Effect of pore size of FSM-16 on the entrapment of flurbiprofen in mesoporous structures

The interaction between FSM-16 and flurbiprofen (FBP) in the mesopores of FSM-16 was investigated by using three types of FSM-16 with different pore diameters, i.e., FSM-16(Oc), FSM-16(Do) and FSM-16(Doc) (pore diameters 16.0, 21.6, 45.0 A, respectively). Solid dispersions of 30% FBP-70% FSM-16 were prepared by solvent evaporation and sealed-heating of the physical mixture at 100 degrees C for 6 h. Changes in the molecular state of FBP were investigated using powder X-ray diffractometry, thermal analysis and FT-IR spectroscopy. The changes in pore diameter and specific surface area of FSM-16 systems were investigated by small angle X-ray scattering and nitrogen gas adsorption. Powder X-ray diffractometry and thermal analysis revealed that FBP was adsorbed onto the mesopores of FSM-16(Do) and FSM-16(Doc), leading to an amorphous state, while no change was observed for FSM-16(Oc). Fourier-transformed IR spectroscopy showed a hydrogen bond interaction between the carbonyl groups of FBP and the silanol groups of FSM-16. The pore diameter and specific surface area of FSM-16 in solid dispersions decreased due to the adsorption of FBP. Improved dissolution of FBP from solid dispersions prepared by the evaporation and the sealed-heating methods was observed in comparison with FBP crystals.     

Adsorption properties of gases on mesoporous chromium silicate

The properties of nitrogen, carbon dioxide, and nitrogen dioxide adsorption onto mesoporous chromium silicates were studied by measurements of both the adsorption isotherms and the IR spectra. The pore sizes of two types of chromium silicates, Cr-FSM-16 (Si/Cr=170 (Cr-FSM-16 [170]) and 390 (Cr-FSM-16 [390])), which contain different amount of Cr, were 2.75 nm. BET surface areas of Cr-FSM-16 were 590 m2/g and they were smaller than that onto FSM-16. The initial heat of adsorption of nitrogen onto Cr-FSM-16 was higher than that onto FSM-16. But the initial heat of adsorption of carbon dioxide onto Cr-FSM-16 was smaller than that onto FSM-16. These results indicated that Cr in Cr-FSM-16 decreased adsorption interaction with carbon dioxide. When nitrogen dioxide was adsorbed on FSM-16 and Cr-FSM-16 at 303 K under no light, an absorption band of nitrogen monoxide adsorbed was measured by IR spectroscopy. This decomposition of nitrogen dioxide by FSM-16 and Cr-FSM-16 was caused by SiOH and Cr, respectively.     

Synthesis of Bioactive Organic-Inorganic Hybrids with γ-Methacryloxypropyltrimethoxysilane

Bioactive organic-inorganic hybrids were synthesized through sol-gel processing starting from -methacryloxypropyltrimethoxysilane. NMR-spectroscopic studies showed the presence of silanol groups (Si–OH) and Si–O–Si bonds. In vitro tests of the hybrids for bioactivity with a simulated body fluid (Kokubo solution) indicated that only calcium-containing hybrids could form apatite on their surfaces. Thus the presence of calcium ions was no less important to deposit apatite than the formation of silanol groups or Si–O–Si bonds.     

Structure of surface compounds formed during chemisorption of BBr3 on dehydrated Aerosil

The chemisorption of boron bromide on the surface of Aerosil calcined at 870 K in vacuo was studied by IR spectroscopy combined with chemical and gravimetric analysis. It was determined that the chemical reaction of structural silanol groups with BBr₃ vapor occurs monofunctionally with the formation of SiOBBr₂ groups. This indicates uniform distribution of isolated silanol groups on the surface of dehydrated Aerosils.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 3, pp. 374–377, May–June, 1989.     

Diffuse-Reflectance IR Spectra of Methane Adsorbed on NaZSM-5 and HZSM-5 Zeolites

Diffuse-reflectance IR spectra of methane adsorbed on high-silica NaZSM-5 and HZSM-5 zeolites point to a stronger adsorption of methane on sodium cations than on protons. For the asymmetric stretching vibration ₃, this form of adsorption is characterized by a doublet with band maxima at 2980 and 3010 cm^–1. For the fully symmetric stretching vibration ₁, it is characterized by a singlet with a maximum at 2880 cm^–1. Methane is also adsorbed on NaZSM-5 in a weaker form, which is characterized by absorption bands with maxima at 3002 (₃) and 2887 (₁) cm^–1. The weaker form of methane adsorption on acidic bridging hydroxy groups of HZSM-5 is characterized by absorption bands at 3001 and 2887 cm^–1 (₃ and ₁, respectively). A difference between this form of adsorption and weak adsorption on sodium-exchanged zeolite reveals itself in the somewhat higher intensity of the band at 2887 cm^–1. For methane adsorbed on NaZSM-5, the frequencies of deformational vibrations and a spectrum in the near IR region are obtained for the first time. It was found that the perturbance of adsorbed methane molecules is seen in the spectrum as in the low-frequency shifts of most of the bands that appear due to composite vibrations and overtones and as new adsorption bands that were not observed for gaseous methane.     

IR Photolysis of Liquid Hexamethyldisiloxane by Pulse CO2Laser Radiation

The IR photolysis of liquid hexamethyldisiloxane [(CH₃)₃Si]₂O by pulse CO₂laser radiation was studied. The experiments were performed both with and without a graphite powder as a sensitizer. The presence of the graphite sensitizer increases the efficiency of dissociation. To provide the highest penetration of the laser emission into a medium, the irradiation of samples were carried out with tuning far from the maximum of the Si–O bond absorption band (1055 cm^–1) using the 10P16 line (_las= 947.78 cm^–1). This tuning makes it possible to separate the process of IR multiphoton dissociation of the vapor over the liquid phase and to carry out the reaction in the liquid at a low (1 J/cm²) energy fluence of laser radiation. The IR spectra of irradiated liquid samples indicate the formation of linear and cyclic polystructures.     

One-pot three-component process for the synthesis of substituted pyrano[2,3-<Emphasis Type="Italic">c</Emphasis>]pyrazoles catalyzed by nanostructured FSM-16-SO<Subscript>3</Subscript>H

A three-component process for the one-pot synthesis of 6-amino-4-aryl-5-cyano-3-methyl-1-phenyl-1,4-dihydropyrano[2,3-c]pyrazoles by the reaction of aldehydes, 3-methyl-1-phenyl-1H-pyrazol-5(4H)-one, and malononitrile in the presence of FSM-16-SO₃H as an efficient mesoporous catalyst. The FSM-16-SO₃H was prepared and characterized by SEM, XRD, BET, and FT-IR techniques. The advantages of the presented method are high yields, short reaction times, easy purification of products, easy work-up, and reusability of the catalyst.     

Rapid adsorption and entrapment of benzoic acid molecules onto mesoporous silica (FSM-16)

Changes in the molecular state of benzoic acid (BA) in the presence of folded sheet mesoporous material (FSM-16), which has uniformly sized cylindrical mesopores and a large surface area, were assessed with several analyses. When BA was blended with FSM-16 for 5 min (BA content=30%), the X-ray diffraction peaks of BA crystals disappeared, suggesting an amorphous state. Fluorescence analysis of the mixture showed a new fluorescence emission peak for BA at 386 nm after mixing with FSM-16. Fluorescence lifetime analysis of the BA component in the mixture at 386 nm showed a longer lifetime in comparison with that of BA crystals. The solid-state (13)C CP/MAS and PST/MAS NMR spectra of the mixture with FSM-16 showed a significantly different spectral pattern from the mixture with nonporous glass, whose NMR spectra were identical to those of BA crystals. These results indicate that BA molecules disperse quickly into the hexagonal channels of FSM-16 by a simple blending procedure and adsorbed BA molecules had clearly different physicochemical properties to BA crystals.     

Infrarot-spektralphotometrische Bestimmung der ?freien? Silanolgruppen in pyrogenen Kiesels?uren

Zusammenfassung Die technischen Eigenschaften pyrogener Kieselsäuren werden entscheidend vom Gehalt an »freien« Silanolgruppen mitbestimmt. Die IR-Absorption dieser Gruppen in CCl₄ gehört zu einer Bande bei 3700 cm^–1. Es wurde festgestellt, daß die maximale Extinktion in CCl₄ unter bestimmten Bedingungen unabhängig von der Anzahl ebenfalls vorhandener »gebundener« Silanolgruppen (max. Extinktion bei etwa 3350–3450 cm^–1) sowie auch weitgehend unabhängig vom Wassergehalt (Feuchtigkeit) ist. Diese Tatsache wurde zur Ausarbeitung eines Routineverfahrens benutzt.

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Infrared-spectrophotometric determination of free silanol groups in pyrogenic silicic acids

Summary The technical properties of pyrogenic silicic acids are decisively co-determined by their content of so-called feee silanol groups. Their infrared absorption in a CCl₄ suspension belongs to a band at about 3,700cm^–1. It has been found that under certain conditions their maximum absorbance in CCl₄ is independent of the number of so-called bonded silanol groups (maximum absorption at about 3,350–3,450cm^–1), additionally existing in all commercial pyrogenic silicic acids, and also in wide ranges of the water content (humidity). This fact has been used as a basis for a quantitative routine determination of free silanol groups.

Zum Gedenken an Heinz Dannenberg     

Investigation of the surface of Ni-Pd catalysts by IR spectroscopy

The reaction of carbon monoxide with the surface of Ni, Pd, and Ni-Pd catalysts, deposited on -Al₂O₃, was investigated at 25°C by IR spectroscopy in conjunction with an adsorption volumetric technique. The IR spectra contained the following absorption bands (v, cm^–1): 2020–2100 (AB1) (linear and subcarbonyl forms of adsorbed CO); 1945–1985 (AB2) (bridging); 1920–1940 (AB3) with a shoulder at 1870–1885 (AB4) (bridging and many-center). In the spectrum of Ni the absorption band AB5 appears at 1770–1780 (CO-Ni⁺). It appears with surface coverage a 1.3 mole CO/mole M. The optical density (A) of AB1 for Ni₉₇Pd₃ is appreciably higher than for the other investigated samples. In the Ni-Pd catalysts the intensity of AB2 in relation to AB1 is higher than in nickel. The introduction of K⁺ ions into the support of the bimetallic sample reduces the optical density of AB1. In modified Ni-Pd-K the AB3 and AB4 bands disappear.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1276–1282, June, 1992.     

Water-activated cellulose-based electrorheological fluids

The performance of electrorheological (ER) fluids containing cellulose particles dispersed in lubricating oil was investigated as a function of particle water content, DC electric field strength, particle concentration, and temperature. Over a range of applied electric fields (0–3 kV/mm), yield stress was observed to increase with increasing cellulose moisture content up to 8.5 wt% followed by a decrease. Water adsorbed by cellulose particles used in these systems was shown to be non-freezing bound water. The maximum ER response for a cellulose-based fluid at 25 °C was observed at a moisture content near the transition of less mobile liquid-like (LM) water to more mobile liquid-like (MM) non-freezing water. At a constant moisture level, yield stress increased linearly with increases in either electrical field strength or particle concentration, while the ER effect decreased with increasing temperature. The present study concludes that the performance of water-activated ER fluids based on cellulose particles is influenced strongly by the mobility of non-freezing bound water adsorbed onto cellulose.     

Conducting Polymer Layers Obtained by Direct-Current Discharge Polymerization of 1-Amino-9,10-anthraquinone

The polymerization of 1-amino-9,10-anthraquinone in a direct-current discharge was studied. It was found that polymer films with a conductivity of 10^–5–10^{–4 –1} cm^–1 were formed at the cathode. It was assumed that the semiconductor properties are due to the presence of a conjugated cyclic moiety in the films. The layers deposited at the anode turned out to be typical dielectrics with a conductivity of 10^{–16 –1} cm^–1.     

Vibrational spectra of 2-biphenylmethanol. Spectrum simulation and molecular structure

The vibrational spectra of a solid crystalline sample of 2-biphenylmethanol have been measured at room temperature. The IR absorption spectra were recorded in the range 400 cm^–1–3600 cm^–1; Raman spectra were measured in the range 10 cm^–1–1640 cm^–1. The direct mechanical and optoelectronic problems were solved using the fragment method realized as Lev-100 software; the intensity distribution in the IR spectrum of 2-biphenylmethanol was obtained by the same method. The experimental Raman and IR absorption spectra were interpreted by analyzing the calculated data on the frequencies and forms of normal vibrations and their intensities in the IR spectra. IR absorption spectra were simulated for several models of 2-biphenylmethanol conformers that differ in the mutual orientation of fragments. Based on the results of simulation and comparison of the calculated and experimental spectra of conformers we suggested a model for the conformer realized in the solid phase under normal conditions.Original Russian Text Copyright © 2004 by L. M. Babkov, J. Baran, N. A. Davydova, J. I. Kukielskii, and S. V. TrukhachevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 624–631, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

IR-Spectroscopic Study of the Binding Isomerism of Adsorbed Molecules

This paper discusses the use of IR spectroscopy in the studies of isomerism in the binding of adsorbed molecules with a surface when a molecule may form several different surface species at the same site. Species whose geometry does not provide minimal adsorption energy can be considered as adsorption complexes in an excited state. The spectral manifestations of such a steric excitation are compared with the electronic and vibrational excitations of surface species. The sterically excited isomeric states existing in thermodynamic equilibrium with ordinary adsorption species are found and studied in detail. Examples are CO molecules bound through C and O atoms with metal cations in zeolites or with surface hydroxyl groups, the thiophene molecule via hydrogen bonding with silanol groups, and HD molecules dissociatively adsorbed on ZnO. A possible role of sterically activated isomeric states in catalysis is discussed.     

Research on furan acetal compounds

When 4-alkyl-2-(5-X-2-furyl)-1,3-dioxolanes are heated in the presence of tert-butyl peroxide the acetal ring is opened at the C-O 3–4 bond to give isomeric esters of 5-substituted furan-2-carboxylic acid. The structure of the product was confirmed by means of the UV and IR spectra, gas-liquid chromatography, and alternative synthesis.See [1] for communication VIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1327–1329, October, 1976.     

Silanol group effect in C18 bonded phases in HPLC

Summary If any residual (free) silanol groups remain at the surface of silica gel after bonding treatment, they may affect the retention of solutes since the dissociated groups (SiO^–) will attract cations. The silanol group effect on the retention of cationic solutes will increase with increasing pH of the mobile phase but the effect will decrease with increasing hydrophobic-ion concentration at the C₁₈ surface because such ions can mask the residual silanol groups. A method for the separation of metal complexes with 2-(5-bromo-2-pyridylazo)-diethylaminephenol (5-Br-PADAP) has been developed. The hydrophobic ion in the MeOH/H₂O mobile phase was tetrabutylammonium (TBA).     

Electrophysical Properties of a Poly(ethylene terephthalate) Film Modified in a Cyclohexane Plasma

The structure of a thin layer applied on a poly(ethylene terephthalate) (PET) film using ion-assisted chemical vapor deposition of cyclohexane was studied by electron spectroscopy for chemical analysis and IR spectroscopy. It was found that the film was composed of linear (–₂–)_n chains bearing six-membered cyclohexane rings, including those containing carbonyl groups as substituents, and carbon chains free of H atoms. The plasma-synthesized cyclohexane film was found to be semiconducting. The deposition of a film 10–120 nm in thickness on the surface of PET 30 m in thickness resulted in an increase in the bulk conductivity over the temperature range 20–200°C and in a considerable increase in the electric strength.     

Vapor-phase hydrogenation of acetone on applied metals of the platinum group

Ruthenium, rhodium, iridium, and platinum, applied on -Al₂O₃, show a high catalytic activity in the vapor-phase hydrogenation of acetone to isopropanol at 337–393K; under these conditions palladium is inactive. A reaction mechanism has been derived from kinetic measurements, adsorption and thermal desorption data, and IR spectra includes as a limiting stage the reaction of acetone adsorbed on the metal with atomic or molecular hydrogen. The kinetic and thermodynamic characteristics of the reaction have been established. The order of the specific catalytic activity of the metals has been determined, the mechanism of adsorption of alcohols on transition metals has been discussed, and the inhibition of the reaction by isopropanol adsorbed on the Ru catalyst has been interpreted.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 6, pp. 698–706, November–December, 1986.     

Molecular electric polarizabilities

The electric field variant (EFV) Gaussian basis sets of double-zeta (2-) quality are used for the calculation of the electric dipole polarizabilities of diatomic molecules in the Hartree-Fock approximation. The explicit external electric field dependence of the GTO basis set, introduced according to the method described in Part I of this series, is shown to account for the major portion of the electric field induced deformation of the wavefunction. The Polarizabilities obtained in the present calculations are quite close to the best Hartree-Fock results. The deviations from near-Hartree-Fock values amount to 3–8 per cent for the parallel component and to 10–15 per cent for the perpendicular one. It was also shown that the same method leads simultaneously to a considerable improvement of the dipole moments.This research was supported by the Institute of Low Temperatures and Structure Research of the Polish Academy of Sciences.     

Effect of alkaline modification of products of thermal vacuum and hydrothermal treatment of NH4Na-Y zeolite according to the IR spectral data

The effect of alkaline modification on the structure of the products of heat treatment of NH₄Na-Y zeolite (53% NH ₄ ⁺ , Si/Al - 2.37) in a vacuum at 573 K and in water vapors at 873 K was investigated with the IR spectrum of vibrations of the zeolite framework in the 400–1200 cm^–1 region. It was shown that the high-frequency shift of the bands in the spectra of the products obtained, the stretching vibration of v_as(TO₄) tetrahedrons in particular (T=Si, Al) at 1023 cm^–1 by 6 and 19 cm^–1, is determined by a decrease in the excess negative charge of the framework due to weakening and hydrolytic splitting of Al-O bonds of the deammoniated units with the formation of bridging Si-O(H)...Al and terminal Si-OHHO-Al hydroxyl groups. Treatment of these samples with an aqueous solution of KOH (pH 13.4) at 293 and 353 K restores the normal framework Si-O-Al bonds at the sites of formation of bridging and terminal hydroxyl groups. In the second case, restoration is hindered by substitution of H⁺ by K⁺ with some silanol groups.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. I. V. Grebenshchikov Institute of Silicate Chemistry, Russian Academy of Sciences, 199164 St. Petersburg. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1733–1739, August, 1992.