Particulate hematite diffusion in sodium polyacrylate solutions. The effect of ionic strength

The diffusion coefficients of hematite particles in polyelectrolyte solution have been investigated using dynamic light scattering. Two apparent diffusion coefficients, a fast and a slow diffusional mode, are observed for the hematite particles in high-molecular-weight sodium polyacrylate solution at pH 10.5. The slow diffusion coefficient (Dslow) shows a decrease with increase in polyelectrolyte concentration. The fast diffusion coefficient (Dfast) shows an increase to a maximum with increasing polyelectrolyte concentration and then a rapid decrease as the polyelectrolyte concentration increases further. With an increase in ionic strength from 10(-4) to 0.1 M NaNO3, the maximum value of Dfast increased in magnitude, while the polyacrylate concentration at which the maximum occurs is seen to increase. The dependence of Dfast on the measurement angle indicates that it is coupled to the fluctuations of the chains. The observed behavior is attributed to the hematite probe particle sensing both macroscopic (viscous) and elastic fluctuations associated with the polyelectrolyte motion.     

Development and characterization of a high-throughput system for assessing cell-surface receptor-ligand engagement

A nonfouling interfacial interpenetrating polymer network (IPN) of poly(acrylamide-co-ethylene glycol/acrylic acid) [p(AAm-co-EG/AAc)] was grafted to polystyrene for use as a novel platform for the development of high-throughput assays for screening of specific bimolecular interactions (i.e., receptor-ligand engagement). For the development of the IPN, a water-soluble hydrogen-abstracting photoinitiator was investigated: (4-benzoylbenzyl)trimethylammonium chloride. IPN-modified polystyrene surfaces were characterized using XPS, contact angle goniometry, and protein adsorption analysis. These IPN surfaces minimized fibrinogen adsorption compared to tissue culture polystyrene (>96% reduction), prevented mammalian cell adhesion, and served as nonfouling surfaces to graft biological ligands. For bimolecular interaction studies, a model peptide ligand from bone sialoprotein (Ac-CGGNGEPRGDTYRAY-NH(2)) was grafted to p(AAm-co-EG/AAc) via a 3400 M(w) linear pEG spacer. Ligand density measurements, cell culture, and a centrifugal adhesion assay were used to study cell adhesion to peptide-modified IPNs (i.e., receptor-ligand engagement). Ligand density (Gamma) was controllable from approximately 1 to 20 pmol/cm(2) by modulating the peptide input concentration (0.02-20 microM). Cell adhesion was directly dependent on the ligand density. This technology creates a powerful high-throughput system to simultaneously probe a myriad of cell-surface receptor-ligand interactions.     

Peptide conformational analysis using the TRIPOS force field

To explain observed electron transfer rates between the terminal aromatic moieties in the arylsubstituted alanine dimer 1 , a conformational analysis of the dipeptide was performed using a standard molecular mechanics force field. The resulting low-energy conformers could conveniently be grouped into two families with an average energy difference of ca. 2 kcal mol^?1 and populations of 64% and 30%, respectively. These results correlate well with the 78:22 ratio of the two experimentally distinguishable decay processes for the radical anion of 1 . © 1992 John Wiley & Sons, Inc.     

A 199Hg NMR spectroscopic study of two and three-coordinate methylmercury(II) complexes, [MeHgL]NO3

¹⁹⁹Hg NMR spectra are reported for the complexes [MeHgL]NO₃ containing either two- (e.g. L = pyridine) or three-coordinate mercury (e.g. L = 2,2′-bipyridyl). For unidentate and bidentate ligands of similar basicity chelation with bidentate ligands to give three-coordinate mercury results in upfield shifts of ¹⁹⁹Hg resonances from that of the linear complexes. For complexes of unidentate ligands shifts correlate with changes in base strength of the ligands, and methyl substitution in the 2 position of pyridine appears to result in an upfield shift of ca. 30 ppm. Effects of substitution in the 2 position are very strong in complexes of unidentate 2-benzylpyridine and 3,3′-dimethyl-2,2′-bipyridyl. Comparison of the ¹⁹⁹Hg shifts with J(¹H-¹⁹⁹Hg) shows the coupling constant to be insensitive to substitution in the 2 position in linear complexes and is a function only of the ligand base strength.     

Effectiveness of temperature modification in decreasing the bias in milk fat test results between the Babcock and Ether extraction methods

Both the Babcock (AOAC Method 989.04, revised Final Action 2000) and modified Mojonnier ether extraction (AOAC Method 989.05) methods are used in the dairy industry to determine the fat content of milk. Prior to revision in 1997, the Babcock method gave consistently higher fat test results than did the ether extraction. In 1997, a modification of the Babcock method was introduced to bring the results of the Babcock test into closer agreement with the ether extraction. The Babcock method was modified by lowering the temperatures used at various points in the method from about 57.5 to 48 degrees C to increase the density of the material in the Babcock column. A collaborative study of the modification indicated it was successful in bringing the Babcock and ether extraction results into agreement but suggested that performance of the modified method was not as good as that of the unmodified method. In the present study, substantial evidence is presented to validate the success of the Babcock modification in bringing test results into agreement with ether extraction, and to document that temperature modification does not adversely affect method performance. Data were evaluated from an on-going proficiency testing program where 8-15 laboratories tested 7 milk samples in blind duplicate once every 2 months. Laboratories used the unmodified method from 1995 through 1996 and the modified method from 1998 through 1999. Compared with ether extraction, test results from the unmodified Babcock test were consistently higher by an average of 0.022% fat. For the modified Babcock test, average test results were -0.003% fat lower than with ether extraction and not significantly different from zero. AOAC method performance statistics (within- and between-laboratory precision) were equivalent for both the unmodified (Sr = 0.027, SR = 0.041, RSDr = 0.73%, RSDR= 1.08%) and modified (Sr = 0.023, SR = 0.038, RSDr = 0.60%, RSDR = 1.02%) Babcock methods. Modification of the Babcock method was successful in bringing test results into agreement with those of ether extraction.     

Preparation of a mercaptopropyl bonded silica intermediate in supercritical carbon dioxide: synthesis, characterisation and chromatography of a quinine based chiral stationary phase

This research examines the preparation of a mercaptopropyl bonded silica intermediate in supercritical carbon dioxide (sc-CO(2)) and the subsequent conversion in sc-CO(2) to a quinine derived chiral stationary phase (CSP). The effects of reaction temperature, pressure and time on the surface coverage of the silica intermediate were investigated when porous silica particles (Exsil-Avanti, 3microm) were reacted with 3-trimethoxymercaptopropylsilane in sc-CO(2). We present results which demonstrate that a stable mercaptopropyl bonded silica intermediate can be successfully prepared under supercritical conditions of 40 degrees C, 483bar, in a substantially reduced reaction time of 1h with superior surface coverages compared to organic solvent based methods. The further utility of this supercritical fluid technology was demonstrated by the free radical addition of a quinine derived chiral selector onto a mercaptopropyl bonded silica intermediate in sc-CO(2). This supercritical fluid generated chiral stationary phase (CSP) was utilised for the direct LC enantioseparation of a series of 3,5-dinitrobenzoyl (DNB) amino acids. Bonded silica samples were characterised using elemental analysis, diffuse reflectance infrared fourier transform (DRIFT) spectroscopy, solid state (13)C and (29)Si CP-MAS NMR spectroscopy, and thermogravimetric analysis (TGA). This supercritical fluid functionalisation approach offers an efficient and cleaner alternative to existing organic solvent based approaches for the preparation of bonded silica phases.     

Photoionization of isooctane and n-octane in intense laser fields. I. Effect of irradiance on ionization rates

The population of ejected electrons following multiphoton ionization of neat liquids isooctane and n-octane is investigated over a large range of ionizing irradiance I(ex). Transient absorption (TA) at 1200 nm in both neat liquids is measured in a 60 mum path at time delays of 0.7 and 2.5 ps following an intense 400 nm (3.1 eV) ionizing pulse. As the irradiance of this pulse is varied over the range from 4 to 410 TWcm(2), the dependence of TA on I(ex) exhibits the periodic structure theoretically predicted for multiphoton channel openings and closings. At low I(ex) (<9 TWcm(2)), TA in isooctane is proportional to I(ex) (n) where n=3, consistent with nonresonant, near threshold ionization (liquid phase ionization potential=8.6 eV). At I(ex)>9 TWcm(2), n declines with increasing I(ex) up to I(ex)=13 TWcm(2), at which point n abruptly increases to 4. The pattern is repeated at I(ex)>13 TWcm(2), albeit with n declining from 4 and then abruptly increasing to 5 as I(ex) becomes greater than 100 TWcm(2). A similar trend is observed in n-octane. The dependence of the TA on I(ex) in the regions of channel openings and closings is compared to the nonperturbative, strong field approximation developed by Reiss [Phys. Rev. A 22, 1786 (1980)].     

Synthesis,Characterization, and Electron-Transfer Properties of Ferrocene–BODIPY–Fullerene Near-Infrared-Absorbing Triads: Are Catecholopyrrolidine-Linked Fullerenes a Good Architecture to Facilitate Electron-Transfer?

A series of covalent ferrocene–BODIPY–fullerene triads with the ferrocene groups conjugated to the BODIPY π-system and the fullerene acceptor linked at the boron hub by a common catecholpyrrolidine bridge were prepared and characterized by 1D and 2D NMR, UV/Vis, steady-state fluorescence spectroscopy, high-resolution mass spectrometry, and, for one of the derivatives, X-ray crystallography. Redox processes of the new compounds were investigated by electrochemical (CV and DPV) methods and spectroelectrochemistry. DFT calculations indicate that the HOMO in all triads was delocalized between ferrocene and BODIPY π-system, the LUMO was always fullerene-centered, and the catechol-centered occupied orbital was close in energy to the HOMO. TDDFT calculations were indicative of the low-energy, low-intensity charge-transfer bands originated from the ferrocene–BODIPY core to fullerene excitation, which explained the similarity of the UV/Vis spectra of the ferrocene–BODIPY dyads and ferrocene–BODIPY–fullerene triads. Photophysical properties of the new triads as well as reference BODIPY–fullerene and ferrocene–BODIPY dyads were investigated by pump-probe spectroscopy in the UV/Vis and NIR spectral regions following selective excitation of the BODIPY-based antenna. Initial charge transfer from the ferrocene to the BODIPY core was shown to outcompete sub-100 fs deactivation of the excited state mediated by the catechol bridge. However, no subsequent electron transfer to the fullerene acceptor was observed. The initial charge separated state relaxes by recombination with a time constant of 150–380 ps.     

AGSE: A Novel Grape Seed Extract Enriched for PP2A Activating Flavonoids That Combats Oxidative Stress and Promotes Skin Health

Environmental stimuli attack the skin daily resulting in the generation of reactive oxygen species (ROS) and inflammation. One pathway that regulates oxidative stress in skin involves Protein Phosphatase 2A (PP2A), a phosphatase which has been previously linked to Alzheimer’s Disease and aging. Oxidative stress decreases PP2A methylation in normal human dermal fibroblasts (NHDFs). Thus, we hypothesize agents that increase PP2A methylation and activity will promote skin health and combat aging. To discover novel inhibitors of PP2A demethylation activity, we screened a library of 32 natural botanical extracts. We discovered Grape Seed Extract (GSE), which has previously been reported to have several benefits for skin, to be the most potent PP2A demethylating extract. Via several fractionation and extraction steps we developed a novel grape seed extract called Activated Grape Seed Extract (AGSE), which is enriched for PP2A activating flavonoids that increase potency in preventing PP2A demethylation when compared to commercial GSE. We then determined that 1% AGSE and 1% commercial GSE exhibit distinct gene expression profiles when topically applied to a 3D human skin model. To begin to characterize AGSE’s activity, we investigated its antioxidant potential and demonstrate it reduces ROS levels in NHDFs and cell-free assays equal to or better than Vitamin C and E. Moreover, AGSE shows anti-inflammatory properties, dose-dependently inhibiting UVA, UVB and chemical-induced inflammation. These results demonstrate AGSE is a novel, multi-functional extract that modulates methylation levels of PP2A and supports the hypothesis of PP2A as a master regulator for oxidative stress signaling and aging in skin.