Applications of Graphene and Its Derivatives in Chemical Analysis.

In this review, the applications of graphene and its derivatives in the chemical analysis have been described. The properties of graphene materials which are essential for their use in chemical and biochemical analysis are characterized. The materials are used in sensors and biosensors, in electrochemistry, in chromatography and in the sample preparation techniques. Chemical and electrochemical sensors containing graphene materials are useful devices for detecting some chemical and biochemical compounds. Chromatographic columns for HPLC with graphene containing stationary phases may be used for separation of polar and nonpolar components of some specific mixtures. Graphene materials could be successfully employed during sample preparation for analysis with SPE, magnetic SPE, and SPME techniques. HighlightsThe review of the applications of graphene (G) and its derivatives, graphene oxide (GO) and reduced graphene oxide (rGO), in chemical and biochemical analysis is proposed.The electron donor-acceptor and proton donor-acceptor interactions for the graphene based materials - analytes systems and their impact on the analysis results are discussed, particularly: i) in electrochemistry,ii) in chromatography,iii) in modern sample preparation techniquesiv) in sensors of different types.The essence of the thermal stability and the nomenclature of the graphene based materials in their different applications in chemical systems of different classes was discussed (and suggested).The benefits of using SPME fibers with immobilized graphene materials have been presented in detail.

Liquid Crystals as Stationary Phases in Chromatography.

The most correct analysis of the compositions of diverse analytes mixtures is significant for analytical studies in different fields; however, many prevalent analytes cannot be identified employing traditional partition gas chromatographic methods. Thus, the increasing requirements on analytes of isomeric compounds and the problems encountered in their separation demand a study of more diverse analytical systems which are characterised by higher selectivity. Therefore, the selectivity and polarities of various liquid crystals (rod-like, banana-shape, biforked, oxygen, sulphur, nitrogen, and metal containing molecules, Schiff-base, and polymeric dendrimers) employed as liquid crystalline stationary phases (LCSPs) have been discussed from both points of views, namely, their analytical applications and thermodynamic characteristics of infinitely diluted probes with different acceptor-donor properties. Extreme particular effort has been paid to the different interdependencies between the bound up chemical structures of liquid crystal molecules with their different acceptor-donor properties and the connected resolution capabilities in the interpretation of the probe-LCSP systems, on the basis of the [Formula: see text] and [Formula: see text] dependencies, with regard to the LCSP compositions, which have been controlled by the counterbalancing of the enthalpy and entropy factors. The properties of binary systems composed of liquid crystalline poly(propyleneimine) dendrimers-rod-like molecules of liquid crystals and effects of the dendrimer structure, the chemical nature, and molecular size of the non-mesogens on the ability to dissolve in the liquid crystalline phases, have been interpreted. Practical applications of metallomesogenes and chiral stationary phases for analytical separation of different organic substances have also been taken into consideration.

Secondary emission influenced fluorescence decay of a homogeneous fluorophore solution.

An analytical expression is found allowing the calculation of the secondary emission influenced fluorescence decay of a homogeneous fluorophore solution. Before starting the calculation one has to know the shape of the primary fluorescence decay of the fluorophore and the value of the parameter κ denoting the ratio of the secondary to primary steady-state fluorescence intensities. The method elaborated by Budó and Ketskeméty is recommended for evaluation of the parameter κ. The main importance of the obtained expression is that it can be used to recover parameters characterizing the fluorescence decay in the absence of secondary emission. The cases of monoexponential, biexponential and multiexponential primary fluorescence decays are discussed in detail.

Synthesis of OMS Materials and Investigation of Their Acceptor-Donor Characteristics.

Three ordered mesoporous siliceous (OMS) materials known as MCM41s-unmodified MCM-41C16 ("C16"), and two MCM41s with different surface functionalities: MCM-41C16-SH ("C16-SH") and MCM-41C16-NH2 ("C16-NH2")-were synthesized and studied by inverse gas chromatography in order to determine their acceptor-donor properties. The specific retention volumes of nonpolar and polar probes that were chromatographed on these ordered mesoporous silica adsorbents were evaluated under infinite dilution conditions. Two methods were employed to calculate the standard free energy of adsorption, ΔGads, of each chromatographed probe on the basis its specific retention volume. These ΔGads values were then employed to estimate the van der Waals contribution and the specific contribution of the free surface energy for each MCM41. DN values (donor numbers, based on the Gutmann scale) and AN* values (acceptor numbers, based on the Riddle-Fowkes scale) were employed to determine the values of parameters that characterize the ability of the MCM41s to act as electron acceptors (parameter: KA) and donors (parameter: KD). Considering the different compositions of the probes, each of which has different acceptor-donor properties, a new chromatographic test to supplement the Grob test is suggested.

Chromatographic characterisation of ordered mesoporous silicas. Part II: Acceptor-donor properties.

The ordered mesoporous siliceous materials: MCM41C16, MCM41C16-SH and MCM41C16-NH(2) (known as MCMs) having different surface functionalities were studied by inverse gas chromatography to characterise their acceptor-donor properties. The DN values denoting the donor number in the Gutmann scale and the AN* values denoting the acceptor number in the Riddle-Fowkes scale have been chosen in the estimation of the electron-acceptor parameter K(A) and electron-donor parameter K(D) values. The number and kind of the employed adsorbates have an influence on the results obtained. The problem of the number of adsorbates employed has been considered in the light of both results obtained in the present study and the data available in the literature for siliceous adsorbents with randomly ordered structures. Complementary information was obtained by X-ray photoelectron spectroscopy and energy dispersive X-ray spectroscopy.

Chromatographic characterisation of ordered mesoporous silicas: part I. Surface free energy of adsorption.

The ordered mesoporous siliceous materials: MCM41C16, MCM41C16-SH and MCM41C16-NH(2) (known as MCMs) having different surface functionalities were studied by inverse gas chromatography at infinite dilution of chromatographed substances to elucidate their adsorption and adhesive properties. The free energies of adsorption, DeltaG(ads), were calculated in two ways on the basis of the primary chromatographic data. The van der Waals component of the surface free energy, gamma(S)(vdW), was calculated by employing the Dorris-Gray method and the Schultz method. The van der Waals, gamma(S)(vdW), and specific, I(SP), components of the surface free energy were temperature dependent, and were expressed as the linear dependences. The suggested approach was also employed for non-ordered silica adsorbents on the basis of various literature data.

Chromatographic determination of the differential isosteric adsorption enthalpies and differential entropies on ordered silica materials.

The adsorption properties of the ordered mesoporous siliceous materials: MCM-41C16 (denoted as C16), MCM-41C16-SH and MCM-41C16-NH(2) (known as MCMs) having different surface functionalities were studied by inverse gas chromatography to assess their suitability for adsorption of analytes from gas and liquid phases. Polar and non-polar adsorbates were employed. The differential isosteric enthalpies, -DeltaH(ads), and differential entropies, -DeltaS(ads), of adsorption of different 'molecular probes' were determined chromatographically. A mathematical link between the -DeltaH(ads), and -DeltaS(ads) magnitudes and experimental data was derived through an Antoine-type equation. The present studies have been entirely restricted to the region of low adsorbate concentration. The problem of the interrelationship between the -DeltaH(ads), and -DeltaS(ads) values, known as the 'thermodynamic compensation effect', and interpretation of chromatographic data for the adsorption of different adsorbates on the MCMs have been considered in the light of both experimental data obtained in the present studies and the data available in the literature for siliceous adsorbents with randomly ordered structures. It was shown chromatographically that there is substantial parallelism between the magnitudes of the differential isosteric enthalpy and differential entropy for some 'molecular probes' chromatographed on C16 and its derivatives. Complementary information was obtained by atomic-force microscopy (AFM), X-ray photoelectron spectroscopy and X-ray diffraction (XRD) spectroscopy.

Resolution of the excitation-emission spectra of FMN in rigid poly(vinyl alcohol) matrices.

The excitation-emission spectra of flavin mononucleotide (FMN) were measured in rigid PVA films for concentrations ranging from 6.92 x 10(-4)M to 1.03 M. The theoretical three-linear decomposition of the excitation-emission spectra indicated the presence of two absorption and emission centers corresponding to FMN monomer and dimer, respectively. The component of the fluorescence profile corresponding to the FMN monomer has a large negative part which is the mirror image of the emission band profile of the dimer. The elimination of this part by taking a linear combination of the emission components of the monomer and of the dimer resulted in emission spectrum, which is in a very good agreement with the monomer spectrum measured directly. The appearance of a negative part of the monomer emission profile obtained by trilinear decomposition of the emission-absorption spectra of FMN can be explained in terms of the non-radiative reverse energy transfer from the FMN dimers to the FMN monomers. The presented results confirm that the FMN molecules in rigid PVA form dimers but not higher order aggregates. Moreover, they enable to obtain fluorescence spectra of dimers and suggest that FMN dimers may take part in the process of non-radiative energy transfer occurring in photoreception phenomena.

Excitation energy transport and trapping in concentrated solid solutions of flavomononucleotide.

Excitation energy transport and trapping is studied for monomer-fluorescent dimer system of flavomononucleotide (FMN) in polyvinyl alcohol films (PVA). It is shown that the theory neglecting reverse energy transfer (RET) from dimers to monomers does not allow for the explanation of concentration quenching and concentration depolarization results presented herein. Much better agreement has been obtained using generalized energy transport theory in which fluorescent dimers are treated as imperfect traps for excitation energy. Such parameters like the dimer quantum yield and its emission anisotropy are estimated.

Spectroscopic manifestations of flavomononucleotide dimers in polyvinyl alcohol films.

Absorption and fluorescence spectra of flavomononucleotide (FMN) in polyvinyl alcohol films (PVA) over a very wide concentration range are investigated. The dimerization constant as well as the pure monomer and dimer spectra are calculated and the structural parameters of FMN dimer are established. Excitation wavelength and temperature dependencies of FMN/PVA fluorescence spectra for different FMN concentrations were carried out. These measurements together with those of absorption reveal that dimers are imperfect traps for excitation energy and that the energy transfer can occur both in forward and in reverse direction. Moreover, it was shown that the observed temperature changes in fluorescence spectra may be qualitatively explained by the effect of inhomogeneous broadening of FMN energy levels and by the presence of fluorescent dimers.

The influence of fluorescence concentration quenching on the emission anisotropy of flavins in glycerine-water solutions.

The measurements of the emission anisotropy r/r0 of flavomononucleotide (FMN) within a range of concentrations of 10(-5)-10(-1) mol/L in glycerine-water solutions of different viscosities--0.056 Pa/s (system I) and 0.256 Pa/s (system II) have been carried out. In the range of high concentrations the repolarization effect due to the sharp drop of the quantum yield has been observed. The experimental results have been compared with theoretical expressions evaluated by taking into account both concentration and rotation depolarization. A good agreement on the values of the theoretical parameters obtained from independent measurements has been found. It has been stated that in the investigated systems the excitation energy transfer may be treated as a Markov process.

Investigations on the fluorescence concentration quenching of flavomononucleotide in glycerine-water solutions.

We measured concentration changes of the fluorescence quantum yield eta/eta 0 of flavomononucleotide (FMN) in glycerine-water solutions of various viscosities. The results obtained show that FMN dimers are traps for the exciting light energy as well as the energy transferred non-radiatively. Very good agreement between the experimental and theoretical eta/eta 0 results was obtained. It has been shown that in the investigated solutions non-radiative energy transfer from monomers to dimers takes place, preceded by the migration of energy. It has been stated that no monomer quenching occurs in these solutions. The contribution of the individual fluorescence concentration quenching mechanisms has been determined.