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The effect of a nanometer confinement on the vibrational and molecular dynamics of a liquid crystals E7 was studied by dielectric spectroscopy (DS) and neutron scattering (NS). E7 undergoes a glass transition phenomenon besides the nematic to isotropic phase transition. As confining host a molecular sieve of the MCM-41 type is used having cylindrical pores with a radius of 1.25 nm. The results obtained by both methods are compared in detail.

Pd-Ho/γAl2O3 catalysts exhibit higher activity for styrene hydrogenation than Pd/γAl2O3 ones. The addition of holmium to Pd catalysts changes the place of the palladium impregnation front depending on the state of the supported palladium. As a consequence of the interaction between holmium and Pd/γAl2O3 support, oxidized forms as holmium aluminate were formed. These forms are catalytically inactive but represent adsorption centers for styrene. On holmium containing catalysts, hydrogenation takes place between the styrene adsorbed on basic centers and the hydrogen spilled over from palladium particles.

The molecular dynamics of 4- n -octyl-4′-cyanobiphenyl (8CB) confined to the nanopores of new SBA-type molecular sieves was investigated in a wide temperature range using broadband dielectric spectroscopy (10 −2 –10 9 Hz). One molecular sieve has a hexagonal structure of the pores while the other is a cellular nanoporous material. To explore the extent of surface interaction effects a high and a low filling degree were considered. For the molecular sieves with a high filling degree two relaxation regions were observed: a bulk-like relaxation process related to molecules, which behave as mesophase, located in the centre of the pores. The second relaxation process has a much lower relaxation rate than the former and is assigned to molecules located in a surface layer. The temperature dependence of its relaxation rates follows the Vogel–Fulcher–Tammann law, characteristic for glassy dynamics. For samples with a low filling degree only one relaxation process due to the surface layer was observed. Moreover, especially at the temperatures lower than the melting point of bulk 8CB, its relaxation rate is situated between the characteristic frequencies of the two relaxation processes observed for the pores with a high filling degree. This behaviour gives a measure of the extension of the influence of the wall on the neighbouring 8CB molecules. In addition, the differences revealed by the molecule dynamics inside the two types of nanoporous materials are related to both surface interactions and geometrical constraints.

Composites were prepared from an aerosil and 4-n-alkyl-4′cyanobiphenyls with five to eight carbon atoms in the alkyl chain. Their high silica density of ∼7 g aerosil in 1 cm3 of liquid crystal (LC) allows the observation of the behaviour of a thin cyanobiphenyl layer (having nearly a monolayer structure) on the silica particles. The systems are investigated by dielectric spectroscopy (10−2–109 Hz) in a large temperature range (220–370 K). All the composites show a (main) relaxation process at frequencies much lower than the processes observed for the bulk LC that was assigned to the dynamics of the molecules in the surface layer. The temperature dependence of its characteristic frequencies obeys the Vogel–Fulcher–Tammann law, which is found to be typical for glass-forming liquids. The quasi two-dimensional character of the glass transition in the surface layer is discussed for the first time. At the nematic-to-isotropic transition temperature of the bulk, the composites show a continuous decrease of the c...

Thermal analysis measurements were applied to study the behavior of composite systems containing a nematic liquid crystal (LC), 4-n-octyl-4′-cyanobiphenyl (8CB) and aerosil particles. The silica density ρs (g of silica per 1 cm3 of LC) was varied from 0.20 to 12 g/cm3 in order to approach the monomolecular structure of the surface layer. Thus, thermogravimetric (TG) measurements were performed to get information on the LC content of the samples. Moreover, they allowed an unusual application, to characterize the interaction of 8CB molecules with aerosil surface because the corresponding curves show multistep processes the temperatures of which depend on the silica density. Differential thermal analysis (DTA) also indicates several processes. Some of them, mostly due to desorption, are endothermal. Other processes are exothermal, and these are assigned to chemical transformations. The sample with silica density of 12 g/cm3 has no endothermal desorption peak at low temperatures, and has the highest shift for the DTA peaks. It was supposed that its surface layer has a monomolecular structure. For representative samples, TG–DTA studies were supported by FTIR investigations. Thus conventional TG–DTA techniques have provided new tools to characterize the nanocomposites. Differential scanning calorimetry gives the behavior of the phase transitions. Samples with low silica density exhibit a depression of the phase transition temperatures characteristic for the bulk 8CB while those with high silica densities do not show any phase transitions.

Composites containing 4- n -octyl-4′-cyanobiphenyl (8CB) either confined to nanopores of molecular sieves with very large pores or coating silica nanoparticles of aerosil type at high silica-to-8CB ratios are investigated by IR spectroscopy. Band shape analysis was performed in wavenumber regions in which the peaks due to CN stretching, CH stretching and CH out-of-plane vibrations appear. Some of molecules confined to molecular sieves show spectroscopic features characteristic to a bulk-like 8CB matter located in the centre of the pores or in the inter-grain space. Other features of the IR spectra are due to 8CB molecules located in the surface layer, mostly forming hydrogen bonds between their CN groups and surface OH groups. Another part of the 8CB molecules in the surface layer may also interact by π electrons of the aromatic rings. Hydrogen bonding is less hindered for the molecules of the surface layers onto aerosil particles than inside pores of the molecular sieves. Comparison is also made with the case of composites based on molecular sieves with small pores.

Broadband dielectric spectroscopy (10 −2 –10 9 Hz) was employed to study in a rather large temperature interval the molecular dynamics of the composite systems containing a nematic liquid crystal (LC), 4- n -pentyl-4′-cyanobiphenyl, confined to NaY, a zeolite with faujasite structure. Thermal analysis was also performed in order to get information concerning the loading of the zeolite and the possible phase transitions. No phase transitions and no relaxation processes of the LC molecules inside the pores were observed. But remarkably, in the presence of these molecules the dielectric behavior of the faujasite host changes due to modifications appeared in the mobility of Na + ions.

A broadband dielectric study of the dispersions of silica spheres (Aerosil 380) in octylcyanobiphenyl (8CB) with densities between 0.083 and 10 g of silica per 1 cm3 of liquid crystal (LC) is reported. High values of silica densities were achieved for the first time to observe the behaviour of the LC monolayer on the surface of the silica particles. The relaxation characteristic of the bulk LC is noticed especially for the samples with low silica densities. Additionally, a slow relaxation was detected, even at temperatures for which the bulk LC is in the crystalline state. It was assigned to the surface layer of LC molecules. Remarkably, the temperature dependence of the relaxation rates for this slow process shows a behaviour typical for glass-forming liquids.

The confinement of a nematic liquid crystal (LC), 4-octyl-4′-cyanobiphenyl, in the molecular sieves of AlMCM-41 and cloverite type is investigated by dielectric spectroscopy, thermal analysis and FTIR spectroscopy. We focus herein on the samples containing the LC not only in the pores and cavities, but also on the external surface of the molecular sieve grains. A bulk-like dynamical behaviour was found for these samples. An interaction of the LC molecules with the surface took place by coordination to Lewis sites and by hydrogen bonding with OH groups.

The molecular dynamics of the liquid crystals 8CB and 5CB confined to the mesopores of the molecular sieve Al-MCM-41 with pore diameter less than 2.5 nm was investigated by broadband dielectric spectroscopy. The phase transitions of the liquid crystal cannot be detected for the molecules confined to the pores. Moreover it has been found that even about 20 K below the melting temperature of the bulk material a relaxation process occurs for molecules confined to the mesoporous material which does not exist in the bulk liquid crystal state. The temperature dependence of the relaxation rate of that process obeys a Vogel-Fulcher-Tammann law.

The gallophosphate cloverite has been investigated because of its applicability to act as a host for larger molecules. 4-n-pentyl-4′-cyanobiphenyl (5CB) and 4-n-octyl-4′-cyanobiphenyl (8CB) liquid crystals were used as guest molecules. The results show that the adsorption of liquid crystals from the gas phase proceeds without destruction of the cloverite structure. The typical phase properties of the liquid crystals remain unchanged after adsorption on cloverite: however, they appear with lower intensity in the DSC curve. A new smectic phase seems to be formed inside the cloverite pore system. FTIR measurements show the interaction of 5CB with the Lewis and Bronsted acid sites of cloverite. Desorption of liquid crystals out of the pore system proceeds slowly under liberation of the POH groups of the lattice. In summary, the results show that the gallophosphate cloverite is a suitable host for large molecules.

Aliquots of waste water from power stations were analyzed by a special procedure in order to put in evidence the presence of renex, a nonionic detergent. The investigations were performed spectroscopically by FTIR technique. Qualitative and quantitative features of the procedure were established as specific peaks, detection limit and method sensibility. The validity of Lambert-Beer law was checked. Taking into account the selectivity of the method it results the necessity of separating renex from nitrogenous bases in the analyzed water.

The embedding of a enantioselective homogeneous catalyst — the chiral manganese(III) cationic complex of salen type (Jacobsen complex I) — into the pores of mesoporous substituted silicates is investigated. The host/guest interaction is studied by different methods: TG-DTA, UV-VIS, and FTIR. The results are consistent with a location of the large Mn complex inside the mesopores. Catalytic tests in olefin epoxidation prove the fully maintenance of the catalytic activity and stereoselectivity of the complex after embedding. This promising result indicates that MCM-like materials might have perspectives as supports for the heterogenization of homogeneous catalysts.

Hemoglobin (Hb) interaction with Hg 2+ ions was investigated by means of laser photolysis and spectroscopic methods. The binding of the gaseous axial ligands to the 3rd and 4th molecules of a Hb tetramer, l 3 ′ and l 4 ′, were found to show more relaxed features than in the absence of Hg 2+ ions. A heme iron oxidation takes also place. The kinetic parameters of this interaction were compared with those of the systems HbCu 2+ and HbSn(IV).

The surface of alumina supported catalysts containing 10 wt.% metal (Fe and/or Ni) has been spectroscopically investigated by CO adsorption. The stretching vibration range characteristic for CO bonded to metallic species shows very large absorptions, indicating a high surface heterogeneity. A certain Fe∶Ni stoichiometry seems to impose the reduction extent and the catalytic properties.

CO conversion to hydrocarbons at various reaction temperatures and atmospheric pressure has been investigated on alumina-supported Fe, Ni and Fe−Ni catalysts. Maxima of activity and selectivity were obtained in hydrocarbon formation as a function of Fe content in the samples, which corresponds to a certain stoichiometry of metallic components.

A series of AlMCM-41 molecular sieves was prepared with constant composition (Si/Al = 14.7) and presumably same pore structure but different pore diameters (from 2.3 to 4.6 nm). The pore size distribution is narrow for each sample. The rotational fluctuations of water molecules confined inside the pores were investigated applying broadband dielectric spectroscopy (10(-2)-10(7) Hz) over a large temperature interval (213-333 K). A relaxation process, slower than that expected for bulk water, was observed which is assigned to water molecules forming a surface layer on the pore walls. The estimated relaxation time has an unusual non-monotonic temperature dependence, which is rationalized and modeled assuming two competing processes: rotational fluctuations of constrained water molecules and defect formation (Ryabov model). This paper focuses on the defects and notably the influence of the hydroxyl groups of the pore walls. The Ryabov model is fitted to the data and characteristic parameters are obtained. Their dependence on pore diameter is considered for the first time. The found results are compared with those obtained for other types of molecular sieves and related materials.

In this paper, we report the successful growth of c-BCN thin films by reactive pulsed laser ablation (RPLA) of a rotating target (3 Hz) formed of two semidisks: one of h-BN and the other one of graphite, with the substrate at room temperature. The irradiations were performed in vacuum (10 -5 Pa) and in N 2 ambient gas (1-100 Pa) using a XeCl excimer laser ( A = 308 nm, τ FWHM = 30 ns) with a fluence of 5 J/cm 2 . Series of 10,000 pulses at a repetition rate of 10 Hz were directed to target. Different analysis techniques pointed out the synthesis of h-BCN and c-BCN. Microhardness measurements at the deposited films evidence high values up to 2.9 GPa. Secondary ion mass spectroscopy (SIMS) profiles showed the presence of layers of 600-700 nm thickness, with uniform concentrations of B. C and N in the films. Uniform signals of BN and CN. which are related to the BCN bond, are also present. X-ray photoelectron spectroscopy (XPS) studies pointed out the BCN compound formation. The deconvolution of B Is recorded spectra evidenced a strong peak (centered at 188 eV) assigned to B bonded in BC 2 N: the N Is and C Is spectra also confirm the BCN formation. Transmission electron microscopy (TEM) and selected area electron diffraction (SAED) analysis evidenced the presence of c-BCN phase (with crystallites of 30-80 nm) and h-BCN phase as well. The N 2 pressure strongly influenced the BCN formation and, consequently, the properties of the deposited films.

An elastic model for the twisted nematic texture observed in nematic cells containing octyloxybenzoic acid is proposed. According to the model the twisted textures are due to the presence of cybotactic groups which are responsible for the chirality of the liquid crystal. We show that by assuming for the density of cybotactic groups a critical temperature behaviour close to a special temperature, the experimental data can be well interpreted by our mechanical model.

Pd-Ln/γ-Al 2 O 3 (Ln-Sm, Gd, Dy, Ho, Tm) catalysts containing 0.1%Pd- 1%Ln, 0.3%Pd -1% Ln and respectively, 0.5% Pd -1% Ln (percentage in wt.%) were investigated. Introduction of Ln leads to an increase of the vinylbenzenes conversion comparatively with monometallic Pd/γ-Al 2 O 3 catalysts. The turnover frequency (TOF) calculus of the latter catalysts suggests that there are no difference among these. In the case of bicomponent Pd-Ln/γ-Al 2 O 3 catalysts, if one considers that the reaction occurs only on the palladium particles, then introduction of Ln seems to increase the TOF and vinylbenzenes hydrogenation seems to be, controlled by the mass transfer processes as indicated by the Koros-Nowak criterion. However, by taking Ln into consideration when calculate the TOF, it results that bicomponent catalysts behave like those monocomponent and the slope of the Koros-Novak dependence is included in a range typical for kinetically controlled reactions. This behavior could be associated to direct participation of Ln to reaction using hydrogen spilled over from the palladium particles.

Summary Modification of ZSM-5 zeolites (Si/Al=25) by impregnation with Ga, In or Tl salts is obtained. The interaction of Py molecules with the modified samples was spectroscopically studied: the components of IR peaks were ascribed to different adsorption sites, among which there are the modifier ions. On this basis, the location of modifier ions inside the zeolitic framework is discussed. Ammonia adsorption and textural measurements as well as recent electrochemical titration data [1] also support the differences regarding the deposition of the three modifiers.

In the presence of tin tetrachloride, the rate constant for the rebinding of CO to the triliganded hemoglobin, l'4, is much increased and the number of molecules participating in the CO ligation is decreasing. The pH drops, but a proton consumption process also takes place at the same time. The heme and its environment do not seem to change much, but the tin complexing to protein is very probable. The oxidation of hemoglobin in the form of either oxy or carbonmonoxy occurs with rather high rate.

Re‐Cr‐Ni composite metallic films were prepared using an original plasma deposition method developed at INFLPR, Bucharest, called thermionic vacuum arc (TVA). The method is based on the evaporation of a metal followed by ignition of a plasma in the vapours. These three-component films/alloy films were deposited using three simultaneous TVA plasma sources in the same vacuum chamber. Surface corrosion at temperatures up to 1000 ◦ Cw as found not to take place in these Re‐Cr‐Ni alloy films as shown by thermogravimetric analysis. The current results demonstrate that the TVA method is a promising candidate tool for the synthesis of multiple compound films. Films of uniform and controlled composition can be simultaneously obtained using this method. Moreover, high melting point metals can be involved in these superalloy films, thus leading to applications in extremely hot conditions such as turbine blades and aircraft parts. (Some figures in this article are in colour only in the electronic version)

The behavior of some supported Ni catalysts for methane synthesis from CO and steam in correlation with the specific metal-support interactions is discussed.

The species resulting in CO, CO+H2 or CO+D2O adsorption on supported Ni catalysts were followed by IR spectroscopy and their role in methane synthesis mechanism is discussed.

IR spectra of adsorbed CO species after prolonged contact with the catalyst surface show that surface carbon is formed and it participates in methane synthesis.