable developments towards successful application in the life sciences. Experimental and methodological advances have made possible on the one hand high-speed X-ray diffraction experiments, and have allowed on the other hand the quantitative derivation of bonding, non-bonding and atomic electronic properties. This has made the investigation of a large number of molecules possible, and moreover, molecules with 200 or more atoms can be subject of experimental ED studies, as has been demonstrated by the example of vitamin B12. Supported by the experimentally verified transferability concept of submolecular electronic properties, a key issue in Bader's The Quantum Theory of Atoms in Molecules, activities have emerged to establish databases for the additive generation of electron densities of macromolecules from submolecular building blocks. It follows that the major aims of any experimental electron density work in the life sciences, namely the generation of electronic information for a series of molecules in a reasonable time and the study of biological macromolecules (proteins, polynucleotides), are within reach in the near future.     

Fast and Precise Quantification of l-Homoarginine in Human Plasma by HILIC-Isotope Dilution-MS–MS

Lowered plasma concentrations of the endogenous amino acid l-homoarginine have been recently identified as an independent risk factor for cardiovascular and all-cause mortality in patients referred for coronary angiography in the LURIC study. To support further investigations into this matter, we describe here a fast and easy LC–MS–MS method for the detection of l-homoarginine in human plasma. The sample preparation consisted only of the addition of the stable isotope-labeled internal standard d ₄-l-homoarginine and protein precipitation. The analytes were separated isocratically on an HILIC silica column. Detection took place by tandem mass spectrometry. The calibration function was linear in the range of 0.1–10 μmol L⁻¹. The intra-day precision was better than 2 % RSD and the inter-day precision better than 4 % RSD in plasma. The accuracy was always better than 5 % deviation. The method was matrix independent owing to the usage of the analogous stable isotope-labeled internal standard.

     

Fast and Precise Quantification of l-Homoarginine in Human Plasma by HILIC-Isotope Dilution-MS–MS

Lowered plasma concentrations of the endogenous amino acid l-homoarginine have been recently identified as an independent risk factor for cardiovascular and all-cause mortality in patients referred for coronary angiography in the LURIC study. To support further investigations into this matter, we describe here a fast and easy LC–MS–MS method for the detection of l-homoarginine in human plasma. The sample preparation consisted only of the addition of the stable isotope-labeled internal standard d ₄-l-homoarginine and protein precipitation. The analytes were separated isocratically on an HILIC silica column. Detection took place by tandem mass spectrometry. The calibration function was linear in the range of 0.1–10 μmol L^?1. The intra-day precision was better than 2 % RSD and the inter-day precision better than 4 % RSD in plasma. The accuracy was always better than 5 % deviation. The method was matrix independent owing to the usage of the analogous stable isotope-labeled internal standard.     

Fast screening of stabilizers in polymeric materials by flow injection–tandem mass spectrometry

In the present study, the applicability of rapid flow injection–triple quadrupole mass spectrometry for simultaneous qualitative screening of different classes of stabilizers in polymeric materials is demonstrated. Electrospray ionization and atmospherical pressure chemical ionization were compared, whereby the latter yielded generally poorer detection limits and only single charged ions that were for some analytes beyond the mass range of the quadrupole mass spectrometry. Positive electrospray ionization allowed the interference-free monitoring of multiple reaction monitoring transitions selective for 36 commonly used stabilizers without chromatographic separation. Real polymer samples were extracted by toluene and the method allowed the detection of analytes down to 0.00001–0.025 wt% depending on the stabilizer.     

Simple,Extremely Fast,and High‐Yielding Oxidation of Thiols to Disulfides

Abstract

Results of oxidation of thiols to disulfides with 1,3‐dibromo‐5,5‐dimethylhydantoin (DBDMH) are described. A simple addition of 0.20–0.25 mol equivalent of solid DBDMH to thiol in chloroform at room temperature yielded the disulfides in excellent yield. The reaction is extremely fast and gave no other oxidized side products.     

Novel Method of Preparation of Monolithic Columns for Fast Separation by γ-Ray Irradiation

A porous monolithic sol-gel column with the solution of methacryloxypropyltrimethoxysilane in toluene with an acid catalyst was prepared in the presence and absence of sodium dodecyl sulfate. In situ polymerization was carried out byγ-ray irradiation within the capillary. Theγ-radiation-initiated synthesis could generate radicals directly on the monomer avoiding use of any initiator. The chromatographic behavior of the capillary monolithic columns were studied in the modes of CEC, p-CEC and low pressure-driven separation, all the tests exhibited reversed-phase character. It provided a viable alternative to either thermally initiated or photo polymerization method for the preparation of monolithic columns.