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1.
J Colloid Interface Sci ; 426: 48-55, 2014 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-24863764

RESUMO

To control the properties of poly(dimethylsiloxane) (PDMS, Oxane 1000) as a bio-inert material, the characteristics of Oxane 1000 were compared for PDMS alone and interacting with silica gel Si-100 and nanosilica PS400. Low-temperature (1)H NMR spectroscopy, applied to static samples at 200-300 K, and differential scanning calorimetry (DSC) at 153-393 K were used to analyze the properties of PDMS and composites. The NMR study shows that liquid and solid-like fractions of PDMS co-exist over a broad temperature range. The cooling-heating cycles give hysteresis loops of intensity of (1)H NMR signals of methyl groups of a liquid fraction of PDMS vs. temperature depending on the silica type. The loop width differs for PDMS alone and bound to silicas, and the samples preheated at 420 K are characterized by much narrower loops. DSC measurements of the samples show a significant difference in the thermograms on the first and second DSC scans that depend on the silica type. For PDMS confined in pores of silica gel, 3D spatial structure of the polymers can be more ordered than that of PDMS located in thin layers at a surface of nanosilica. Therefore, both melting endotherms and crystallization exotherms are observed for PDMS/silica gel. However, for PDMS/nanosilica, both thermal features are much weaker and observed during only the first DSC scan.


Assuntos
Temperatura Baixa , Dimetilpolisiloxanos/química , Temperatura Alta , Nanoestruturas , Dióxido de Silício/química , Varredura Diferencial de Calorimetria
2.
J Colloid Interface Sci ; 404: 140-9, 2013 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-23721830

RESUMO

Detailed analysis of the interfacial behavior of water and weakly polar or nonpolar organics adsorbed alone or co-adsorbed onto activated carbons (AC) at different temperatures is a complex problem important for practical applications of adsorbents. Interaction of water, 1-decanol, and n-decane with AC possessing highly developed porosity (pore volume Vp≈1.4-2.3 cm(3)/g, specific surface area S(BET)≈1500-3500 m(2)/g) was studied over a broad temperature range using differential scanning calorimetry (DSC), thermoporometry, (1)H NMR spectroscopy, cryoporometry, and temperature-programmed desorption with mass-spectrometry control methods. Comparison of the pore size distributions (PSD) calculated using the DSC thermoporometry, NMR cryoporometry, and nitrogen adsorption isotherms allows us to determine localization of adsorbates in different pores, as well as changes in the PSD of AC due to freezing of adsorbates in pores. Theoretical calculations (using ab initio HF/6-31G(d,p), DFT B3LYP/6-31G(d,p), and PM7 methods) explain certain aspects of the interfacial behavior of water, decane, and decanol adsorbed onto AC that appear in the experimental data. Obtained results show strong temperature dependence (above and below the freezing point, Tf, of bulk liquids) of the interfacial behavior of adsorbates on the textural characteristics and hydrophilic/hydrophobic properties of AC and the adsorbate amounts that affect the distributions of adsorbates unfrozen at T

3.
J Colloid Interface Sci ; 394: 467-74, 2013 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-23313347

RESUMO

The interfacial behavior of silicone oils Oxane 1000 and Oxane 5700 (polydimethylsiloxanes, PDMS) interacting with dried or hydrated (hydration h=0.005 or 0.1g/g) silica gels Si-60 and Si-100 or nanosilica A-400 was studied using low-temperature (1)H NMR spectroscopy over the 210-310 K range. Broadening of the melting temperature range toward both sides from the freezing point is observed for silicone oils confined in mesopores (2-15 nm in radius) of silica gel particles (0.2-0.5 mm in size) or voids (1-100 nm) between silica nanoparticles (5-10 nm in size) in their aggregates. This effect is a consequence of the phase state heterogeneity, since both liquid and solid-like fractions of adsorbed PDMS are observed over a large temperature range. The adsorbed PDMS heterogeneity depends on the pore size distribution (confined space effect), and it is lower for silica gel Si-100 possessing broader pores than Si-60. An increase in the amounts of adsorbed polymer and water diminishes the effects of confined space on PDMS because a fraction of the polymers is located in broader pores or out of pores (voids). This leads to relative decrease in interactions of PDMS with the silica surface. (1)H NMR spectra of PDMS and n-decane bound to silica gels reveal much stronger heterogenization of adsorbed PDMS (depending on the polymer length) than that of the alkane.


Assuntos
Dimetilpolisiloxanos/química , Sílica Gel/química , Dióxido de Silício/química , Óleos de Silicone/química , Adsorção , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Nanopartículas/química , Porosidade , Propriedades de Superfície , Temperatura de Transição
4.
J Therm Anal Calorim ; 108(3): 1085-1092, 2012.
Artigo em Inglês | MEDLINE | ID: mdl-25999781

RESUMO

Mesoporous titanium-containing silicas with different Titania contents were investigated. The structural parameters of the materials were characterized by low-temperature adsorption/desorption of nitrogen and X-ray diffraction analysis. The thermodesorption of water using the quasi-isothermal thermogravimetry as well as the differential scanning calorimetry were used to characterize thermal and surface properties of these materials. The adsorbed water layers and the concentration of weakly and strongly bound water as well as the surface free energy on the adsorbent/water interfaces were calculated. It was stated that the increase of Titania content causes a gradual decrease of specific surface area and formation of biporous structure inside the tested materials. The water thermodesorption from the surface proceeds in two or three stages, which is connected mainly with pore distribution and TiO2 content. One can observe the increase of the total surface free energy (ΔGΣ) with the increasing TiO2 content, but the largest ΔGΣ value at the adsorbent/strongly bound water interface is exhibited by the adsorbent of intermediate content (30%) of TiO2. Freezing temperature of water contained in the pores of the studied materials is connected largely with their porous structure. Due to the well developed porous structure, the water freezing process is a multi-stage one.

5.
J Colloid Interface Sci ; 355(2): 300-11, 2011 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-21227443

RESUMO

The structural, textural, and adsorption characteristics of mechanochemically activated (MCA) fumed silica A-300 as dry or water, ethanol, or water/ethanol-wetted powders (0.5 g of a solvent per gram of silica) in a ball mill for 1-6 h were studied in comparison with those of the initial powder. The MCA treatment enhances bulk density (ρ(b)) of the powder (from 0.045 g/cm(3) for the initial silica to 0.4 g/cm(3) for 6 h-MCA-treated water-wetted silica) depending on medium type and MCA time (t(MCA)). Stronger effects are observed for the MCA treatment of water-wetted silica than of dry or ethanol- or water/ethanol-wetted samples. The MCA treatment weakly affects the specific surface area (S(BET)). However, void (pore) size distribution, porosity, particle aggregation and size distribution in aqueous suspension, behavior of interfacial water, properties of poly(vinyl alcohol)/silica composites and adsorption of gelatin depend more strongly on the t(MCA) and ρ(b) values. Some of the observed changes in the characteristics (e.g., gelatin adsorption) depend on the ρ(b) value but are independent of the medium type used on the MCA. Other characteristics are nonlinear functions of both t(MCA) and ρ(b) values.


Assuntos
Gelatina/química , Nanoestruturas/química , Dióxido de Silício/química , Adsorção , Gelatina/metabolismo , Tamanho da Partícula , Porosidade , Dióxido de Silício/metabolismo , Solventes/química , Propriedades de Superfície , Suspensões , Água/química , Molhabilidade
6.
J Colloid Interface Sci ; 348(2): 546-58, 2010 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-20621822

RESUMO

Adsorption of low-molecular adsorbates (nonpolar hexane, nitrogen, weakly polar acetonitrile, and polar diethylamine, triethylamine, and water) onto individual (silica, alumina, titania), binary (silica/alumina (SA), silica/titania (ST)), and ternary (alumina/silica/titania, AST) fumed oxides was studied to analyse the effects of morphology and surface composition of the materials. Certain aspects of the interfacial phenomena dependent on the structural characteristics of oxides were analysed using calorimetry, (1)H NMR, and Raman spectroscopies, XRD, and ab initio quantum-chemical calculations. The specific surface area S(BET,X)-to-S(BET,N(2)) ratio (X is an organic adsorbate) changes from 0.68 for hexane adsorbed onto amorphous SA8 (degassed at 200 degrees C) to 1.85 for acetonitrile adsorbed onto crystalline alumina (degassed at 900 degrees C). These changes are relatively large because of variations in orientation, lateral interactions, and adsorption compressing of molecules adsorbed onto oxide surfaces. Larger S(BET,X)/S(BET,N(2)) values are observed for mixed oxides with higher crystallinity of titania or/and alumina phases in larger primary nanoparticles with greater surface roughness and hydrophilicity. Polar adsorbates can change the structure of aggregates of oxide nanoparticles that can, in turn, affect the results of adsorption measurements.


Assuntos
Óxido de Alumínio/química , Nanopartículas/química , Óxidos/química , Dióxido de Silício/química , Titânio/química , Acetonitrilas/química , Adsorção , Dietilaminas/química , Etilaminas/química , Hexanos/química , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Nitrogênio/química , Propriedades de Superfície , Água/química
7.
J Colloid Interface Sci ; 338(2): 376-88, 2009 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-19596124

RESUMO

Fe2O3/SiO2 nanocomposites based on fumed silica A-300 (S(BET)=337 m2/g) with iron oxide deposits at different content were synthesized using Fe(III) acetylacetonate (Fe(acac)3) dissolved in isopropyl alcohol or carbon tetrachloride for impregnation of the nanosilica powder at different amounts of Fe(acac)3 then oxidized in air at 400-900 degrees C. Samples with Fe(acac)3 adsorbed onto nanosilica and samples with Fe2O3/SiO2 including 6-17 wt% of Fe2O3 were investigated using XRD, XPS, TG/DTA, TPD MS, FTIR, AFM, nitrogen adsorption, Mössbauer spectroscopy, and quantum chemistry methods. The structural characteristics and phase composition of Fe2O3 deposits depend on reaction conditions, solvent type, content of grafted iron oxide, and post-reaction treatments. The iron oxide deposits on A-300 (impregnated by the Fe(acac)3 solution in isopropanol) treated at 500-600 degrees C include several phases characterized by different nanoparticle size distributions; however, in the case of impregnation of A-300 by the Fe(acac)3 solution in carbon tetrachloride only alpha-Fe2O3 phase is formed in addition to amorphous Fe2O3. The Fe2O3/SiO2 materials remain loose (similar to the A-300 matrix) at the bulk density of 0.12-0.15 g/cm3 and S(BET)=265-310 m2/g.


Assuntos
Compostos Férricos/química , Nanocompostos/química , Dióxido de Silício/química , 2-Propanol/química , Adsorção , Tetracloreto de Carbono/química , Oxirredução , Solventes/química , Propriedades de Superfície , Temperatura , Tolueno/química
8.
J Colloid Interface Sci ; 323(1): 6-17, 2008 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-18440015

RESUMO

The structural and adsorption characteristics of polymer adsorbent LiChrolut EN and the behavior of adsorbed water and water/organic mixtures were studied using adsorption, microcalorimetry, transmission and scanning electron microscopy, mass spectrometry, infrared spectroscopy, 1H NMR spectroscopy with layer-by-layer freezing-out of liquids (190-273 K), and thermally stimulated depolarization current method (90-265 K). This adsorbent is characterized by large specific surface area (approximately 1500 m2/g) and pore volume (0.83 cm3/g) with a major contribution of narrow pores (R<10 nm) of a complicated shape (long hysteresis loop is in nitrogen adsorption-desorption isotherm). The adsorbent includes aromatic and aliphatic structures and oxygen-containing functionalities and can effectively adsorb organics and water/organic mixtures. On co-adsorption of water and organics (dimethyl sulfoxide, chloroform, methane), there is a weak influence of one on another adsorbate due to their poor mixing in pores. Weakly polar chloroform displaces a fraction of water from narrow pores. These effects can explain high efficiency of the adsorbent in solid-phase extraction of organics from aqueous solutions. The influence of structural features of several carbon and polymer adsorbents on adsorbed nitrogen, water and water/organics is compared on the basis of the adsorption and 1H NMR data.

9.
J Colloid Interface Sci ; 314(1): 119-30, 2007 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-17570390

RESUMO

A variety of fumed oxides such as silica, alumina, titania, silica/alumina (SA), silica/titania (ST), and alumina/silica/titania (AST) were characterized. These oxides have different specific surface areas and different primary particle composition in the bulk and at the surface. These materials were studied by FTIR, NMR, Auger electron spectroscopy, one-pass temperature-programmed desorption with mass spectrometry control (OP TPDMS), microcalorimetry, and nitrogen adsorption. Nonlinear changes in the surface content of alumina in SA and AST and titania in ST and AST samples with increasing oxide content along with simultaneous changes in their specific surface area cause complex dependencies of the heat of immersion in water and desorption of water on heating on the structural parameters. Simultaneous analysis of changes in the surface phase composition, in the concentration of hydroxyls, and in the structural characteristics reveals that at a low content of the second phase the structural characteristics (e.g., S(BET)) are predominant; however, at a large content of these oxides the phase composition plays a more important role.


Assuntos
Óxido de Alumínio/química , Óxidos/química , Dióxido de Silício/química , Titânio/química , Espectroscopia de Ressonância Magnética , Teste de Materiais , Espectroscopia de Infravermelho com Transformada de Fourier , Propriedades de Superfície , Termodinâmica
10.
J Colloid Interface Sci ; 312(2): 201-13, 2007 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-17482636

RESUMO

Interaction of poly(vinyl alcohol) (PVA) with fumed silica was investigated in the gas phase and aqueous media using adsorption, broadband dielectric relaxation spectroscopy (DRS), thermally stimulated depolarization current (TSDC), infrared spectroscopy, thermal analysis, and one-pass temperature-programmed desorption (OPTPD) mass-spectrometry (MS) methods. PVA monolayer formation leads to certain textural changes in the system (after suspension and drying) because of strong hydrogen bonding of the polymer molecules to silica nanoparticles preventing strong interaction between silica particles themselves. This strong interaction promotes associative desorption of water molecules at lower temperatures than in the case of silica alone. Interaction of PVA with silica and residual water leads to depression of glass transition temperature (T(g)). There are three types of dipolar relaxations at temperatures lower and higher than the T(g) value. A small amount of adsorbed water leads to significant conductivity with elevating temperature.


Assuntos
Álcool de Polivinil/química , Dióxido de Silício/química , Propriedades de Superfície , Adsorção , Ligação de Hidrogênio , Espectrometria de Massas , Espectrofotometria Infravermelho , Análise Espectral , Temperatura , Água/química
11.
Langmuir ; 23(6): 3184-92, 2007 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-17261043

RESUMO

Structural characterization of different silicas (ordered mesoporous silicas MCM-41, MCM-48, and SBA-15, amorphous silica gels Si-40, Si-60, and Si-100, and initial and wetted-dried fumed silica A-300) and bio-objects (fibrinogen solution, yeast cells, wheat seeds, and bone tissues) has been done using two versions of cryoporometry based on integral Gibbs-Thomson (IGT) equation for freezing point depression of pore liquids measured by 1H NMR spectroscopy (180-200 < T < 273 K) and thermally stimulated depolarization current (TSDC) method (90 < T < 273 K). The IGT equation was solved using a self-consisting regularization procedure including the maximum entropy principle applied to the distribution function of pore size (PSD). Comparison of the PSDs calculated by using the cryoporometry and nitrogen adsorption methods for the mentioned silicas demonstrates that IGT equation provides satisfactory fit which is better than that obtained with nonintegral Gibbs-Thomson (GT) equation (based on the GT equation) proposed by Aksnes and Kimtys. The NMR- and TSDC-cryoporometry methods applied to probe biosystems give clear pictures of changes in the structural characteristics caused, e.g., by hydration and swelling of wheat seeds and yeast cells, coagulation and interaction of fibrinogen with solid nanoparticles in the aqueous media, and human bone tissue disease.


Assuntos
Biofísica/métodos , Adsorção , Osso e Ossos/metabolismo , Físico-Química/métodos , Entropia , Fibrinogênio/química , Humanos , Espectroscopia de Ressonância Magnética/métodos , Modelos Químicos , Modelos Estatísticos , Nanopartículas , Nitrogênio/química , Termodinâmica , Triticum/metabolismo , Leveduras/metabolismo
12.
J Colloid Interface Sci ; 308(1): 142-56, 2007 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-17257612

RESUMO

Polymethylsiloxane (PMS) hydrogel (C(PMS)=10 wt%, soft paste-like hydrogel), diluted aqueous suspensions, and dried/wetted xerogel (powder) were studied in comparison with suspensions and dry powders of unmodified and silylated nanosilicas and silica gels using (1)H NMR, thermally stimulated depolarization current (TSDC), quasielastic light scattering (QELS), rheometry, and adsorption methods. Nanosized primary PMS particles, which are softer and less dense than silica ones because of the presence of CH(3) groups attached to each Si atom and residual silanols, form soft secondary particles (soft paste-like hydrogel) that can be completely decomposed to nanoparticles with sizes smaller than 10 nm on sonication of the aqueous suspensions. Despite the soft character of the secondary particles, the aqueous suspensions of PMS are characterized by a higher viscosity (at concentration C(PMS)=3-5 wt%) than the suspension of fumed silica at a higher concentration. Three types of structured water are observed in dry PMS xerogel (adsorbed water of 3 wt%). These structures, characterized by the chemical shift of the proton resonance at delta(H) approximately 1.7,3.7, and 5 ppm, correspond to weakly associated but strongly bound water and to strongly associated but weakly or strongly bound waters, respectively. NMR cryoporometry and QELS results suggest that PMS is a mesoporous-macroporous material with the textural porosity caused by voids between primary particles forming aggregates and agglomerates of aggregates. PMS is characterized by a much smaller adsorption capacity with respect to proteins (gelatin, ovalbumin) than unmodified fumed silica A-300.

13.
Adv Colloid Interface Sci ; 131(1-2): 1-89, 2007 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-17188637

RESUMO

Applications of thermally stimulated depolarisation current (TSDC) technique to a variety of systems with different dispersion phases such as disperse and porous metal oxides, polymers, liquid crystals, amorphous and crystalline solids, composites, solid solutions, biomacromolecules, cells, tissues, etc. in gaseous or liquid dispersion media are analysed. The effects of dipolar, direct current (dc) and space charge relaxations are linked to the temperature dependent mobility of molecules, their fragments, protons, anions, and electrons and depend on thermal treatment, temperature and field intensity of polarisation, heating rate on depolarisation or cooling rate on polarisation. Features of the relaxation mechanisms are affected not only by the mentioned factors but also by morphological, structural and chemical characteristics of materials. The interfacial phenomena, especially the role of interfacial water, received significant attention on analysis of the TSDC data. Comparison of the data of TSDC and dielectric relaxation spectroscopy (DRS), differential scanning calorimetry (DSC), 1H NMR spectroscopy with layer-by-layer freezing-out of bulk and interfacial water, adsorption/desorption of nitrogen, water and dissolved organics demonstrates high sensitivity and information content of the TSDC technique, allowing a deeper understanding of interfacial phenomena.

14.
Colloids Surf B Biointerfaces ; 53(1): 29-36, 2006 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-16959475

RESUMO

Water bound in human bone tissues healthy (sample S1) and affected by osteoporosis (sample S2) was investigated by using 1H NMR spectroscopy with layer-by-layer freezing-out of bulk and interfacial waters at T< 273 K. The 1H NMR spectra of the bound water include two signals which can be assigned to strongly associated typical water (chemical shift of the proton resonance at delta(H) approximately 5 ppm) and weakly associated water at delta(H) approximately 1.4 ppm. Approximately, half of the bound water is in the weakly associated state in S1. A fraction of similar water in S2 is smaller because of the structural difference of the studied samples. The pore size distribution of S2 (in aqueous medium) calculated using the cryoporometry method is characterized by much larger intensity of mesopores and macropores in comparison with that of S1. The total porosity and the surface area of the biostructures (accessible for water molecules and estimated on the basis of the cryoporometry data using a model of cylindrical pores) are larger for S2. Weakly polar chloroform-d has a significant influence on the organization of water in a spongy component of bone tissue. This effect depends on the porosity of the bone matrix and the amounts of CDCl3.


Assuntos
Osso e Ossos/química , Osso e Ossos/anatomia & histologia , Humanos , Espectroscopia de Ressonância Magnética/métodos , Osteoporose/fisiopatologia , Porosidade
15.
Colloids Surf B Biointerfaces ; 48(2): 167-75, 2006 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-16531020

RESUMO

Water bound in bone of rat tail vertebrae was investigated by 1H NMR spectroscopy at 210-300 K and by the thermally stimulated depolarization current (TSDC) method at 190-265 K. The 1H NMR spectra of water clusters were calculated by the GIAO method with the B3LYP/6-31G(d,p) basis set, and the solvent effects were analyzed by the HF/SM5.45/6-31G(d) method. The 1H NMR spectra of water in bone tissue include two signals that can be assigned to typical water (chemical shift of proton resonance deltaH=4-5 ppm) and unusual water (deltaH=1.2-1.7 ppm). According to the quantum chemical calculations, the latter can be attributed to water molecules without the hydrogen bonds through the hydrogen atoms, e.g., interacting with hydrophobic environment. An increase in the amount of water in bone leads to an increase in the amount of typical water, which is characterized by higher associativity (i.e., a larger average number of hydrogen bonds per molecule) and fills larger pores, cavities and pockets in bone tissue.


Assuntos
Osso e Ossos/química , Espectroscopia de Ressonância Magnética , Água/química , Algoritmos , Animais , Eletricidade , Congelamento , Temperatura Alta , Porosidade , Teoria Quântica , Ratos , Ratos Wistar , Coluna Vertebral/química , Eletricidade Estática , Cauda , Termodinâmica
16.
J Colloid Interface Sci ; 294(1): 53-68, 2006 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-16081086

RESUMO

Several activated carbons differently pretreated (de-ashed, oxidized, reduced, wetted, frozen, and dried) were investigated using static (equilibrium adsorption of nitrogen and benzene) and dynamic (tert-butylbenzene (TBB)) adsorption methods. Treatments of carbons at relatively mild conditions leading to not great changes in their textural characteristics affect the TBB breakthrough concentration because of changes in the chemistry of the surfaces (oxidized or reduced) and the presence of water in airstream or pre-adsorbed on carbon beds. Oxygen-containing functionalities at a carbon surface change condition of competitive adsorption of nonpolar TBB and polar water molecules. Calculations of distribution functions of adsorption potential (A), energy (E), Gibbs free energy (Delta G) of adsorption of benzene and TBB and effective adsorption (first-order) rate pseudoconstant beta e over different ranges of relative exit TBB concentration c(t)/c(0) (from approximately 10(-5) to 0.01-0.4) reveal nonlinear effects caused by the size of carbon granules, the pore size distributions, the presence of water, oxidation or reduction of the surfaces and other treatments resulting in distribution functions f(y) with nonzero intensity in relatively broad ranges of the A, E, Delta G, and beta e values. There are many factors affecting the breakthrough parameters; therefore, simple linear relationships between these parameters and the structural characteristics (S(BET), S(DS), Vp, and V(DS)) are not observed.

17.
Adv Colloid Interface Sci ; 118(1-3): 125-72, 2005 Dec 30.
Artigo em Inglês | MEDLINE | ID: mdl-16213452

RESUMO

The behaviour of water at mosaic hydrophilic/hydrophobic surfaces of different silicas and in biosystems (biomacromolecules, yeast cells, wheat seeds, bone and muscular tissues) was studied in different dispersion media over wide temperature range using 1H NMR spectroscopy with layer-by-layer freezing-out of bulk water (close to 273 K) and interfacial water (180 < T < 273 K), thermally stimulated depolarization current (TSDC) (90 < T < 270 K), infrared (IR) spectroscopy, and quantum chemical methods. Bulk water and water bound to hydrophilic/hydrophobic interfaces can be assigned to different structural types. There are (i) weakly associated interfacial water (1H NMR chemical shift delta(H) = 1.1-1.7 ppm) that can be assigned to high-density water (HDW) with collapsed structure (CS), representing individual molecules in hydrophobic pockets, small clusters and interstitial water with strongly distorted hydrogen bonds or without them, and (ii) strongly associated interfacial water (delta(H) = 4-5 ppm) with larger clusters, nano- and microdomains, and continuous interfacial layer with both HDW and low-density water (LDW). The molecular mobility of weakly associated bound water is higher (because hydrogen bonds are distorted and weakened and their number is smaller than that for strongly associated water) than that of strongly associated bound water (with strong hydrogen bonds but nevertheless weaker than that in ice Ih) that results in the difference in the temperature dependences of the 1H NMR spectra at T < 273 K. These different waters are also appear in changes in the IR and TSDC spectra.


Assuntos
Modelos Químicos , Dióxido de Silício/química , Água/química , Físico-Química/métodos , Interações Hidrofóbicas e Hidrofílicas , Propriedades de Superfície , Temperatura
18.
J Colloid Interface Sci ; 289(2): 427-45, 2005 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-16024031

RESUMO

Several series of fumed silicas and mixed fumed oxides produced and treated under different conditions were studied in gaseous and liquid media using nitrogen and water adsorption-desorption, mass spectrometry, FTIR, NMR, thermally stimulated depolarization current (TSDC), photon correlation spectroscopy (PCS), zeta potential, potentiometric titration, and Auger electron spectroscopy methods. Aggregation of primary particles and adsorption capacity (Vp) decrease and hysteresis loops of nitrogen adsorption-desorption isotherms becomes shorter with decreasing specific surface area (S(BET)). However, the shape of nitrogen adsorption-desorption isotherms can be assigned to the same type independent of S(BET) value. The main maximum of pore size distribution (gaps between primary nonporous particles in aggregates and agglomerates) shifts toward larger pore size and its intensity decreases with decreasing S(BET) value. The water adsorption increases with increasing S(BET) value; however, the opposite effect is observed for the content of surface hydroxyls (in mmol/m2). Associative desorption of water (2(SiOH)-->SiOSi+H2O) depends on both the morphology and synthesis conditions of fumed silica. The silica dissolution rate increases with increasing S(BET) and pH values. However, surface charge density and the modulus of zeta-potential increase with decreasing S(BET) value. The PCS, 1H NMR, and TSDC spectra demonstrate rearrangement of the fumed silica dispersion depending on the S(BET) value and the silica concentration (C(SiO2)) in the aqueous suspensions. A specific state of the dispersion is observed at the C(SiO2) values corresponding to the bulk density of the initial silica powder.

19.
J Colloid Interface Sci ; 283(2): 329-43, 2005 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-15721902

RESUMO

Nonfreezable water structured due to interaction with endocellular objects in yeast cells (endocellular water) or with partially hydrophobic fumed silica (interfacial water) was studied by means of (1)H NMR spectroscopy with layer-by-layer freezing-out of bulk water and quantum chemical methods applied to water clusters in the gas and liquid (chloroform and cyclohexene) phases and adsorbed on silylated silica. Variation in cell hydration as well as in amount of water adsorbed on modified fumed silica leads to changes in the ratio between contributions of two water states characterized by NMR chemical shifts at delta(H)=1.1-1.7 and 4-5 ppm. Lowering of hydration and temperature results in an enhancement of the first signal, and the opposite result is observed for the second signal. These effects may be explained by structured water distribution in the form of relatively large nanodroplets (delta(H)=4-5 ppm is close to that for bulk water) and small clusters of the 2D structure, in which the fraction of hydrogen atoms out of the hydrogen bonds (delta(H)=1.1-1.7 ppm) is larger than that in nanodroplets.


Assuntos
Interações Hidrofóbicas e Hidrofílicas , Saccharomyces cerevisiae/química , Saccharomyces cerevisiae/citologia , Dióxido de Silício/química , Água/química , Dessecação , Espectroscopia de Ressonância Magnética/métodos , Espectroscopia de Ressonância Magnética/normas , Modelos Químicos , Modelos Moleculares , Tamanho da Partícula , Teoria Quântica , Padrões de Referência , Saccharomyces cerevisiae/fisiologia , Sensibilidade e Especificidade , Espectroscopia de Infravermelho com Transformada de Fourier , Propriedades de Superfície , Temperatura
20.
J Colloid Interface Sci ; 282(2): 261-9, 2005 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-15589530

RESUMO

The process of concentrating amphetamine (1-phenyl-2-propanamine, C6H5CH2CH(NH2)CH3) and its N-alkyl substituted derivatives C6H5CH2CH(NHR)CH3 and C6H5CH2CH(N(CH3)R)CH3 (R=(CH2)(n)CH3 at n=0, 1, 2, and 3) from diluted aqueous solution was investigated using six adsorbents having different textures and chemical compositions. Three chemically modified carbon adsorbents prepared from plum stones and routinely used SPE cartridges packed with graphitized adsorbents such as Hypercarb and Envicarb and polymeric LiChrolut EN were applied. Recovery rates of amphetamines increase nearly linearly with growing free energy of solvation due to better adsorption of amphetamines with larger side groups from polar solution. Reduction of a carbon surface leads to a decrease in the recovery rate. Its minimal values are observed for the adsorption of amphetamines on graphitized carbons due to both lower adsorption and worse desorption (elution) in comparison with those for activated carbons.


Assuntos
Anfetaminas/química , Anfetaminas/farmacologia , Adsorção , Carbono/química , Química Farmacêutica/métodos , Interações Medicamentosas , Modelos Estatísticos , Nitrogênio/química , Preparações Farmacêuticas , Espectroscopia de Infravermelho com Transformada de Fourier , Termodinâmica
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