The review article is devoted mainly to the description of applications of gold nanoparticles (GNPs) in separation sciences, especially in electromigration and chromatographic techniques. The applications of GNPs in particular separation methods, CE, microchip CE, MEKC, CEC, HPLC and GC, are classified according to the molecular size of the analytes from low-molecular-mass compounds via medium sized substances to biopolymers (proteins and nucleic acids). A very recent and promising utilization of GNPs for sample preparation, preconcentration and preseparation of selected analytes from complex matrices is presented as well. Moreover, in two introductory sections, typical preparation procedures of the GNPs and their modifications are presented and physicochemical and analytical methods employed for characterization of the native and modified GNPs are briefly introduced.
The systematic study of structures with gold and silver nanoparticles (MeNPs) of various shapes and dielectric functions immobilized onto the silver grating is performed. The structures may serve as double resonance SERS (surface-enhanced Raman spectroscopy) systems with coupling between surface plasmon polariton (SPP) supported by the silver grating and localized surface plasmons (LSPs) excited on the grafted metal nanoparticles (MeNPs). The silver grating supports SPP excitation under the 785 nm wavelength illumination. Spherical silver and gold nanoparticles, triangular silver nanoprisms and gold nanorods are prepared and used with the aim to gradually cover the LSP excitation in the 400–850 nm wavelength range. MeNPs are grafted through the 4,4′-biphenyldithiol (BFDT) linkers. Rhodamine 6G (R6G) molecules are added onto SERS substrates and located above and between the MeNPs. Several wavelengths (470, 532, and 785 nm) are applied to probe the SERS response. Depending on the nanoparticles type and excitation wavelength a significant SERS signal is produced by R6G or BFDT molecules. Properties of the prepared structures are simulated using the Finite-difference time-domain method (FDTD). The measured and simulated SERS data are in reasonable agreement, the measured values being lower than those calculated.
In this work, a simple method for alcohol synthesis with high enantiomeric purity was proposed. For this, colloidal gold and silver surface modifications with 3-mercaptopropanoic acid and cysteamine were used to generate carboxyl and amine functionalized gold and silver nanoparticles of 15 and 45 nm, respectively. Alcohol dehydrogenase from Thermoanaerobium brockii (TbADH) and its cofactor (NADPH) were physical and covalent (through direct adsorption and using cross-linker) immobilized on nanoparticles' surface. In contrast to the physical and covalent immobilizations that led to a loss of 90% of the initial enzyme activity and 98% immobilization, the use of a cross-linker in immobilization process promoted a loss to 30% of the initial enzyme activity and >92% immobilization. The yield of NADPH immobilization was about 80%. The best results in terms of activity were obtained with Ag-citr nanoparticle functionalized with carboxyl groups (Ag-COOH), Au-COOH(CTAB), and Au-citr functionalized with amine groups and stabilized with CTAB (Au-NH2(CTAB)) nanoparticles treated with 0.7% and 1.0% glutaraldehyde. Enzyme conformation upon immobilization was studied using fluorescence and circular dichroism spectroscopies. Shift in ellipticity at 222 nm with about 4 to 7 nm and significant decreasing in fluorescence emission for all bioconjugates were observed by binding of TbADH to silver/gold nanoparticles. Emission redshifting of 5 nm only for Ag-COOH-TbADH bioconjugate demonstrated change in the microenvironment of TbADH. Enzyme immobilization on glutaraldehyde-treated Au-NH2(CTAB) nanoparticles promotes an additional stabilization preserving about 50% of enzyme activity after 15 days storage. Nanoparticles attached-TbADH-NADPH systems were used for enantioselective (ee > 99%) synthesis of (S)-7-hydroxy-2-tetralol.
Mixed‐mode phases have become very popular in the last decade, and the number of new mixed/multi‐mode sorbents is growing fast. Unlike single‐mode stationary phases, perfectly suited for the separation of the analytes possessing similar physicochemical properties, for instance reversed‐phase chromatography for hydrophobic solutes, mixed‐mode sorbents providing multimodal interactions can render better separation selectivity for complex mixtures of solutes differing significantly in their physicochemical characteristics. The most frequent modern mixed‐mode stationary phases are di/tri‐mode sorbents embracing the following interactions, hydrophobic, electrostatic (coulombic), and hydrophilic. According to their structures, it is possible to distinguish silica‐based, polymer‐based, hybrid, and monolithic mixed‐mode stationary phases. Herewith, newly synthesized mixed‐mode sorbents developed within the last two and half years are categorized, discussed, and summarized. The main attention is devoted to the description of the synthetic routes and characterization methods applied for the new stationary phases.
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