Oil pollution is today one of the main factors of the technogenic impact on the environment. Emergency oil spills are the main source of the oil pollution. The causes, scales, and environmental consequences of emergency spills are considered. The advantages and drawbacks of methods for eliminating the spills of crude oil and petroleum products on the surface of water bodies are discussed. The features of the sorption method for oil collection from the water surface, which is the most widely used method, are described in detail. Requirements to petroleum sorbents are analyzed, and classes of the sorbents are described. Synthetic polymer sorbents have a set of advantages over other types of oil-absorbing materials. Fighting emergency oil spills should include the activity aimed at their prevention. This is particularly topical for Russia, which starts active operation of the Northern Sea Route and of shelf deposits of fossil fuels in seas of the Russian Arctic.
This review is devoted to the development, properties, and application of biosensors based on graphene nanomaterials. It is shown that such biosensors are characterized by their sensitivity, specificity of detection of analytes, high speed, and small size. Examples of the use of graphene biosensors for the detection of viruses, bacteria, markers of socially significant diseases, and various toxins are given.
This article provides a brief review of the current scientific literature on the structure, properties, and preparation of graphene nanomaterials (GNM) and their potential uses in pharmacology and biomedicine. The most important members of the graphene family are graphene itself and its oxide. GNM have been shown to have a set of unique physicochemical properties and have been studied intensely as substances for targeted drug delivery, gene transfection, hyperthermia, etc. GNM are regarded as potential nanomaterials for making implants and prostheses, and also as antibacterial substances. Problems facing researchers and requiring solution for successful introduction of GNM into practice are discussed.
Properties of graphene and its derivatives, allowing these materials to be used as effective sorbents, membranes, and sensitive elements of gas sensors, are considered. Data on procedures for preparing graphene and its oxide are presented. The literature survey demonstrates the possibility of developing selective sorbents based on graphene nanomaterials for many industrial processes including water desalination and recovery of radionuclides from process solutions. As judged from the results of laboratory experiments, membranes containing graphene and its oxides can be used in foreseeable future for nanofiltration, water treatment, and gas drying. Large-scale commercial use of graphene is yet restricted by the lack of economically acceptable procedures for preparing graphene nanomaterials of large linear size. For fabricating gas and biosensors, the millimeter size of receptor elements containing graphene and its derivatives is sufficient, and this size is achievable today.
Methods of graphene preparation, its structure, physical and chemical properties are reviewed. Two stages of chemical modification of graphene are described—primary (functionalization) and secondary (covalent attachment of organic compounds) modification. The main attention is paid to methods for the synthesis of graphene derivatives: oxide, graphane, halides, nitrogen-containing compounds, and conjugates of graphene and graphene oxide with organic and bioorganic molecules. The main areas of potential application of modified graphene materials are briefly considered. Biomedicine and medical diagnostics are the most promising areas of practical use of graphene conjugates and materials based on it. However, detailed studies of the toxicity of graphene and its derivatives should be carried out.
There were illustrated the main questions of development of new generation drug delivery systems as hybrid nanomaterials as follows: selection of nanocarrier, its standardization and the methods of immobilization of biologically active and medicinal substances. The basic organs of distribution and accumulation of advanced carbon nanocarrier - detonation nanodiamond were identified. It was shown that antihypoxic effect of the nanodiamond-glycine conjugate increased in comparison with a native Glycine and Mexidolum® as reference drugs.
The published and the authors’ own data on the methods of chlorination of the surface of diamond micropowders are critically assessed. The features of different methods of chlorination of detonation nanodiamond (DND) are compared; the optimum process conditions are revealed. The method of gas-phase chlorination with molecular chlorine at elevated temperatures is preferable when using DND in biomedical applications; this method also helps lower the concentration of metal impurities. The use of thionyl chloride and sulfuryl chloride results in the contamination of DND-Cl samples with sulfur. It is shown that the DND-Cl samples have satisfactory hydrolytic stability.
The effect of the chemical nature of the surface of detonation nanodiamond on the adsorption of an antibiotic is revealed with the help of tritium-labeled amikacin. It is found that nanodiamonds with a carboxylated surface (Ssp = 283 ± 5 m2/g) chemisorbed twice as much amikacin as nanodiamonds with a hydrogenated surface (Ssp = 289 ± 5 m2/g): 48 and 22 mg/g, respectively. Maintaining nanodiamonds with immobilized amikacin in the form of hydrosol for 1 month results in a release of up to 9.6 and 6.4 mg/g of the antibiotic, respectively. The results demonstrate the possibility of creating an amikacin delivery system based on nanodiamonds.
Detonation nanodiamonds (NDs) with chlorinated (ND-Cl) and carboxylated (ND-COOH) surfaces were obtained. The broad-spectrum antibiotic Amikacin (Amik) was covalently grafted to the chlorinated surface (ND-Amik) and immobilized by adsorption to carboxylated surface (Amik/ND-COOH). Biological testing in vitro showed the presence of antibacterial activity of the obtained samples against Staphylococcus aureus FDA P209 and Escherichia coli ATCC 25922, close to activity of free amikacin. It was revealed that to maintain antibacterial activity of the samples after their preliminary treatment, important factors such as the use of antioxidants (hydrosulfite and sodium citrate) and lyophilization were necessary.
There were illustrated the main questions of development of new generation drug delivery systems as hybrid nanomaterials as follows: selection of nanocarrier, its standardization and the methods of immobilization of biologically active and medicinal substances. The basic organs of distribution and accumulation of advanced carbon nanocarrier - detonation nanodiamond were identified. It was shown that antihypoxic effect of the nanodiamond-glycine conjugate increased in comparison with a native Glycine and Mexidolum® as reference drugs.
The authors compare IR spectra of diamonds of different origins, both natural and synthetic ones—produced by detonation, dynamic, and static syntheses, and subjected to purifying treatment under various conditions. It is shown that in the IR-spectral range there are absorption bands at 421, 945, 1022, 2854, 2920, and 3368 cm–1, which are typical of the majority of the samples studied. Whatever the origin of diamonds, their IR spectra have been found to contain absorption bands of S–S, C–S bonds (upon treatment with sulfuric acid), and C–N bonds (after treatment with nitric acid). The presence of functional C–H and–OH groups has been confirmed.
In recent years, detonation nanodiamond is regarded as a promising material for biomedical applications. However, a significant problem that stops of intensive development of this area is a absence of commercial NDs standardization. This article presents the results of the study of physicochemical properties of several industrial nanodiamonds available in the international market. The differences of physicochemical characteristics of nanodiamonds produced, selected and purified in various ways are shown. A method is developed for industrial processing of nanodiamonds, that represents high-temperature hydrogenation of diamond surface and allows to unify their properties. It is shown that after these processing nanodiamonds have the same surface chemistry and can form stable hydrosols. The proposed method of industrial nanodiamonds unification can become a universal method of its standardization.
Исследована каталитическая активность наноалмаза детонационного синтеза и его Ni-содержащих форм в конверсии 1,2-дихлорэтана и сопоставлена с активностью других углеродных и наноуглеродных материалов: углеродных нанотрубок, синтетического алмаза “Далан” и фторированного графита. Для характеристики поверхности и структуры углеродных материалов использованы методы: РФА, ИК-спектроскопии диффузного отражения, РФЭС, БЭТ, ТПВ. Каталитические свойства материалов изучены с помощью импульсного микрокаталитического метода. Установлено, что синтетический алмаз, наноалмаз и его Ni-содержащие формы являются катализаторами конверсии дихлорэтана в атмосфере азота, где основным продуктом является этилен. Отмечено, что дезактивированные алмазные катализаторы восстанавливают свою каталитическую активность при обработке водородом. Показано, что углеродная структура наноалмаза и синтетического алмаза “Далан” c находящимися на ней водородными группами играет ключевую роль в конверсии дихлорэтана. Установлено, что наноалмаз является одновременно и катализатором, и адсорбентом хлорсодержащих продуктов конверсии дихлорэтана.
This paper describes the use of gamma activation analysis methods for determining impurities in detonation nanodiamonds (DNDs) from different manufacturers, in different probes of the same batch from the same manufacturer, in chemically modified DNDs, and in DND–glycine conjugate. Twelve impurity elements were detected and quantified in DND samples: Cl, Ti, Cr, Fe, Ni, Zr, Mo, Sb, Sr, Mn, U and Eu. The content of impurity elements in DND samples varies from 0.1 to 3wt.%. Considering possible medical applications of DND, compliance with approved maximum permissible concentrations of heavy metals in medicinal agents is required.
The catalytic activity of a detonation nanodiamond and its Ni-containing forms in the conversion of 1,2-dichloroethane is studied and compared with the activity of other carbon and nanocarbon materials: carbon nanotubes, "Dalan" synthetic diamond, and fluorinated graphite. The surface and structure of the carbon materials are characterized using XRD, diffuse reflectance IR spectroscopy, XPS, BET, and TPR. The catalytic properties of the materials are studied using the pulsed microcatalytic method. It is found that the synthetic diamond, the nanodiamond, and its Ni-containing forms are catalysts for dichloroethane conversion in a nitrogen atmosphere, where the main product is ethylene. It is noted that the catalytic activity of deactivated diamond catalysts is restored after hydrogen treatment. It is shown that the carbon structure of the nanodiamond and the "Dalan" synthetic diamond with hydrogen groups located on it plays a key role in the dichloroethane conversion. It is found that the nanodiamond acts simultaneously as a catalyst and an adsorbent of chlorine-containing products of dichloroethane conversion.