This article presents successful incorporation of ibuprofen in polylactic acid (PLA) nanofibers to create scaffolds for the treatment of both acute and chronic wounds. Nanofibrous PLA scaffolds containing 10, 20, or 30 wt % ibuprofen were... more
This article presents successful incorporation of ibuprofen in polylactic acid (PLA) nanofibers to create scaffolds for the treatment of both acute and chronic wounds. Nanofibrous PLA scaffolds containing 10, 20, or 30 wt % ibuprofen were created and ibuprofen release profiles quantified. In vitro cytotoxicity to human epidermal keratinocytes (HEK) and human dermal fibroblasts (HDF) of the three scaffolds with varying ibuprofen concentrations were evaluated and compared to pure PLA nanofibrous scaffolds. Thereafter, scaffolds loaded with ibuprofen at the concentration that promoted human skin cell viability and proliferation (20 wt %) were evaluated in vivo in nude mice using a full thickness skin incision model to determine the ability of these scaffolds to promote skin regeneration and/or assist with scarless healing. Both acellular and HEK and HDF cell‐seeded 20 wt % ibuprofen loaded nanofibrous bandages reduced wound contraction compared with wounds treated with Tegaderm™ and st...
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Internal motions at specific locations through yeast phenylalanine tRNA were measured by using nucleic acid biosynthetically enriched in 13C at modified base methyl groups. Carbon NMR spectra of isotopically enriched tRNA(Phe) reveal 12... more
Internal motions at specific locations through yeast phenylalanine tRNA were measured by using nucleic acid biosynthetically enriched in 13C at modified base methyl groups. Carbon NMR spectra of isotopically enriched tRNA(Phe) reveal 12 individual peaks for 13 of the 14 methyl groups known to be present. The two methyls of N2,N2-dimethylguanosine (m22G-26) have indistinguishable resonances, whereas the fourteenth methyl bound to ring carbon-11 of the hypermodified nucleoside 3' adjacent to the anticodon, wyosine (Y-37), does not come from the [methyl-13C]methionine substrate. Assignments to individual nucleosides within the tRNA were made on the basis of chemical shifts of the mononucleosides [Agris, P. F., Kovacs, S. A. H., Smith, C., Kopper, R. A., & Schmidt, P. G. (1983) Biochemistry 22, 1402-1408; Smith, C., Schmidt, P. G., Petsch, J., & Agris, P. F. (1985) Biochemistry 24, 1434-1440] and correlation of 13C resonances with proton NMR chemical shifts via two-dimensional heteronuclear proton-carbon correlation spectroscopy [Agris, P. F., Sierzputowska-Gracz, H., & Smith, C. (1986) Biochemistry 25, 5126-5131]. Values of 13C longitudinal relaxation (T1) and the nuclear Overhauser enhancements (NOE) were determined at 22.5, 75.5, and 118 MHz for tRNA(Phe) in a physiological buffer solution with 10 mM MgCl2, at 22 degrees C. These data were used to extract two physical parameters that define the system with regard to fast internal motion: the generalized order parameters (S2) and effective correlation times (tau e) for internal motion of the C-H internuclear vectors.(ABSTRACT TRUNCATED AT 250 WORDS)
Research Interests: Biochemistry, Chemistry, Nuclear Magnetic Resonance, Magnetic Resonance Spectroscopy, Medicine, and 15 moreCarbon Isotopes, Magnetic Resonance, Carbon Isotope, Amino Acid Profile, Chemical Shift, Base Sequence, Order Parameter, Nuclear Overhauser Effect, Methyl Ester, Nucleic Acid Conformation, Biochemistry and cell biology, Organic Acid, Nucleic Acid, Medical biochemistry and metabolomics, and Anticodon
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ABSTRACT The gel phase of a cationic surfactant/polyanion system consisting of tetradecyltrimethylammonium bromide (TTAB) and sodium hyaluronate was studied by multifield C-13 relaxation and differential line broadening. A series of... more
ABSTRACT The gel phase of a cationic surfactant/polyanion system consisting of tetradecyltrimethylammonium bromide (TTAB) and sodium hyaluronate was studied by multifield C-13 relaxation and differential line broadening. A series of TTAB/D2O/NaBr micellar samples were also studied for comparison. The relaxation results show that the surfactant molecules in the surfactant/polyanion gels form relatively small micelle-like aggregates which are adsorbed on the polyelectrolyte chains. The reorientation of the aggregates in the presence of the polyelectrolyte is not isotropic. The relaxation data cannot be interpreted in terms of the two-step model, and the contribution from the motion of the polyelectrolyte chains to the relaxation has to be included. At high polyelectrolyte/surfactant ratios (above 0.5 by weight), however, the surfactant aggregates appear to be completely covered with polyelectrolyte chains. This is evidenced by the observation from NMR relaxation that the reorientation of the micelles becomes isotropic. This conclusion is in agreement with that inferred from proton self-diffusion and fluorescence quenching studies of the same system.
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Abstract: An NMR realization of a two-qubit quantum gate which processes quantum information indirectly via couplings to a spectator qubit is presented in the context of the Deutsch-Jozsa algorithm. This enables a successful comprehensive... more
Abstract: An NMR realization of a two-qubit quantum gate which processes quantum information indirectly via couplings to a spectator qubit is presented in the context of the Deutsch-Jozsa algorithm. This enables a successful comprehensive NMR implementation ...
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The possibility of positively charged nucleosides in tRNA has been suspected because certain posttranscriptional methylations produce quaternary nitrogens. To investigate this possibility and the importance of such methylations to tRNA... more
The possibility of positively charged nucleosides in tRNA has been suspected because certain posttranscriptional methylations produce quaternary nitrogens. To investigate this possibility and the importance of such methylations to tRNA structure, we have continued our studies of [13C]methyl-enriched phenylalanine tRNA of Escherichia coli [Kopper, R.A., Schmidt, P.G., & Agris, P.F. (1983) Biochemistry 22, 1307-1401] and yeast [Smith, C., Petsch, J., Schmidt, P.G., & Agris, P.F. (1985) Biochemistry 24, 1434-1440]. E. coli and yeast tRNA were 13C-enriched in their methyl groups in vivo, and phenylalanine-specific tRNA was isolated. Methyl proton and carbon signal assignments were confirmed and correlated for the purified tRNAs under native conditions via the first application of two-dimensional carbon-proton correlation NMR spectroscopy to a native nucleic acid. The methyl proton chemical shift of the 7-methylguanosine (m7G) signal from tRNA was easily determined, although by conventional 1H NMR spectroscopy it would have been hidden by ribose resonances and H2O. The chemical shift for 1-methyladenosine (m1A) protons was shown to be 3.01 ppm. Resolution of close or overlapping peaks was greatly enhanced by the two-dimensional experiment especially for the proton methyl resonances. In addition, proton-carbon chemical shift correspondence has been determined for the two 5-methylcytidines (m5C's), the methyl esters of wybutosine (Y), and the two ribose methyl groups, Gm and Cm, of yeast tRNAPhe. Thermal denaturation and Mg2+ depletion affect the methyl carbon NMR chemical shifts of tRNA.(ABSTRACT TRUNCATED AT 250 WORDS)
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Modeling of polystyrene (PS) with various stereosequences in γ-cyclodextrin (γ-CD) channels has been conducted and it was found that only isotactic PS stereoisomers can fit into the γ-CD cavity. Thus, based on the modeling of... more
Modeling of polystyrene (PS) with various stereosequences in γ-cyclodextrin (γ-CD) channels has been conducted and it was found that only isotactic PS stereoisomers can fit into the γ-CD cavity. Thus, based on the modeling of stereoisomeric polystyrenes in narrow γ-CD ...
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Research Interests: The and CHEMICAL SCIENCES
A detailed description of the development of a three qubit NMR realization of the Deutsch-Jozsa algorithm [Collins et.al., Phys. Rev. A 62, 022304 (2000)] is provided. The theoretical and experimental techniques used for the reduction of... more
A detailed description of the development of a three qubit NMR realization of the Deutsch-Jozsa algorithm [Collins et.al., Phys. Rev. A 62, 022304 (2000)] is provided. The theoretical and experimental techniques used for the reduction of the algorithm's evolution steps into a sequence of NMR pulses are discussed at length. This includes the description of general pulse sequence compilation techniques, various schemes for indirectly coupled gate realizations, experimental pulse parameterization techniques and bookkeeping methods for pulse phases.
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Modeling of polystyrene (PS) with various stereosequences in γ-cyclodextrin (γ-CD) channels has been conducted and it was found that only isotactic PS stereoisomers can fit into the γ-CD cavity. Thus, based on the modeling of... more
Modeling of polystyrene (PS) with various stereosequences in γ-cyclodextrin (γ-CD) channels has been conducted and it was found that only isotactic PS stereoisomers can fit into the γ-CD cavity. Thus, based on the modeling of stereoisomeric polystyrenes in narrow γ-CD channels, it was suggested that PSs with unusual microstructures might be produced via constrained polymerization of styrene monomer in its
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We investigate the elasticity of two types of single-stranded synthetic DNA homopolydeoxynucletides, poly(dA) and poly(dT), by AFM-based single-molecule force spectroscopy. We find that poly(dT) exhibits the expected entropic elasticity... more
We investigate the elasticity of two types of single-stranded synthetic DNA homopolydeoxynucletides, poly(dA) and poly(dT), by AFM-based single-molecule force spectroscopy. We find that poly(dT) exhibits the expected entropic elasticity behavior, while poly(dA) unexpectedly displays two overstretching transitions in the force-extension relationship. We suggest that these transitions, which occur at approximately 23 pN and approximately 113 pN, directly capture, for the first time, the mechanical signature of base-stacking interactions among adenines in DNA, in the absence of base pairing.
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Cloprostenol sodium salt (referred as cloprostenol) may be used for the synchronization of estrous cycles in farm animal species. Cyclodextrins (CDs) have potential as drug delivery systems through the formation of inclusion complexes... more
Cloprostenol sodium salt (referred as cloprostenol) may be used for the synchronization of estrous cycles in farm animal species. Cyclodextrins (CDs) have potential as drug delivery systems through the formation of inclusion complexes between CDs and drugs. This is the first study of the inclusion complex of cloprostenol with beta-cyclodextrin (beta-CD) in aqueous solution using NMR and 3D molecular dynamics simulations. 1D proton NMR spectra of beta-CD, a complex of cloprostenol with beta-CD, and cloprostenol in D(2)O were assigned and confirmed. The cross relaxation interactions from ROESY were used as constraints for 3D molecular modeling studies. In the 2D ROESY of the complex, cross-peaks were observed between the aromatic protons of cloprostenol and protons of the beta-CD as well as between aliphatic protons and protons of the beta-CD. The stoichiometry of the complex was found that beta-CD forms a 1:1 inclusion complex with cloprostenol. The association constant K was 968 +/- 120 M(-1) at 298 K. Aromatic side and/or aliphatic side chains of the cloprostenol is included in the beta-CD while aliphatic side and/or aromatic side chains wraps around beta-CD, respectively. The molecular modeling also confirms that beta-CD forms a 1:1 inclusion complex with cloprostenol.
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Pine Kraft-AQ pulp was biobleached with pressurized dioxygen at 40°C in laccase-mediator system (LMS), i.e. in acetate buffer (pH 4.5) containing Coriolus-laccase and 1-hydroxy-benzotriazole (HOBT), the latter being as a mediator. The... more
Pine Kraft-AQ pulp was biobleached with pressurized dioxygen at 40°C in laccase-mediator system (LMS), i.e. in acetate buffer (pH 4.5) containing Coriolus-laccase and 1-hydroxy-benzotriazole (HOBT), the latter being as a mediator. The LMS-treatment was followed by alkaline extraction (E) under standard conditions. The structures of the residual lignins before and after the biobleaching did not differ appreciably. This indicates that
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Pine kraft-anthraquinone (kraft-AQ) pulp was bleached in alkaline solution with hydrogen peroxide catalyzed by either [L(1)Mn(IV)(micro-O)(3)Mn(IV)L(1)](PF(6))(2)] (C1) or [LMn(IV)(2)(micro-O)(3)] (ClO(4))(2) (C2) at 60 and 80 degrees C... more
Pine kraft-anthraquinone (kraft-AQ) pulp was bleached in alkaline solution with hydrogen peroxide catalyzed by either [L(1)Mn(IV)(micro-O)(3)Mn(IV)L(1)](PF(6))(2)] (C1) or [LMn(IV)(2)(micro-O)(3)] (ClO(4))(2) (C2) at 60 and 80 degrees C for 120 min with a catalyst charge of 10 ppm on pulp. The resulting bleached pulp was hydrolyzed with cellulase to obtain insoluble and soluble residual lignins. The alkaline bleaching effluents were acidified to precipitate alkaline-soluble lignins. These lignin preparations were then characterized by 2D heteronuclear multiple-quantum coherence (HMQC) NMR spectroscopic techniques. The results showed that biphenyl (5-5) and stilbene structures of the residual lignin in the pulp are preferentially degraded in both the C1- and C2-catalyzed bleachings, whereas beta-O-4, beta-5, and beta-beta structures undergo degradation to a lesser extent. In both cases, the degradation of the residual lignin increased with the increase in reaction temperature from 60 to 80 degrees C. Thus, the result of C1-catalyzed delignification is not in agreement with the observed decrease in the disappearance rate for substrates in the C1-catalyzed oxidation of lignin model compounds with hydrogen peroxide when the reaction temperature is increased from 60 to 80 degrees C. In addition, the resulting residual lignins in the C2-catalyzed bleaching at 80 degrees C are less degraded than the corresponding lignins in the C1-catalyzed bleaching at both 60 and 80 degrees C. Thus, C1 is more effective than C2 as catalyst in the binucleus Mn(IV) complex-catalyzed bleaching of pine kraft-AQ pulp with hydrogen peroxide.
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Pine Kraft-AQ pulp was bleached with hydrogen peroxide catalyzed by [LMn(IV)(2) (mu-O)(3)](ClO(4))(2) at 80 degrees C for 120 min under optimum reaction conditions. The resulting bleached pulp was hydrolyzed with cellulase to obtain... more
Pine Kraft-AQ pulp was bleached with hydrogen peroxide catalyzed by [LMn(IV)(2) (mu-O)(3)](ClO(4))(2) at 80 degrees C for 120 min under optimum reaction conditions. The resulting bleached pulp was hydrolyzed with cellulase to obtain insoluble and soluble residual lignins. The alkaline effluent from the bleaching was acidified to precipitate alkaline soluble lignin. These lignin preparations were purified, and then analyzed by 2D HMQC NMR spectroscopic techniques. The results showed that biphenyl (5-5) and stilbene structures are preferentially degraded in the bleaching process, while beta-O-4, beta-5, and beta-beta structures undergo degradation only to a lesser extent. This implies that hydrogen peroxide bleaching using the catalyst is more effective in delignification of softwood pulps than hardwood pulps. The possible reaction mechanisms for the delignification of residual lignin in the pine Kraft-AQ pulp in the bleaching process are discussed on the basis of the 2D HMQC NMR spectroscopic data and the model compound experiments.
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Phosphatase enzymes are responsible for mineralization of organic-phosphorus (P) compounds in soil where they hydrolyze the organic phosphate esters to inorganic phosphate. One way to monitor the mineralization process in soils receiving... more
Phosphatase enzymes are responsible for mineralization of organic-phosphorus (P) compounds in soil where they hydrolyze the organic phosphate esters to inorganic phosphate. One way to monitor the mineralization process in soils receiving poultry manure is by assessing the activity of phosphatase in a soil amended with poultry manure relative to a soil that is not amended. In a laboratory incubation, soil phosphomonoesterase activity and soil phosphodiesterase activity were measured 0, 1, 2, 4, 8, 12, 16, and 20 weeks after soil incorporation of poultry litter. Two soils, both Fine-loamy siliceous, thermic Typic Kandiudults, were used in the study. Both soils differed in their previous management. The first soil was from a conventionally tilled field that received annual poultry litter applications for 18 consecutive years. The second soil was from an adjacent recently cleared woodland that had no history of manure application. In the previously non-manured soil, soil phosphodiesterase activity following poultry litter addition increased from 4 to 66 μg p-nitrophenol g soil hour by the second week. However, in the same soil, after 8 weeks, phosphodiesterase activity resulting from poultry litter applications was not evident. There was a net increase in phosphomonoesterase activity from week 0 to 20 in the previously manured and previously non-manured soils that were amended with poultry litter. A simultaneous study was conducted to measure the relative concentration of organic P forms during the mineralization process using P nuclear magnetic resonance. Subsamples from the poultry manure-amended soil were extracted with 0.25 M NaOH+0.05 M EDTA following 0, 1, 2, 4, 8, 12, 16, and 20 weeks after manure addition and incorporation. The concentration of organic P compounds decreased from the time of poultry litter incorporation until week 20 whereas orthophosphate concentration increased during this period.
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Research Interests: Organic Chemistry, Magnetic Resonance Spectroscopy, Humans, Solubility, Liquid Chromatography / Electrospray Ionization Mass Spectrometry, and 7 moreBreast carcinoma, Bioorganic and medicinal Chemistry, Structure activity Relationship, Structure Function, Cations, Antineoplastic Agents, and Ceramides
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Recently, genetic studies have revealed the entire amino acid sequence of Bombyx mori silk fibroin. It is known from X-ray diffraction studies that the beta-sheet crystalline structure (silk II) of fibroin is composed of hexaamino acid... more
Recently, genetic studies have revealed the entire amino acid sequence of Bombyx mori silk fibroin. It is known from X-ray diffraction studies that the beta-sheet crystalline structure (silk II) of fibroin is composed of hexaamino acid sequences of GAGAGS. However, in the heavy chain of B. mori silk fibroin, there are also present 11 irregular sequences, with about 31 amino acid residues (irregular GT approximately GT sequences). The structure and role of these irregular sequences have remained unknown. One of the most frequently appearing irregular sequences was synthesized and its 3-D solution structure was studied by high-resolution 2-D NMR techniques. The 3-D structure determined for this peptide shows that it makes a loop structure (distorted omega shape), which implies that the preceding backbone direction is changed by 180 degrees, i.e., reversed, by this sequence. This may facilitate the beta-sheet formation between the crystal-forming building blocks, GAGAGS/GY approximately GY sequences, in the fibroin heavy chain.