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1.
Inorg Chem ; 57(12): 7151-7167, 2018 Jun 18.
Artículo en Inglés | MEDLINE | ID: mdl-29874059

RESUMEN

A procedure is developed for defining a compositionally and structurally realistic, atomic-scale description of exfoliated clay nanoparticles from the kaolinite family of phylloaluminosilicates. By use of coordination chemical principles, chemical environments within a nanoparticle can be separated into inner, outer, and peripheral spheres. The edges of the molecular models of nanoparticles were protonated in a validated manner to achieve charge neutrality. Structural optimizations using semiempirical methods (NDDO Hamiltonians and DFTB formalism) and ab initio density functionals with a saturated basis set revealed previously overlooked molecular origins of morphological changes as a result of exfoliation. While the use of semiempirical methods is desirable for the treatment of nanoparticles composed of tens of thousands of atoms, the structural accuracy is rather modest in comparison to DFT methods. We report a comparative survey of our infrared data for untreated crystalline and various exfoliated states of kaolinite and halloysite. Given the limited availability of experimental techniques for providing direct structural information about nano-kaolinite, the vibrational spectra can be considered as an essential tool for validating structural models. The comparison of experimental and calculated stretching and bending frequencies further justified the use of the preferred level of theory. Overall, an optimal molecular model of the defect-free, ideal nano-kaolinite can be composed with respect to stationary structure and curvature of the potential energy surface using the PW91/SVP level of theory with empirical dispersion correction (PW91+D) and polarizable continuum solvation model (PCM) without the need for a scaled quantum chemical force field. This validated theoretical approach is essential in order to follow the formation of exfoliated clays and their surface reactivity that is experimentally unattainable.

2.
Langmuir ; 33(14): 3534-3547, 2017 04 11.
Artículo en Inglés | MEDLINE | ID: mdl-28290695

RESUMEN

Surface modifications fundamentally influence the morphology of kaolinite nanostructures as a function of crystallinity and the presence of contaminants. Besides morphology, the catalytic properties of 1:1-type exfoliated aluminosilicates are also influenced by the presence of defect sites that can be generated in a controlled manner by mechanochemical activation. In this work, we investigated exfoliated halloysite nanoparticles with a quasi-homogeneous, scroll-type secondary structure toward developing structural/functional relationships for composition, atomic structure, and morphology. The surface properties of thin-walled nanoscrolls were studied as a function of mechanochemical activation expressed by the duration of dry-grinding. The surface characterizations were carried out using N2, NH3, and CO2 adsorption measurements. The effects of grinding on the nanohalloysite structure were followed using thermoanalytical thermogravimetric/derivative thermogravimetric (TG/DTG) and infrared spectroscopic [Fourier transform infrared/attenuated total reflection (FTIR/ATR)] techniques. Grinding results in partial dehydroxylation with similar changes as those observed for heat treatment above 300 °C. Mechanochemical activation shows a decrease in the dehydroxylation mass loss and the DTG peak temperature, a decrease in the specific surface area and the number of mesopores, an increase in the surface acidity, blue shift of surface hydroxide bands, and a decrease in the intensity of FTIR/ATR bands as a function of the grinding time. The experimental observations were used to guide atomic-scale structural and energetic simulations using realistic molecular cluster models for a nanohalloysite particle. A full potential energy surface description was developed for the mechanochemical activation and/or heating toward nanometahalloysite formation that aids the interpretation of experimental results. The calculated differences upon dehydroxylation show a remarkable agreement with the mass loss values from DTG measurements.

3.
Conscious Cogn ; 42: 1-8, 2016 05.
Artículo en Inglés | MEDLINE | ID: mdl-26954487

RESUMEN

Flow is a special mental state characterized by deep concentration that occurs during the performance of optimally challenging tasks. In prior studies, proneness to experience flow has been found to be moderately heritable. In the present study, we investigated whether individual differences in flow proneness are related to a polymorphism of the dopamine D2 receptor coding gene (DRD2 C957T rs6277). This polymorphism affects striatal D2 receptor availability, a factor that has been shown to be related to flow proneness. To our knowledge, this is the first study to investigate the association between this trait and a specific gene variant. In a sample of 236 healthy Hungarian adults, we found that CC homozygotes report higher flow proneness than do T allele carriers, but only during mandatory activities (i.e., studying and working), not during leisure time. We discuss implications of this result, e.g., the potential mediators of the relationship.


Asunto(s)
Atención/fisiología , Individualidad , Receptores de Dopamina D2/genética , Análisis y Desempeño de Tareas , Adulto , Femenino , Humanos , Masculino , Adulto Joven
4.
Haematologica ; 100(12): 1508-16, 2015 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-26315932

RESUMEN

Sickle cell disease is a risk factor for invasive bacterial infections, and splenic dysfunction is believed to be the main underlying cause. We have previously shown that the liberation of heme in acute hemolysis can induce heme oxygenase-1 during granulopoiesis, impairing the ability of developing neutrophils to mount a bactericidal oxidative burst, and increasing susceptibility to bacterial infection. We hypothesized that this may also occur with the chronic hemolysis of sickle cell disease, potentially contributing to susceptibility to infections. We found that neutrophil oxidative burst activity was significantly lower in treatment-naïve children with sickle cell disease compared to age-, gender- and ethnicity-matched controls, whilst degranulation was similar. The defect in neutrophil oxidative burst was quantitatively related to both systemic heme oxygenase-1 activity (assessed by carboxyhemoglobin concentration) and neutrophil mobilization. A distinct population of heme oxygenase-1-expressing cells was present in the bone marrow of children with sickle cell disease, but not in healthy children, with a surface marker profile consistent with neutrophil progenitors (CD49d(Hi) CD24(Lo) CD15(Int) CD16(Int) CD11b(+/-)). Incubation of promyelocytic HL-60 cells with the heme oxygenase-1 substrate and inducer, hemin, demonstrated that heme oxygenase-1 induction during neutrophilic differentiation could reduce oxidative burst capacity. These findings indicate that impairment of neutrophil oxidative burst activity in sickle cell disease is associated with hemolysis and heme oxygenase-1 expression. Neutrophil dysfunction might contribute to risk of infection in sickle cell disease, and measurement of neutrophil oxidative burst might be used to identify patients at greatest risk of infection, who might benefit from enhanced prophylaxis.


Asunto(s)
Anemia de Células Falciformes/enzimología , Hemo-Oxigenasa 1/metabolismo , Neutrófilos/enzimología , Estallido Respiratorio , Adolescente , Anemia de Células Falciformes/patología , Antígenos CD/metabolismo , Niño , Preescolar , Femenino , Células HL-60 , Humanos , Lactante , Masculino , Neutrófilos/patología
5.
Pediatr Transplant ; 16(4): 350-6, 2012 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-22409370

RESUMEN

CV disease is the major cause of death in patients with CKD. Recently, CMR imaging emerges as a complementary method providing advantages in cardiac assessment; however, data on CMR in pediatric CKD are scarce. We performed CMR in 15 children: two with CKD, six on peritoneal dialysis, seven on hemodialysis, and in 18 children 5.1 (0.4-15.4) yr after kidney Tx. Eight children underwent CMR six months before and after Tx. Results are presented as mean z score ± SD. LV EF was higher and in the normal range in Tx patients compared with CKD (-0.3 ± 1 vs. -2.1 ± 1.6, respectively, p < 0.05), whereas RV EF was similar (-0.9 ± 1.4 vs. -0.9 ± 1.8, p = n.s.). End-diastolic and end-systolic LV volume index (0 ± 1.7 vs. 2.1 ± 3.1; 0.2 ± 1.2 vs. 3.1 ± 3.7, both p < 0.05) and LV mass index (1.4 ± 1.5 vs. 3.4 ± 2.9, p < 0.05) were lower in Tx children. All parameters improved in the eight children after Tx. In conclusion, our CMR analysis suggests marked improvement of cardiac function and morphology in children after kidney Tx. CMR might be an appropriate complementary method for measuring detailed cardiac status in children with CKD.


Asunto(s)
Hipertrofia Ventricular Izquierda/diagnóstico , Trasplante de Riñón , Imagen por Resonancia Magnética , Insuficiencia Renal Crónica/complicaciones , Disfunción Ventricular Izquierda/diagnóstico , Adolescente , Niño , Estudios Transversales , Femenino , Humanos , Hipertrofia Ventricular Izquierda/etiología , Masculino , Estudios Prospectivos , Insuficiencia Renal Crónica/cirugía , Insuficiencia Renal Crónica/terapia , Volumen Sistólico , Resultado del Tratamiento , Disfunción Ventricular Izquierda/etiología , Adulto Joven
6.
Oxid Med Cell Longev ; 2019: 8156592, 2019.
Artículo en Inglés | MEDLINE | ID: mdl-30800210

RESUMEN

Ascorbate requiring Fe2+/2-oxoglutarate-dependent dioxygenases located in the nucleoplasm have been shown to participate in epigenetic regulation of gene expression via histone and DNA demethylation. Transport of dehydroascorbic acid is impaired in the endomembranes of fibroblasts from arterial tortuosity syndrome (ATS) patients, due to the mutation in the gene coding for glucose transporter GLUT10. We hypothesized that altered nuclear ascorbate concentration might be present in ATS fibroblasts, affecting dioxygenase activity and DNA demethylation. Therefore, our aim was to characterize the subcellular distribution of vitamin C, the global and site-specific changes in 5-methylcytosine and 5-hydroxymethylcytosine levels, and the effect of ascorbate supplementation in control and ATS fibroblast cultures. Diminished nuclear accumulation of ascorbate was found in ATS fibroblasts upon ascorbate or dehydroascorbic acid addition. Analyzing DNA samples of cultured fibroblasts from controls and ATS patients, a lower global 5-hydroxymethylcytosine level was found in ATS fibroblasts, which could not be significantly modified by ascorbate addition. Investigation of the (hydroxy)methylation status of specific regions in six candidate genes related to ascorbate metabolism and function showed that ascorbate addition could stimulate hydroxymethylation and active DNA demethylation at the PPAR-γ gene region in control fibroblasts only. The altered DNA hydroxymethylation patterns in patient cells both at the global level and at specific gene regions accompanied with decreased nuclear accumulation of ascorbate suggests the epigenetic role of vitamin C in the pathomechanism of ATS. The present findings represent the first example for the role of vitamin C transport in epigenetic regulation suggesting that ATS is a compartmentalization disease.


Asunto(s)
Arterias/anomalías , Ácido Ascórbico/metabolismo , Núcleo Celular/metabolismo , Metilación de ADN/genética , Fibroblastos/metabolismo , Fibroblastos/patología , Genoma Humano , Inestabilidad de la Articulación/genética , Enfermedades Cutáneas Genéticas/genética , Malformaciones Vasculares/genética , 5-Metilcitosina/análogos & derivados , 5-Metilcitosina/metabolismo , Células Cultivadas , Epigénesis Genética , Humanos , Modelos Biológicos , PPAR gamma/genética , PPAR gamma/metabolismo
7.
J Colloid Interface Sci ; 318(2): 302-8, 2008 Feb 15.
Artículo en Inglés | MEDLINE | ID: mdl-17991479

RESUMEN

The mechanism for the decomposition of hydrotalcite remains unsolved. Controlled rate thermal analysis enables this decomposition pathway to be explored. Hydrotalcites containing carbonate, vanadate and molybdate were prepared by coprecipitation. The resulting materials were characterised by XRD, simultaneous TG-DTG-DTA and controlled rate thermal analysis (CRTA) to determine the stability and thermal decomposition pathway of the synthesised hydrotalcites. For the carbonate intercalated hydrotalcite dehydration takes place in three steps two of which are quasi-isothermal and one non-isothermal. Dehydroxylation and decarbonation occur separately over the 235-330 and 330-370 degrees C temperature range. A second non-isothermal decarbonation step is observed in the 371-541 degrees C range. In comparison the mixed carbonate-vanadate and carbonate-molybdate hydrotalcites show two dehydration steps and the dehydroxylation and decarbonation occur simultaneously. The observation of three dehydration steps is used to support the model of water molecules in three structurally distinct environments in the hydrotalcite interlayer. CRTA technology provides a mechanism for the decomposition of hydrotalcites.

8.
J Colloid Interface Sci ; 317(2): 523-9, 2008 Jan 15.
Artículo en Inglés | MEDLINE | ID: mdl-17976636

RESUMEN

The effect of mechanochemical activation (dry grinding), formamide intercalation, and thermal deintercalation on high- and low-defect kaolinite surfaces was studied by thermogravimetry and diffuse reflectance Fourier transform infrared spectroscopy. These investigations were completed with specific surface area and pore size distribution measurements. The surface acidity of the ground and the ground-and-intercalated kaolinites was probed with ammonia adsorption. The surface area and the pore volume as well as the amount of adsorbed ammonia increased with the rate of mechanochemical activation. At the same time the thermally deintercalated minerals showed increased surface area but decreased pore volume with the time of grinding. Adsorbed ammonia was detected as ammonium ion in the 1400-1500 cm(-1) spectral range.

9.
Psychiatry Res ; 268: 388-391, 2018 10.
Artículo en Inglés | MEDLINE | ID: mdl-30121542

RESUMEN

Our aim was to introduce more homogenous phenotypes for studying genetic variations in the clinically heterogeneous obsessive compulsive disorder (OCD) beside classical case-control analysis. Symptoms were assessed with Children's Yale-Brown Obsessive Compulsive Scale (CY-BOCS), and principle component analysis of the lifetime symptom categories yielded four factors (Cleaning, Obsessive, Compulsive, Sexual). The comparison of serotonin transporter linked polymorphic region (5-HTTLPR) in 102 OCD patients and 223 controls showed an increased L-allele frequency but no difference was observed when rs25531 was included. Intronic variants of the serotonin transporter gene did not show association with either OCD, nor with the obtained factors.


Asunto(s)
Trastorno Obsesivo Compulsivo/genética , Trastorno Obsesivo Compulsivo/psicología , Polimorfismo Genético/genética , Proteínas de Transporte de Serotonina en la Membrana Plasmática/genética , Adolescente , Adulto , Estudios de Casos y Controles , Niño , Femenino , Frecuencia de los Genes/genética , Variación Genética/genética , Humanos , Masculino , Trastorno Obsesivo Compulsivo/diagnóstico , Proyectos Piloto , Análisis de Componente Principal/métodos , Conducta Sexual/psicología , Adulto Joven
10.
Prog Neuropsychopharmacol Biol Psychiatry ; 84(Pt A): 122-128, 2018 06 08.
Artículo en Inglés | MEDLINE | ID: mdl-29374517

RESUMEN

AIMS: Methylphenidate (MPH) is the most frequently prescribed drug in Attention Deficit Hyperactivity Disorder (ADHD). Hitherto mostly the dopamine transporter gene has been studied in MPH-response and only a few studies analyzed the norepinephrine transporter (NET, SLC6A2) gene, although MPH is a potent inhibitor of both dopamine and norepinephrine transporters. We aimed to analyze this monoamine transporter gene in relation to ADHD per se and MPH-response in particular to gain further knowledge in ADHD pharmacogenetics using a Caucasian sample. METHODS: Six single nucleotide polymorphisms (rs28386840, rs2242446, rs3785143, rs3785157, rs5569, rs7194256 SNP) were studied across the NET gene in 163 ADHD children (age: 9.3±2.6; 86.5% male) using ADHD-RS hyperactivity-impulsivity and inattention scales. For case-control analysis 486 control subjects were also genotyped. At the MPH-response analysis responders had minimum 25% decrease of ADHD-RS total score after 2months of treatment, and chi-square test compared 90 responders and 32 non-responders, whereas ANOVA was used to assess symptom improvement after the first month among the 122 ADHD patients. RESULTS: The classical case-control analysis did not yield any association with ADHD diagnosis, which was supported by meta-analysis conducted on the available genetic data (combining previously published and the present studies). On the other hand, the intronic rs3785143 showed nominal association with inattention symptoms (p=0.01). The haplotype analysis supported this association, and indicated the importance of the first haploblock encompassing the intronic and 2 promoter SNPs. With MPH-response only the promoter rs28386840 showed nominal association: Those with at least one T-allele were overrepresented in the responder group (42% vs 19%, p=0.08), and they had better improvement on the hyperactivity-impulsivity scale compared to the AA genotype (p=0.04). CONCLUSION: Although none of our single SNP findings remained significant after correcting for multiple testing, our results from the MPH-response analysis indicate the potential importance of promoter variants in the NET gene.


Asunto(s)
Trastorno por Déficit de Atención con Hiperactividad/tratamiento farmacológico , Trastorno por Déficit de Atención con Hiperactividad/genética , Estimulantes del Sistema Nervioso Central/uso terapéutico , Metilfenidato/uso terapéutico , Proteínas de Transporte de Noradrenalina a través de la Membrana Plasmática/genética , Variantes Farmacogenómicas , Atención , Estudios de Casos y Controles , Niño , Femenino , Estudios de Asociación Genética , Haplotipos , Humanos , Intrones , Desequilibrio de Ligamiento , Masculino , Polimorfismo de Nucleótido Simple , Regiones Promotoras Genéticas
11.
Ideggyogy Sz ; 60(3-4): 205-8, 2007 Mar 30.
Artículo en Inglés | MEDLINE | ID: mdl-17451070

RESUMEN

BACKGROUND AND PURPOSE: In view of the known functional differences, the neurochemical character of the thoracic and sacral intermediolateral nuclei were compared. METHODS: Neurons and the afferent fiber components were labeled using antibodies raised against neurofilament, neural nuclear protein, cholinacetyltransferase, nitric oxide synthase, neurokinin receptor-1, substance P, calcitonin gene-related peptide, micro-opiate receptor-1 and vesicular glutamate transporter type 1 in rats. Biontinylated isolectin IB4 was used to label unmyelinated primary afferent fibers. Specimens were analyzed with confocal laser microscope. RESULTS AND CONCLUSIONS: The thoracic and sacral intermediolateral nuclei are similar in the chemical character of the neurons. In the thoracic segments the dendrites of the labeled neurons followed a transverse path towards the neurons located at both sides of the midline above the central canal. The transverse orientation of the dendrites in the sacral segment was less evident. Calcitonin gene-related peptide, isolectin IB4 and micro-opiate receptor-1 immunopositive afferent fibers arborize only in the sacral intermediolateral nucleus. We conclude that fine caliber primary afferent fibers, departing from the adjacent superficial dorsal horn, terminate in the sacral intermediolateral nucleus. It is probable that the preganglionic parasympathetic neurons in the nucleus receive synapses from the primary afferent fibers.


Asunto(s)
Fibras Autónomas Preganglionares/química , Biomarcadores/análisis , Vías Aferentes , Animales , Péptido Relacionado con Gen de Calcitonina/análisis , Colina O-Acetiltransferasa/análisis , Lectinas , Región Lumbosacra , Microscopía Confocal , Neuronas , Óxido Nítrico Sintasa/análisis , Proteínas Nucleares/análisis , Ratas , Receptores de Neuroquinina-1/análisis , Receptores Opioides/análisis , Sustancia P/análisis , Tórax , Proteína 1 de Transporte Vesicular de Glutamato/análisis , Receptor de Nociceptina
12.
Magy Onkol ; 50(1): 25-32, 2006.
Artículo en Húngaro | MEDLINE | ID: mdl-16617380

RESUMEN

OBJECTIVES: The use of anthracyclines are limited by their cardiotoxic side effects (first of all congestive cardiomyopathy). In this study we analyzed the anthracycline-induced cardiotoxicity and the possible preventive role of dexrazoxane in children. PATIENTS: 158 anthracycline-treated long-term survivors could be analyzed. Sixty-one children received dexrazoxane (group D) and 97 patients received anthracyclines only (group C). METHODS: Cardiac ultrasound examinations (ECHO) and electrocardiograms (ECG) were performed regularly from the beginning of chemotherapy and yearly thereafter. Shortening fraction (FS) was used as indicator of the ventricular function. RESULTS: The incidence of reduced left ventricular function (FS) was 13.4% in C, and 8.2% in D (p=ns). Two years after completion of the chemotherapy FS was reduced in 13.7% in C and 0% in D, respectively (p=0.056), and 5 years after therapy in 11.0% in C and 2.4% in D, respectively (P=0.034). Left chamber wall diameter was abnormal in systole in 6% in C and 2% in D, in diastole in 11% in C and 7% in D (p=ns) after 3 years of follow-up. CONCLUSION: Anthracycline-induced subacute cardiotoxicity can be significantly diminished by the concomitant use of dexrazoxane. For the final conclusions longer follow-up is necessary.


Asunto(s)
Antraciclinas/efectos adversos , Antibióticos Antineoplásicos/efectos adversos , Cardiomiopatía Dilatada/prevención & control , Cardiotónicos/uso terapéutico , Corazón/efectos de los fármacos , Razoxano/uso terapéutico , Adolescente , Antraciclinas/administración & dosificación , Antibióticos Antineoplásicos/administración & dosificación , Cardiomiopatía Dilatada/inducido químicamente , Cardiomiopatía Dilatada/fisiopatología , Niño , Preescolar , Femenino , Humanos , Masculino , Estudios Retrospectivos , Resultado del Tratamiento , Función Ventricular Izquierda/efectos de los fármacos
13.
J Colloid Interface Sci ; 289(1): 132-8, 2005 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-16009224

RESUMEN

The thermal behavior of a formamide-intercalated mechanochemically activated (dry-ground) kaolinite was investigated by thermogravimetry-mass spectrometry (TG-MS) and diffuse reflectance Fourier transform infrared spectroscopy (DRIFT). After the removal of adsorbed and intercalated formamide, a third type of bonded reagent was identified in the temperature range 230-350 degrees C decomposing in situ to CO and NH3. The presence of formamide decomposition products, as well as CO2 and various carbonates identified by DRIFT spectroscopy, indicates the formation of superactive centers as a result of mechanochemical activation and heat treatment (thermal deintercalation). The structural variance of surface species decreases with the increase of grinding time. The unground mineral contains a small amount of weakly acidic and basic centers. After 3 h of grinding, the number of acidic centers increases significantly, while on further grinding the superactive centers show increased basicity. With the increase of grinding time and treatment temperature the number of bicarbonate- and bidentate-type structures decreases in favor of the carboxylate- and monodentate-type ones.


Asunto(s)
Formamidas/química , Sustancias Intercalantes/química , Caolín/química , Temperatura , Estructura Molecular , Propiedades de Superficie , Difracción de Rayos X
14.
J Colloid Interface Sci ; 270(2): 337-46, 2004 Feb 15.
Artículo en Inglés | MEDLINE | ID: mdl-14697699

RESUMEN

A comparison is made of the mechanochemical activation of three low- and one high-defect kaolinite using a combination of X-ray diffraction, thermal analysis, and DRIFT spectroscopy. The effect of mechanochemical alteration of the kaolinites is greater for the low-defect kaolinites. The effectiveness of the mechanochemical treatment is represented by the slope of the d(001) peakwidth-grinding time line. High-defect kaolinite is not significantly altered by the grinding treatment. The effect of mechanochemical treatment on peakwidth was independent of the presence of quartz; the quartz acts as an additional grinding medium. The effectiveness of the mechanochemical treatment depends on the crystallinity of the kaolinite. Two processes are identified in the mechanochemical activation of the kaolinite: first the delamination of kaolinite appears to take place in the first hour of grinding and second a recombination process results in the reaggregation of the ground crystals. During this process proton hopping occurs and reaction to form water takes place. This water is then adsorbed and coordinated to surface-active sites created during mechanochemical treatment.

15.
J Colloid Interface Sci ; 246(1): 164-74, 2002 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-16290397

RESUMEN

The deintercalation of hydrazine-intercalated kaolinite has been followed using a combination of X-ray diffraction and diffuse reflectance Fourier transform infrared spectroscopy. Upon intercalation of the kaolinite with hydrazine, the kaolinite layers are expanded to 10.66 A and remain expanded for up to 22 h upon exposure to moist air. Only upon deintercalation are the peak at 10.39 A and a minor peak at 9.6 A observed. Complete deintercalation takes up to 18 days more. Upon intercalation with hydrazine an intense band is observed at 3628 cm(-1) and is attributed to the inner-surface hydroxyls hydrogen bonded to the hydrazine, which upon deintercalation decreased in intensity. This rate of deintercalation is affected by the presence or absence of moist air. Deintercalation in the presence of water vapor results in the observation of two additional bands at 3550 and 3598 cm(-1), which are attributed to the hydroxyl stretching modes of adsorbed water during deintercalation. The intensity of NH stretching vibrations observed at 3360, 3300, and 3200 cm(-1) also decrease in intensity with deintercalation time. Changes in the hydroxyl deformation modes of kaolinite in the 915 cm(-1) region and in the HNH deformation modes show strong interactions between the kaolinite surface and the inserting hydrazine molecule.

16.
J Colloid Interface Sci ; 265(2): 386-95, 2003 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-12962673

RESUMEN

The effect of mechanochemical activation upon the intercalation of formamide into a high-defect kaolinite has been studied using a combination of X-ray diffraction, thermal analysis, and DRIFT spectroscopy. X-ray diffraction shows that the intensity of the d(001) spacing decreases with grinding time and that the intercalated high-defect kaolinite expands to 10.2 A. The intensity of the peak of the expanded phase of the formamide-intercalated kaolinite decreases with grinding time. Thermal analysis reveals that the evolution temperature of the adsorbed formamide and loss of the inserting molecule increases with increased grinding time. The temperature of the dehydroxylation of the formamide-intercalated high-defect kaolinite decreases from 495 to 470 degrees C with mechanochemical activation. Changes in the surface structure of the mechanochemically activated formamide-intercalated high-defect kaolinite were followed by DRIFT spectroscopy. Fundamentally the intensity of the high-defect kaolinite hydroxyl stretching bands decreases exponentially with grinding time and simultaneously the intensity of the bands attributed to the OH stretching vibrations of water increased. It is proposed that the mechanochemical activation of the high-defect kaolinite caused the conversion of the hydroxyls to water which coordinates the kaolinite surface. Significant changes in the infrared bands assigned to the hydroxyl deformation and amide stretching and bending modes were observed. The intensity decrease of these bands was exponentially related to the grinding time. The position of the amide C=O vibrational mode was found to be sensitive to grinding time. The effect of mechanochemical activation of the high-defect kaolinite reduces the capacity of the kaolinite to be intercalated with formamide.

17.
J Colloid Interface Sci ; 251(2): 350-9, 2002 Jul 15.
Artículo en Inglés | MEDLINE | ID: mdl-16290740

RESUMEN

Controlled rate thermal analysis (CRTA) allows the separation of adsorbed and intercalated hydrazine. CRTA displays the presence of three different types of hydrogen-bonded hydrazine in the intercalation complex: (a) The first is adsorbed loosely bonded on the kaolinite structure fully expanded by hydrazine-hydrate and liberated between approx 50 and 70 degrees C (b) The second intercalated hydrazine is lost between approx 70 and 85 degrees C. (c) The third type of intercalated-hydrazine molecule is lost in the 85-130 degrees C range. CRTA at 70 degrees C enables the removal of hydrazine-water and results in the partial collapse of the hydrazine-intercalated kaolinite structure to form a hydrazine-intercalated kaolinite. Removal of the adsorbed hydrazine enables the DRIFT spectra of the hydrazine-intercalated complex without any adsorbed hydrazine to be obtained. A band at 3626 cm(-1) attributed to the inner surface hydroxyls of kaolinite hydrogen bonded to hydrazine is observed. The intercalation of hydrazine-hydrate into kaolinite is complex and results from the different types of surface interactions of the hydrazine with the kaolinite surfaces.

18.
Spectrochim Acta A Mol Biomol Spectrosc ; 59(6): 1183-94, 2003 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-12659887

RESUMEN

Kaolinite has been mechanochemically activated by dry grinding for periods of time up to 10 h. The kaolinite was then intercalated with potassium acetate and the changes in the structure followed by DRIFT spectroscopy. Intercalation of the kaolinite with potassium acetate is difficult and only the layers, which remain hydrogen bonded, are intercalated. The mechanochemical activation of the kaolinite may be followed by the loss of intensity of the hydroxyl-stretching vibrations. The intensity of the 3695 and 3619 cm(-1) bands reach a minimum after 10 h of grinding. The observation of a band at 3602 cm(-1) is indicative of the intercalation of the kaolinite with potassium acetate. The degree of intercalation decreases with mechanochemical treatment. The effect of exposure of the intercalated mechanochemically activated kaolinite to moist air results in de-intercalation. The effect of the mechanochemical treatment is loss of layer stacking, which prevents the intercalation of the kaolinite.


Asunto(s)
Caolín/química , Acetato de Potasio/química , Espectrometría Raman/métodos , Hidrógeno/química , Radical Hidroxilo/química , Sustancias Intercalantes/farmacología , Caolín/análisis , Factores de Tiempo , Difracción de Rayos X
19.
J Colloid Interface Sci ; 406: 196-208, 2013 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-23791228

RESUMEN

Montmorillonite (MMT) was converted to organoclays by intercalation of cationic surfactants into its interlayer space. Two types of organoclays were prepared from different surfactants (DDTMA and DDDMA) at different surfactant loadings, and the structural changes in the clays investigated using various techniques. The arrangements of surfactant molecules in the interlayer space was visually aided by molecular mechanical calculation (MM calculation), and the adsorption capacities of MMT and the organoclays for the removal of p-chlorophenol (PCP) and p-nitrophenol (PNP) from aqueous solutions were tested under different conditions. Two adsorption isotherm models (Langmuir and Freundlich isotherms) were used to determine the best fit model and the Freundlich isotherm was found to provide better fit for both PCP and PNP. Due to its hydrophobic properties, the adsorption is more favourable for PNP than PCP. Overall, the adsorption capacity of the organoclays was significantly improved by intercalation with large surfactant molecules as well as highly loaded surfactants as the intercalation with large surfactant molecules created the partitioning phase, which strongly attracted large amounts of organic pollutants. Possible mechanisms and the implications of the results for the use of these organoclays as adsorbents for the removal of phenols from the environment are discussed.


Asunto(s)
Silicatos de Aluminio/química , Clorofenoles/aislamiento & purificación , Nitrofenoles/aislamiento & purificación , Contaminantes Químicos del Agua/aislamiento & purificación , Adsorción , Bentonita/química , Arcilla , Fenoles , Compuestos de Amonio Cuaternario/química , Tensoactivos/química , Difracción de Rayos X
20.
J Colloid Interface Sci ; 393: 319-34, 2013 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-23207051

RESUMEN

Modified montmorillonite was prepared at different surfactant (HDTMA) loadings through ion exchange. The conformational arrangement of the loaded surfactants within the interlayer space of MMT was obtained by computational modelling. The conformational change of surfactant molecules enhance the visual understanding of the results obtained from characterization methods such as XRD and surface analysis of the organoclays. Batch experiments were carried out for the adsorption of p-chlorophenol (PCP) and different conditions (pH and temperature) were used in order to determine the optimum sorption. For comparison purpose, the experiments were repeated under the same conditions for p-nitrophenol (PNP). Langmuir and Freundlich equations were applied to the adsorption isotherm of PCP and PNP. The Freundlich isotherm model was found to be the best fit for both of the phenolic compounds. This involved multilayer adsorptions in the adsorption process. In particular, the binding affinity value of PNP was higher than that of PCP and this is attributable to their hydrophobicities. The adsorption of the phenolic compounds by organoclays intercalated with highly loaded surfactants was markedly improved possibly due to the fact that the intercalated surfactant molecules within the interlayer space contribute to the partition phases, which result in greater adsorption of the organic pollutants.


Asunto(s)
Silicatos de Aluminio/química , Compuestos de Cetrimonio/química , Clorofenoles/aislamiento & purificación , Nitrofenoles/aislamiento & purificación , Tensoactivos/química , Adsorción , Cetrimonio , Arcilla , Simulación de Dinámica Molecular , Estructura Molecular , Propiedades de Superficie
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