Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 13 de 13
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
Sci Rep ; 7(1): 2942, 2017 06 07.
Artigo em Inglês | MEDLINE | ID: mdl-28592891

RESUMO

Moisture uptake and outgassing can be detrimental to a system by altering the chemical and mechanical properties of materials within the system over time. In this work, we conducted isotherm experiments to investigate dynamic moisture sorption and desorption in markedly different materials, i.e., a polymeric material, Sylgard-184 and a ceramic aluminosilicate material, Zircar RS-1200, at different temperatures (30 °C-70 °C) by varying the water activity (0.0-0.90). Sylgard-184 showed a linear sorption and outgassing behavior with no-hysteresis over the entire temperature and water activity range considered here. Whereas, the sorption and outgassing of Zircar RS-1200 was highly non-linear with significant hysteresis, especially at higher water activities, at all temperatures considered here. The type of hysteresis suggested the presence of mesopores in Zircar RS-1200, whereas the lack of hysteresis in Sylgard-184 indicates that it has a nonporous structure. A diffusion model coupled with a dynamic, triple-mode sorption (Langmuir, Henry, and pooling modes) model employed in this study matched our experimental data very well and provides mechanistic insight into the processes. Our triple-mode sorption model was adaptive enough to (1) model these distinctly different materials and (2) predict sorption and outgassing under conditions that are distinctly different from the parameterization experiments.

2.
Chemphyschem ; 16(14): 3072-83, 2015 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-26274619

RESUMO

A high-fidelity model of kinetic and equilibrium sorption and diffusion is developed and exercised. The gas-diffusion model is coupled with a triple-sorption mechanism: Henry's law absorption, Langmuir adsorption, and pooling or clustering of molecules at higher partial pressures. Sorption experiments are conducted and span a range of relative humidities (0-95 %) and temperatures (30-60 °C). Kinetic and equilibrium sorption properties and effective diffusivity are determined by minimizing the absolute difference between measured and modeled uptakes. Uncertainty quantification and sensitivity analysis methods are described and exercised herein to demonstrate the capability of this modeling approach. Water uptake in silica-filled and unfilled poly(dimethylsiloxane) networks is investigated; however, the model is versatile enough to be used with a wide range of materials and vapors.

3.
Angew Chem Int Ed Engl ; 53(37): 9788-91, 2014 Sep 08.
Artigo em Inglês | MEDLINE | ID: mdl-24989120

RESUMO

A non-magnetic piston-cylinder pressure cell is presented for solution-state NMR spectroscopy at geochemical pressures. The probe has been calibrated up to 20 kbar using in situ ruby fluorescence and allows for the measurement of pressure dependencies of a wide variety of NMR-active nuclei with as little as 10 µL of sample in a microcoil. Initial (11)B NMR spectroscopy of the H3BO3-catechol equilibria reveals a large pressure-driven exchange rate and a negative pressure-dependent activation volume, reflecting increased solvation and electrostriction upon boron-catecholate formation. The inexpensive probe design doubles the current pressure range available for solution NMR spectroscopy and is particularly important to advance the field of aqueous geochemistry.

4.
Chemphyschem ; 15(9): 1809-20, 2014 Jun 23.
Artigo em Inglês | MEDLINE | ID: mdl-24819028

RESUMO

Water-vapor-uptake experiments were performed on a silica-filled poly(dimethylsiloxane) (PDMS) network and modeled by using two different approaches. The data was modeled by using established methods and the model parameters were used to predict moisture uptake in a sample. The predictions are reasonably good, but not outstanding; many of the shortcomings of the modeling are discussed. A high-fidelity modeling approach is derived and used to improve the modeling of moisture uptake and diffusion. Our modeling approach captures the physics and kinetics of diffusion and adsorption/desorption, simultaneously. It predicts uptake better than the established method; more importantly, it is also able to predict outgassing. The material used for these studies is a filled-PDMS network; physical interpretations concerning the sorption and diffusion of moisture in this network are discussed.

5.
Inorg Chem ; 53(8): 4202-8, 2014 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-24689949

RESUMO

Carbonate ligand-exchange rates on the [NpO2(CO3)3]4­ ion were determined using a saturation-transfer 13C nuclear magnetic resonance (NMR) pulse sequence in the pH range of 8.1 ≤ pH ≤ 10.5. Over the pH range 9.3 ≤ pH ≤ 10.5, which compares most directly with previous work of Stout et al.,1 we find an average rate, activation energy, enthalpy, and entropy of kex298 = 40.6(±4.3) s­1, Ea =45.1(±3.8) kJ mol­1, ΔH‡ = 42.6(±3.8) kJ mol­1, and ΔS‡ = −72(±13) J mol­1 K­1, respectively. These activation parameters are similar to the Stout et al. results at pH 9.4. However, their room-temperature rate at pH 9.4, kex298 = 143(±1.0) s­1, is 3 times faster than what we experimentally determined at pH 9.3: kex298 = 45.4(±5.3) s­1. Our rates for [NpO2(CO3)3]4­ are also faster by a factor of 3 relative to the isoelectronic [UO2(CO3)3]4­ as reported by Brucher et al.2 of kex298 = 13(±3) s­1. Consistent with results for the [UO2(CO3)3]4­ ion, we find evidence for a proton-enhanced pathway for carbonate exchange for the [NpO2(CO3)3]4­ ion at pH < 9.0.

6.
J Phys Chem B ; 116(48): 14183-90, 2012 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-23153278

RESUMO

The dynamic and equilibrium water vapor sorption properties of Sylgard-184, a commercially available poly(dimethylsiloxane) elastomer (PDMS), were determined via gravimetric analysis from 30 to 70 °C. Described here is a methodology for quantitatively assessing how water vapor diffuses and ad/absorbs into polymeric materials that are traditionally considered hydrophobic. PDMS materials are frequently chosen for their moisture barrier properties; our results, however, demonstrate that moisture is able to penetrate the material over a range of temperatures and humidities. The sorption values measured here ranged from ca. 0.1 to 1.4 cm(3) (STP) H(2)O/g Sylgard. The isotherms exhibited sigmoidal character and were fit to a triple mode sorption model. Asymptotic behavior at low water activities was characterized using a Langmuir type adsorption model, linear behavior was fit to a Henry's law type dependence, and the convex portion at higher activities was fit with good agreement to Park's equation for pooling or clustering. The thermal dependence of these sorption modes was also explored and reported. The dynamics of the sorption process were fit to a Fickian model and effective diffusivities are reported along with corresponding activation energies. The diffusivity values measured here ranged from ca. 0.5 to 3.5 × 10(-5) cm(2)/s depending on the temperature and relative humidity. The concentration dependence of the diffusivity showed a direct correlation with the three modes of uptake obtained from the isotherms. Corrections to the diffusivities were calculated using existing models that take into account adsorption and pooling.

7.
Chemistry ; 18(34): 10476-9, 2012 Aug 20.
Artigo em Inglês | MEDLINE | ID: mdl-22806772

RESUMO

Beneath the sheets: (31) P NMR data suggests that phosphates are liberated freely in the interlayer of a cobalt-hydroxide water-oxidation catalyst. The cobalt-hydroxide sheets are separated by an interlayer region with water, counterions and phosphate, which help to shuttle protons as the layer develops charge.

8.
Inorg Chem ; 51(12): 6731-8, 2012 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-22671440

RESUMO

The ammonium salt of [Fe(4)O(OH)(hpdta)(2)(H(2)O)(4)](-) is soluble and makes a monospecific solution of [Fe(4)(OH)(2)(hpdta)(2)(H(2)O)(4)](0)(aq) in acidic solutions (hpdta = 2-hydroxypropane-1,3-diamino-N,N,N',N'-tetraacetate). This tetramer is a diprotic acid with pK(a)(1) estimated at 5.7 ± 0.2 and pK(a)(2) = 8.8(5) ± 0.2. In the pH region below pK(a)(1), the molecule is stable in solution and (17)O NMR line widths can be interpreted using the Swift-Connick equations to acquire rates of ligand substitution at the four isolated bound water sites. Averaging five measurements at pH < 5, where contribution from the less-reactive conjugate base are minimal, we estimate: k(ex)(298) = 8.1 (±2.6) × 10(5) s(-1), ΔH(++) = 46 (±4.6) kJ mol(-1), ΔS(++) = 22 (±18) J mol(-1) K(-1), and ΔV(++) = +1.85 (±0.2) cm(3) mol(-1) for waters bound to the fully protonated, neutral molecule. Regressing the experimental rate coefficients versus 1/[H(+)] to account for the small pH variation in rate yields a similar value of k(ex)(298) = 8.3 (±0.8) × 10(5) s(-1). These rates are ∼10(4) times faster than those of the [Fe(OH(2))(6)](3+) ion (k(ex)(298) = 1.6 × 10(2) s(-1)) but are about an order of magnitude slower than other studied aminocarboxylate complexes, although these complexes have seven-coordinated Fe(III), not six as in the [Fe(4)(OH)(2)(hpdta)(2)(H(2)O)(4)](0)(aq) molecule. As pH approaches pK(a1), the rates decrease and a compensatory relation is evident between the experimental ΔH(++) and ΔS(++) values. Such variation cannot be caused by enthalpy from the deprotonation reaction and is not well understood. A correlation between bond lengths and the logarithm of k(ex)(298) is geochemically important because it could be used to estimate rate coefficients for geochemical materials for which only DFT calculations are possible. This molecule is the only neutral, oxo-bridged Fe(III) multimer for which rate data are available.


Assuntos
Compostos Ferrosos/química , Água/química , Compostos Ferrosos/síntese química , Modelos Moleculares
9.
Environ Sci Technol ; 46(5): 2806-12, 2012 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-22316095

RESUMO

Environmental and geochemical systems containing paramagnetic species could benefit by using nuclear magnetic resonance (NMR) spectroscopy due to the sensitivity of the spectral response to small amounts paramagnetic interactions. In this study, we apply commonly used solid-state NMR spectroscopic methods combined with chemometrics analysis to probe sorption behavior of the paramagnetic cations Cu(2+) and Ni(2+)at the amorphous silica surface. We exploit the unique properties of paramagnets to derive meaningful structural information in these systems at low, environmentally relevant cation surface loadings by comparing the NMR response of sorption samples to paramagnetic free samples. These data suggest that a simple sorption model where the cation sorbs as inner sphere complexes at negatively charged, deprotonated silanol sites is appropriate. These results help constrain sorption models that are used to describe metal fate and transport.


Assuntos
Cátions Bivalentes/química , Espectroscopia de Ressonância Magnética/métodos , Metais/química , Elementos de Transição/química , Adsorção , Concentração de Íons de Hidrogênio , Ligantes , Modelos Químicos , Soluções , Propriedades de Superfície , Fatores de Tempo
11.
Chemistry ; 17(16): 4408-17, 2011 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-21416515

RESUMO

Polyoxometalate ions are used as ligands in water-oxidation processes related to solar energy production. An important step in these reactions is the association and dissociation of water from the catalytic sites, the rates of which are unknown. Here we report the exchange rates of water ligated to Co(II) atoms in two polyoxotungstate sandwich molecules using the (17)O-NMR-based Swift-Connick method. The compounds were the [Co(4)(H(2)O)(2)(B-α-PW(9)O(34))(2)](10-) and the larger αßßα-[Co(4)(H(2)O)(2)(P(2)W(15)O(56))(2)](16-) ions, each with two water molecules bound trans to one another in a Co(II) sandwich between the tungstate ligands. The clusters, in both solid and solution state, were characterized by a range of methods, including NMR, EPR, FT-IR, UV-Vis, and EXAFS spectroscopy, ESI-MS, single-crystal X-ray crystallography, and potentiometry. For [Co(4)(H(2)O)(2)(B-α-PW(9)O(34))(2)](10-) at pH 5.4, we estimate: k(298)=1.5(5)±0.3×10(6) s(-1), ΔH(≠)=39.8±0.4 kJ mol(-1), ΔS(≠)=+7.1±1.2 J mol(-1) K(-1) and ΔV(≠)=5.6 ±1.6 cm(3) mol(-1). For the Wells-Dawson sandwich cluster (αßßα-[Co(4)(H(2)O)(2)(P(2)W(15)O(56))(2)](16-)) at pH 5.54, we find: k(298)=1.6(2)±0.3×10(6) s(-1), ΔH(≠)=27.6±0.4 kJ mol(-1) ΔS(≠)=-33±1.3 J mol(-1) K(-1) and ΔV(≠)=2.2±1.4 cm(3) mol(-1) at pH 5.2. The molecules are clearly stable and monospecific in slightly acidic solutions, but dissociate in strongly acidic solutions. This dissociation is detectable by EPR spectroscopy as S=3/2 Co(II) species (such as the [Co(H(2)O)(6)](2+) monomer ion) and by the significant reduction of the Co-Co vector in the XAS spectra.


Assuntos
Cobalto/química , Modelos Químicos , Polímeros/química , Compostos de Tungstênio/química , Água/química , Espectroscopia de Ressonância de Spin Eletrônica , Concentração de Íons de Hidrogênio , Oxirredução , Soluções , Espectroscopia por Absorção de Raios X
12.
Proc Natl Acad Sci U S A ; 103(10): 3557-62, 2006 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-16505368

RESUMO

Current strategies for the production of therapeutic mAbs include the use of mammalian cell systems to recombinantly produce Abs derived from mice bearing human Ig transgenes, humanization of rodent Abs, or phage libraries. Generation of hybridomas secreting human mAbs has been previously reported; however, this approach has not been fully exploited for immunotherapy development. We previously reported the use of transient regulation of cellular DNA mismatch repair processes to enhance traits (e.g., affinity and titers) of mAb-producing cell lines, including hybridomas. We reasoned that this process, named morphogenics, could be used to improve suboptimal hybridoma cells generated by means of ex vivo immunization and immortalization of antigen-specific human B cells for therapeutic Ab development. Here we present a platform process that combines hybridoma and morphogenics technologies for the generation of fully human mAbs specific for disease-associated human antigens. We were able to generate hybridoma lines secreting mAbs with high binding specificity and biological activity. One mAb with strong neutralizing activity against human granulocyte-macrophage colony-stimulating factor was identified that is now considered for preclinical development for autoimmune disease indications. Moreover, these hybridoma cells have proven suitable for genetic optimization using the morphogenics process and have shown potential for large-scale manufacturing.


Assuntos
Anticorpos Monoclonais/biossíntese , Anticorpos Monoclonais/uso terapêutico , Linfócitos B/imunologia , Hibridomas/imunologia , Imunoterapia/métodos , Sequência de Aminoácidos , Animais , Antígenos/genética , Doenças Autoimunes/imunologia , Doenças Autoimunes/terapia , Pareamento Incorreto de Bases , Células Cultivadas , Reparo do DNA , Epitopos/genética , Fator Estimulador de Colônias de Granulócitos e Macrófagos/imunologia , Humanos , Switching de Imunoglobulina , Técnicas In Vitro , Camundongos , Dados de Sequência Molecular , Testes de Neutralização
13.
J Neurovirol ; 8(2): 86-99, 2002 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-11935461

RESUMO

Our recent studies have demonstrated that extracellular, recombinant human immunodeficiency virus type I (HIV-1) Vpr protein is highly neurotoxic in the microenvironment of differentiated mature human neurons and undifferentiated neuronal precursors. Although most of the direct neurotoxic effects of HIV-1 have been attributed previously to the envelope gene product, gp120, and the Tat regulatory protein, it was demonstrated that Vpr protein caused apoptosis comparable to that induced by gp120 protein in a dose-dependent manner in the neuronal system. Having observed the neurocytopathic effects of extracellular Vpr protein previously, the effects of virally expressed Vpr on nondividing, terminally differentiated human neurons were investigated. An HIV-1-based three-plasmid expression vector system was utilized to study the effects of intracellularly expressed Vpr. These virion preparations were then used to transduce neurons generated from the human neuronal precursor NT2 cell-line. Intracellularly expressed Vpr induced apoptosis within terminally differentiated neurons, as demonstrated by TUNEL assays. Additionally, virions lacking Vpr expression did not significantly induce apoptosis within these neurons. These results suggest that HIV-1 Vpr may also be leading directly to selective neurotoxicity through intracellular expression. Furthermore, human apoptosis gene microarray comparisons exhibited an up-regulation of Bcl-2-related mRNA, as well as other apoptosis genes involved in the mitochondrial apoptotic pathway, for the Vpr-transduced neuronal cells, when compared to Vpr-negative controls. Thus, Vpr delivered intracellularly, as well as extracellularly, is involved in the induction of significant neuronal apoptosis and may be one of the molecular mechanisms in HIV-1-induced encephalopathy.


Assuntos
Apoptose , Produtos do Gene vpr/genética , Neurônios/citologia , Neurônios/virologia , Complexo AIDS Demência/patologia , Complexo AIDS Demência/virologia , Células Cultivadas , Regulação Viral da Expressão Gênica , Vetores Genéticos , Humanos , Marcação In Situ das Extremidades Cortadas , Lentivirus/genética , Análise de Sequência com Séries de Oligonucleotídeos , Produtos do Gene vpr do Vírus da Imunodeficiência Humana
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA
...