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.

Fragmentation of molecular ions in differential mobility spectrometry as a method for identification of chemical warfare agents.

The subject of the work is the use of differential mobility spectrometry (DMS) for the detection of chemical warfare agents (CWA). Studies were performed for mustard gas, i.e., bis(2-chloroethyl)sulfide (HD), sarin, i.e., O-isopropyl methylphosphonofluoridate (GB) and methyl salicylate (MS) used as test compounds. Measurements were conducted with two ceramic DMS analyzers of different constructions allowing the generation of an electric field with an intensity of more than 120 Td. Detector signals were measured for positive and negative modes of operation in a temperature range from 0 to 80 °C. Fragmentations of ions containing analyte molecules were observed for all tested compounds. The effective temperatures of fragmentation estimated on the basis of dispersion plots were equal from about 148 °C for GB to 178 °C for MS. It was found that values of separation voltage (SV) and compensation voltage (CV) at which the fragmentation of sample ions is observed may be the parameters improving the certainty of detection for different analytes. The DMS analyzers enabling the observation of ion fragmentation can be successfully used for effective CWA detection.

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.

Capillary gas chromatography-atomic emission spectroscopy-mass spectrometry analysis of sulphur mustard and transformation products in a block recovered from the Baltic Sea.

A block of yperite fished up from the Baltic Sea was analysed by gas chromatography coupled with atomic emission spectrometry and mass spectrometry. In the samples of the block about 50 compounds were detected, out of which 30 were identified. The identification of the compounds was performed by using the element chromatograms of the investigated compounds, and the data obtained by mass spectrometric detection. Thiodiglycol was not found among the compounds present in the investigated block. The calculations of the contents of sulphur mustard and some products in the block were performed by an external calibration method using bis(2-chloroethyl) sulphide as the standard. A satisfactory precision of elements determinations was obtained (RSD from 4.4 to 14.3%).

Chromatographic analysis of chemical warfare agents.

The usefulness and applications of the particular types of chromatography in the analysis of chemical warfare agents have been reviewed. A major problem in the chromatographic analysis of chemical warfare agents is the collection and preparation of the samples. The importance of this problem differs for the various types of chromatography. Significant differences occur in the way in which samples are collected from air, water, soil, vegetables or animal organisms. The analyses are characterized by the main groups of chemical warfare agents, e.g., organophosphorus, vesicants, irritants, etc. Account has been taken of the relationships between their properties and the possibilities of their chromatographic analysis. The advantages and disadvantages of particular types of chromatography in the analysis of the particular groups and individual agents have been considered. The detectability of particular chemical warfare agents has been assessed, together with the separating efficiency for their mixtures. Examples of applications of chromatographic systems and conditions of chromatographing are summarized in tables. It is concluded that chromatography is a very useful tool in the analysis of chemical warfare agents; GC and TLC have the most advantageous properties, HPLC being slightly inferior.

The application of piezoelectric detectors for investigations of environmental pollution.

The general properties of piezoelectric sorption detectors utilised in the detection of air pollution have been characterised. Examples of detection, with the aid of these detectors, of the organophosphorus compounds, sulphur dioxide, ammonia, hydrocarbons and their derivatives and other air pollutants have been given. Based on information given in this paper, general conclusions including advantages, and difficulties of using piezoelectric detectors in practice have been described.

Piezoelectric detectors coated with liquid-crystal materials.

The usefulness of liquid crystals as coating materials for quartz resonators in piezoelectric detectors of air-pollution has been tested. The concentration characteristics of the detector with respect to benzene, toluene, chlorobenzene, o- and m-dichlorobenzene, nitrobenzene, and o-, m- and p- diethylbenzene have been determined with the use of 4-pentyl-4'-cyanodiphenyl, 4-pentyl-4'-propylazo-benzene, 4-propyl-4'-methylazoxybenzene, and cholesteryl oleylcarbonate as coating materials. The effects of the quantity of coating material and of temperature on the sensitivity of the piezoelectric detector have been tested. The influence of the ordered structure of the liquid-crystal coating materials on the selectivity of the detector is discussed. Experiments have been performed to test the usefulness of the detector with liquid-crystal coating for detecting organophosphorus pesticides (DDVP and Phosdrin).

Overpressured thin-layer chromatography.

The properties, apparatus and applications of overpressured thin-layer chromatography (OPTLC) have been reviewed. In the Introduction planar chromatography has been briefly characterized, with particular attention to TLC. The general properties of OPTLC and methods of development of chromatograms in this technique have been then given. The construction of chambers and equipment for OPTLC has been described, paying attention to two-dimensional columns. The properties of chambers for OPTLC have been characterized considering the flow of eluent, sorbent-eluent interactions and the efficiency of various systems. OPTLC, TLC and HPTLC have been compared and also a comparison between OPTLC with a constant (linear) eluent flow-rate and with a decreasing eluent flow-rate has been made. Analytical applications of OPTLC have been described and examples of separations of mixtures have been given.