[show abstract][hide abstract] ABSTRACT: While the popularity of the usage of room temperature microfluidic systems is booming in different technologies such as bio-technology, micro-scale chemistry, micro-printing and many others, systems applicable under high temperature and pressure are still remarkably under-developed. The main drawback of the existing systems is the inadequate quality of the available construction materials. In this work, extrusion of metal-oxo-alkoxide sol–gel precursors through the nozzle is utilized to produce the liquid thread that is allowed to self-transform into ceramic microtubes by a chemical curing process. The focus is on YSZ (8% Y2O3 stabilized ZrO2), which exhibits a stable 100% tetragonal phase nanocrystalline structure up to 1000 °C. These tubes have excellent mechanical characteristics and can withstand 1000 atm pressure inside the tubes. Owing to these and other physical, chemical and mechanical properties, there are many potential applications for these tubes, one example being that the high optical quality of the YSZ tubes could be useful for guiding of light. Ionic conductivity with no electronic component makes these tubes suitable for ionic membrane applications like solid oxide fuel cells (SOFCs) or corresponding gas sensors. Finally, we demonstrate a single-tube-based miniature plasma jet device potentially applicable as an ion source for local surface treatment or possibly as a micro plasma propulsion device for space applications.
[show abstract][hide abstract] ABSTRACT: 5-Ethoxymethylfurfural (EMF) can be prepared from the corresponding halomethylfurfural and absolute ethanol in good yield. The use of significantly more affordable 96% ethanol results in formation of levulinic acid or its ester in considerable amount (up to 16%), which is difficult to separate from the desired EMF. In the present study we report that the addition of oil shale ash prevents the hydrolysis of the furan ring and enables the use of 96% ethanol with great success. The developed procedure is applicable to a wide range of aqueous alcohols, is operationally simple and utilizes an inexpensive basic ash, which is deposited in millions of tons per year. Notably, the basicity of the ash is decreased during the process, making its deposits less hazardous to the environment.
[show abstract][hide abstract] ABSTRACT: In the present study, polymerizable ionic liquids (ILs), 1-[n-(methacryloyloxy)alkyl]-3-methylimidazolium bromides (n = 2, 6, 7, or 10), were synthesized in high yields. Moreover, the compounds obtained (n = 6, 7, or 10) were used in the preparation of composite materials comprising a polymerized IL matrix and a nonpolymerizable IL additive, 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]) in various proportions (up to 75% vol/vol of [EMIM][BF4]). The UV-radiation-initiated photopolymerization process was monitored in situ by measuring the resistivities of the mixtures. An increase in [EMIM][BF4] content in the composites led to an increase in the ionic conductivities of the materials while retaining their solid state at levels as high as 40% vol/vol of the [EMIM][BF4] content. The 40% vol/vol composites had conductivities of approximately 10−4 S/cm compared to the conductivities of 10−5 S/cm for the corresponding neat polymerized ILs. Above this [EMIM][BF4] content, the materials were sticky gels, and from 50% vol/vol onwards, entirely liquid.
[show abstract][hide abstract] ABSTRACT: Palladium-catalyzed allylation of hydrazines using allyl alcohols is reported. This highly efficient protocol furnishes monoallylated hydrazines selectively, in 27-99% yields. Following an optimization of the reaction conditions and of the Pd-ligands, the allylations of both mono- and disubstituted hydrazines were investigated, as well as the effects of C2-substitution on the allylating agent. Of particular interest, a novel method for the selective monoallylation of monosubstituted hydrazines is demonstrated.
[show abstract][hide abstract] ABSTRACT: The influence of different parameters on the conversion of carbohydrates and biomass into the potential biofuel intermediate 5-bromomethylfurfural (BMF) has been studied. Our optimized conditions avoid the use of lithium salt additives, making this method cheaper and environmentally more benign compared to previously reported methods. Different wood species and their potential as a raw material in BMF and furfural production have also been evaluated. In addition, we report a very simple and efficient procedure for conversion of 5-hydroxymethylfurfural (HMF) into BMF or 5-chloromethylfurfural (CMF).
Carbohydrate research 04/2013; 375C:63-67. · 2.03 Impact Factor
[show abstract][hide abstract] ABSTRACT: An electrochemical study of Au electrodes electrografted with azobenzene (AB), Fast Garnet GBC (GBC) and Fast Black K (FBK) diazonium compounds is presented. Electrochemical quartz crystal microbalance, ellipsometry and atomic force microscopy investigations reveal the formation of multilayer films. The elemental composition of the aryl layers is examined by X-ray photoelectron spectroscopy. The electrochemical measurements reveal a quasi-reversible voltammogram of the Fe(CN)(6) (3-/4-) redox couple on bare Au and a sigmoidal shape for the GBC- and FBK-modified Au electrodes, thus demonstrating that electron transfer is blocked due to the surface modification. The electrografted AB layer results in strongest inhibition of the Fe(CN)(6) (3-/4-) response compared with other aryl layers. The same tendencies are observed for oxygen reduction; however, the blocking effect is not as strong as in the Fe(CN)(6) (3-/4-) redox system. The electrochemical impedance spectroscopy measurements allowed the calculation of low charge-transfer rates to the Fe(CN)(6) (3-) probe for the GBC- and FBK-modified Au electrodes in relation to bare Au. From these measurements it can be concluded that the FBK film is less compact or presents more pinholes than the electrografted GBC layer.
[show abstract][hide abstract] ABSTRACT: The cluster crystals of Na2[SiF6] were obtained in the aqueous solutions of different methylalkylimidazolium (ethyl-, butyl- and decyl-) tetrafluoroborate ionic liquids (IL) in borosilicate glassware. It is demonstrated that sodium hexafluorosilicate crystalline compounds with good regularity and narrow size distribution containing dialkyl imidazolium ions between the hexagonal crystalline clusters interconnected to each other to a whole hexagonal aggregate can be obtained in large quantities. This characteristic phenomenon of crystallization of sodium hexafluorosilicate containing IL ions is reported for the first time. The mechanism of formation of various [RMIm]BF4–Na2[SiF6] microcrystalline morphologies and the influence of temperature on the growth kinetics are discussed. Crystallographic studies of the product were carried out by X-ray diffractometer (XRD), characterization by scanning electron microscopy (SEM) and optical microscopies; also infrared spectra (IR) were recorded. Thermal analysis were performed by differential scanning calorimetry–thermogravimetric analyzer (TGA–DSC). Presence of ionic liquid cations was confirmed by high resolution mass spectrometry (HRMS).
Journal of Crystal Growth 12/2012; 361:51–56. · 1.55 Impact Factor
[show abstract][hide abstract] ABSTRACT: An efficient method for the synthesis of cyclic hydrazine derivatives starting from disubstituted hydrazines is reported. The method is based on the selective alkylation of hydrazine dianions with bromoalkenes and subsequent cyclization using Grubbs’ catalysts. The described method provides fast and easy access to the substrates for ring-closing metathesis and the corresponding heterocycles containing a hydrazine moiety. The scope and limitations of the new method are also demonstrated.
[show abstract][hide abstract] ABSTRACT: In the present work, it is shown that carbon nanotube-doped transition metal oxides are potential candidates for use as ceramic transparent electrode materials. Electrodes in shape of fibers are obtained via inexpensive and low temperature sol-gel method. Fiber electrodes are characterised by SEM-FIB and rheological analizes. Due to extraordinary electrical and optical properties of CNT-s and good chemical and physical stability of metal oxide ceramics, resulting composites could be an interesting subject for industry.
IOP Conference Series Materials Science and Engineering 01/2012; 38(1).
[show abstract][hide abstract] ABSTRACT: The invention of electrospinning has solved the problem of producing micro- and nanoscaled metal oxide fibres in bulk quantities. However, until now no methods have been available for preparing a single nanofibre of a metal oxide. In this work, the direct drawing method was successfully applied to produce metal oxide (SnO2, TiO2, ZrO2, HfO2 and CeO2) fibres with a high aspect ratio (up to 10 000) and a diameter as small as 200 nm. The sol–gel processing includes consumption of precursors obtained from alkoxides by aqueous or non-aqueous polymerization. Shear thinning of the precursors enables pulling a material into a fibre. This rheological behaviour can be explained by sliding of particles owing to external forces. Transmission (propagation) of light along microscaled fibres and their excellent surface morphology suggest that metal oxide nanofibres can be directly drawn from sol precursors for use in integrated photonic systems.
Science and Technology of Advanced Materials 06/2011; 12(3):034412. · 3.75 Impact Factor
[show abstract][hide abstract] ABSTRACT: The electrochemical response of 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) on aryl-modified glassy carbon (GC) electrodes has been investigated. The electrochemical modification of GC surface with 4-nitrophenyl (NP) and 4-carboxyphenyl (CP) groups was performed using the diazonium reduction method. The 4-aminophenyl-modified GC electrodes were obtained by electroreduction of NP films. The surface coverage of aryl groups was altered by varying the number of potential scans during electrografting experiments. The electrochemical behaviour of ABTS was studied on bare and aryl-modified GC electrodes using cyclic voltammetry and the rotating disk electrode (RDE) methods. Electrochemical measurements were performed in acetate and phosphate buffers (pH=4–8) to study the effect of pH on the electron transfer process. The response of ABTS was independent of pH for bare GC and GC/NP electrodes (modified by 20 electrografting scans), whereas a slight pH-dependence was observed for other electrodes. The strongest blocking action was observed for the NP-modified GC electrodes of higher surface coverage and the lowest for reduced NP films (modified by a single electrografting scan).
Journal of Electroanalytical Chemistry - J ELECTROANAL CHEM. 01/2011; 661(2):343-350.
[show abstract][hide abstract] ABSTRACT: A new method for the synthesis of 3-hydrazinopropyl trimethoxysilane is proposed. The method is relatively simple and is based on hydrosilylation like the synthesis of analogous aminosilanes. For drying allylhydrazine hydrate a new efficient silyl hydride base method is proposed. The product, a new hydrazino-ormosil (organically modified silicate), can be applied in chemical modification of SiO 2 surfaces, thus offering an alternative to aminosilane modification, which is widely applied in several surface coating technologies.
Proceedings of the Estonian Academy of Sciences 01/2011; 60(1):64-68. · 0.31 Impact Factor
[show abstract][hide abstract] ABSTRACT: The 2,2,2-trichloroethoxycarbonyl (Troc) protecting group was efficiently removed from Troc-protected aliphatic and aromatic amines and also some Troc, Tos- and Troc, Ac-protected amines using activated mischmetal (MM). All reactions were performed by refluxing in dry tetrahydrofuran under an argon atmosphere and gave moderate to excellent yields. Several new compounds were synthesized, and new data about reactivity of Troc group were obtained.
[show abstract][hide abstract] ABSTRACT: The scope of a set of recently reported hydrazine reagents has been explored with respect to arylation. Compounds of type R1NHNHCOR2 can be selectively arylated under very mild conditions using triarylbismuth diacetates.
[show abstract][hide abstract] ABSTRACT: Ionic Polymer Metal Composites (IPMCs) are soft electroactive polymer materials that bend in response to the voltage stimulus (1 - 4 V). They can be used as actuators or sensors. In this paper, we introduce two new highly-porous carbon materials for assembling high specific area electrodes for IPMC actuators and compare their electromechanical performance with recently reported IPMCs based on RuO2 electrodes. We synthesize ionic liquid (Emi-Tf) actuators with either Carbide-Derived Carbon (CDC) (derived from TiC) or coconut shell based activated carbon electrodes. The carbon electrodes are applied onto ionic liquid-swollen Nafion membranes using the direct assembly process. Our results show that actuators assembled with CDC electrodes have the greatest peak-to-peak strain output, reaching up to 20.4 mε (equivalent to >2%) at a 2 V actuation signal, exceeding that of the RuO2 electrodes by more than 100%. The electrodes synthesized from TiC-derived carbon also revealed significantly higher maximum strain rate. The differences between the materials are discussed in terms of molecular interactions and mechanisms upon actuation in the different electrodes.
[show abstract][hide abstract] ABSTRACT: Ionic polymer metal composites (IPMCs) are electroactive material devices that bend at low applied voltage (1–4 V). Inversely, a voltage is generated when the materials are deformed, which makes them useful both as sensors and actuators. In this paper, we propose two new highly porous carbon materials as electrodes for IPMC actuators, generating a high specific area, and compare their electromechanical performance with recently reported RuO2 electrodes and conventional IPMCs. Using a direct assembly process (DAP), we synthesize ionic liquid (Emi-Tf) actuators with either carbide-derived carbon (CDC) or coconut-shell-based activated carbon-based electrodes. The carbon electrodes were applied onto ionic liquid-swollen Nafion membranes using a direct assembly process. The study demonstrates that actuators based on carbon electrodes derived from TiC have the greatest peak-to-peak strain output, reaching up to 20.4 mε (equivalent to>2%) at a 2 V actuation signal, exceeding that of the RuO2 electrodes by more than 100%. The electrodes synthesized from TiC-derived carbon also exhibit significantly higher maximum strain rate. The differences between the materials are discussed in terms of molecular interactions and mechanisms upon actuation in the different electrodes.
Smart Materials and Structures 08/2009; 18(9):095028. · 2.02 Impact Factor
[show abstract][hide abstract] ABSTRACT: A novel method for the synthesis of cyclic hydrazine derivatives is reported. The new method for the generation of nitrogen-containing heterocycles is based on a polyanion strategy. The described method provides a convenient access to cyclic hydrazine derivatives, which are extensively used in drug industry and agriculture. The advantages and limitations of the new method are also demonstrated.