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991.
Park JS Shim JY Park JS Lee MJ Kang JM Lee SH Kwon MC Choi YW Jeong SH 《Chemical & pharmaceutical bulletin》2011,59(5):529-535
In order to develop a preferable once-a-day oral tablet formulation, various formulations of three-layered tablets containing tamsulosin HCl as a hydrophilic model drug were evaluated and compared with a commercial reference, tamsulosin OCAS?. When the test tablet was exposed to a release medium, the medium quickly permeated to the mid-layer and the two barrier layers swelled surrounding the mid-layer rapidly. Volume expansion showed faster and enough swelling of the three-layered tablet up to 2 h. Larger amount of barrier layers caused reduced release kinetics and a high molecular weight polymer showed more resistance against agitation force. A formulation with water-soluble mid-layer showed fast erosion decreasing its volume significantly. On the pharmacokinetic study, the mean ratio of area under the curve (AUC) and C(max) for the test formulation to the reference was 0.69 and 0.84, respectively, showing that the absorption of the drug was less complete than the reference. Plasma concentration at 24 h of the test formulation was higher than the reference. The Wagner-Nelson method showed that decreased initial dissolution rate might be the cause of the less complete absorption. On considering in vitro-in vivo correlation (IVIVC), level A, the reference (R2=0.981) showed more linear relationship than the test (R2=0.918) due to the decreased dissolution and absorption rate of the formulation. This result suggests that the in vitro dissolution profiles and release kinetics might be useful in correlating absorption kinetics as well as overall plasma drug concentration-time profiles for formulation studies. 相似文献
992.
The wetting property of a superhydrophobic glass surface with a micro-network of nanopillars fabricated from colloidal lithography and plasma etching is investigated in this paper. The micro-network distribution of nanospheres can be modulated by diluting the nanosphere concentration and controlling the spin rate. The micro-network of nanospheres spun on the glass surface serves as a mask for nanopillars during the plasma etching process. After the fabrication, the nano-structured surface is treated with fluoroalkylsilane self-assembled monolayers to obtain superhydrophobicity. Among several spin rates, the minimum colloidal network area density from a 100 nm polystyrene nanosphere solution diluted to 0.026% was found at a spin rate of 4000 rpm. The sample with the lowest network area density shows a good quality of superhydrophobicity, having the highest water contact angle and the lowest sliding angle among samples with other network area densities. In particular, samples with a micro-network of pillars also showed mechanical robustness against finger rubbing. To assess the superhydrophobic behavior in-depth, a size-dependent contact angle equation is proposed for use with a high contact angle (>135°) and with a Bo (Bond number) ? 1. Furmidge's sliding angle equation is also modified; it is derived considering a static contact angle to simplify the prediction of the sliding angle. The contact and sliding angle measurements from samples with a micro-network of nanopillars show good agreement with the proposed equations. 相似文献
993.
Different kinds of highly ordered patterns of NaYF(4):Yb,Er nanoparticles on gold substrates were fabricated using a simple method combining micro-contact printing and "breath figures" techniques. Ordered arrays of water droplets were first formed in the hydrophilic regions of patterned self-assembled monolayers (SAMs). This was subsequently submerged in a chloroform solution of NaYF(4):Yb,Er nanoparticles. The particles were spontaneously assembled at the interface of chloroform/water droplet surface, leading to different kinds of uniform patterns after solvent evaporation. The structures of NaYF(4):Yb,Er particles patterns depended on the dimension of the substrate, the concentration of the NaYF(4):Yb,Er nanoparticles and the water condensation process. 相似文献
994.
995.
Wu HL Tsai HR Hung YT Lao KU Liao CW Chung PJ Huang JS Chen IC Huang MH 《Inorganic chemistry》2011,50(17):8106-8111
Gold nanocubes, octahedra, and rhombic dodecahedra with roughly two sets of particle sizes have been successfully synthesized via a seed-mediated growth approach. All six samples were analyzed for comparative surface-enhanced Raman scattering (SERS) activity. All of these Au nanostructures were found to yield strong enhancement at a thiophenol concentration of 10(-7) M and are excellent SERS substrates. Rhombic dodecahedra with a rhombus edge length of 32 nm showed significantly better enhancement than the other samples and can reach a detection limit of 10(-8) M. Simulations of the binding energies of thiophenol on the different faces of gold and electric near-field intensities of these nanocrystals have been performed to evaluate the experimental results. Superior SERS activity of these nanocrystals can be expected toward the detection of many other molecules. 相似文献
996.
At room temperature, cobalt oxide cations directly convert methane to methanol with high selectivity but very low efficiency. Two potential intermediates of this reaction, the [HO-Co-CH(3)](+) insertion intermediate and [H(2)O-Co=CH(2)](+) aquo-carbene complex are produced in a laser ablation source and characterized by electronic and vibrational spectroscopy. Reaction of laser-ablated cobalt cations with different organic precursors seeded in a carrier gas produces the intermediates, which subsequently expand into vacuum and cool. Ions are extracted into a time-of-flight mass spectrometer and spectra are measured via photofragment spectroscopy. Photodissociation of [HO-Co-CH(3)](+) in the visible and via infrared multiple photon dissociation (IRMPD) makes only Co(+) + CH(3)OH, while photodissociation of [H(2)O-Co=CH(2)](+) produces CoCH(2)(+) + H(2)O. The electronic spectrum of [HO-Co-CH(3)](+) shows progressions in the excited state Co-C stretch (335 cm(-1)) and O-Co-C bend (90 cm(-1)); the IRMPD spectrum gives ν(OH) = 3630 cm(-1). The [HO-Co-CH(3)](+)(Ar) complex has been synthesized and its vibrational spectrum measured in the O-H stretching region. The resulting spectrum is sharper than that obtained via IRMPD and gives ν(OH) = 3642 cm(-1). Also, an improved potential energy surface for the reaction of CoO(+) with methane has been developed using single point energies calculated by the CBS-QB3 method for reactants, intermediates, transition states and products. 相似文献
997.
The static and dynamic properties of liquid Ga close to the melting line have been studied by first-principles molecular dynamics simulations at ambient and elevated pressure up to 5.8 GPa. Below 2.5 GPa, the nearest neighbor Ga-Ga separation shows little change, while the second and third coordination shells are compressed to shorter distances. This behavior is attributed to the gradual occupation of the interstitial sites. Detail analysis of the local geometry and dynamical behavior refutes the proposed existence of Ga(2) dimers in the liquid state. In fact, both the structure and electronic properties of the liquid are found to closely resemble that of the underlying Ga-II and Ga-III crystalline phases. 相似文献
998.
To overcome the unfavorable steric pressures associated with 2,6-disubstitution in encumbering pyridine ligands, the coordination chemistry of a 2,5-disubstituted variant, namely, 2,5-dimesitylpyridine (2,5-Mes(2)py), is reported. This diaryl pyridine shows good binding ability to a range of transition-metal fragments with varying formal oxidation states and coligands. Treatment of 2.0 equiv of 2,5-Mes(2)py with monovalent Cu and Ag triflate sources generates complexes of the type [M(2,5-Mes(2)py)(2)]OTf (M = Cu, Ag; OTf = OSO(2)CF(3)), which feature long M-OTf distances and a substrate-accessible primary coordination sphere. Combination of 2,5-Mes(2)py with Cu(OTf)(2) and Pd(OAc)(2) produces four-coordinate complexes featuring cis- and trans-2,5-Mes(2)py orientations, respectively. The four-coordinate palladium complex Pd(OAc)(2)(2,5-Mes(2)py)(2) is found to resist py-ligand dissociation at room temperature in solution, but functions as a precatalyst for the aerobic C-H bond olefination of benzene at elevated temperatures. This C-H bond activation chemistry is compared with a similar Pd-based system featuring 2,6-disubstituted pyridines. 2,5-Mes(2)py also readily supports mono- and dinuclear divalent Co complexes, and the solution-phase equilibria between such species are detailed. The coordination studies presented highlight the potential of 2,5-Mes(2)py to function as an encumbering ancillary for the stabilization of low-coordinate complexes and as a supporting ligand for metal-mediated transformations. 相似文献
999.
Aspinall HC Bacsa J Jones AC Wrench JS Black K Chalker PR King PJ Marshall P Werner M Davies HO Odedra R 《Inorganic chemistry》2011,50(22):11644-11652
Thin films of ceria (CeO(2)) have many applications, and their synthesis by liquid-injection MOCVD (metal-organic chemical vapor deposition) or ALD (atomic layer deposition) requires volatile precursor compounds. Here we report the synthesis of a series of homoleptic and heteroleptic Ce(IV) complexes with donor-functionalized alkoxide ligands mmp (1-methoxy-2-methylpropan-2-olate), dmap (1-(dimethylamino)propan-2-olate), and dmop (2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)propan-2-olate) and their potential as precursors for MOCVD and ALD of CeO(2). New complexes were synthesized by alcohol exchange reactions with [Ce(OBu(t))(4)]. [Ce(mmp)(4)] and [Ce(dmap)(4)] were both found to be excellent precursors for liquid-injection MOCVD of CeO(2), depositing high purity thin films with very low carbon contamination, and both have a large temperature window for diffusion controlled growth (350-600 °C for [Ce(mmp)(4)]; 300-600 °C for [Ce(dmap)(4)]). [Ce(mmp)(4)] is also an excellent precursor for liquid-injection ALD of CeO(2) using H(2)O as oxygen source and demonstrates self-limiting growth from 150 to 350 °C. [Ce(dmap)(4)] has lower thermal stability than [Ce(mmp)(4)] and does not show self-limiting growth in ALD. Heteroleptic complexes show a tendency to undergo ligand redistribution reactions to form mixtures in solution and are unsuitable as precursors for liquid-injection CVD. 相似文献
1000.
Kudavalli JS Boyd DR Sharma ND More O'Ferrall RA 《The Journal of organic chemistry》2011,76(22):9338-9343
Acid-catalyzed dehydrations of substituted naphthalene-cis-1,2-dihydrodiols occur with loss of the 1- or 2-OH group to form 2- and 1-naphthols, respectively. Effects of substituents MeO, Me, H, F, Br, I, and CN at 3-, 6-, and 7-positions of the naphthalene ring are consistent with rate-determining formation of β-hydroxynaphthalenium ion (carbocation) intermediates. For reaction of the 1-hydroxyl group the 3-substituents are correlated by the Yukawa-Tsuno relationship with ρ = -4.7 and r = 0.25 or by σ(p) constants with ρ = -4.25; for reaction of the 2-hydroxyl group the 3-substituents are correlated by σ(m) constants with ρ = -8.1. The correlations for the 1-hydroxyl imply a surprisingly weak resonance interaction of +M substituents (MeO, Me) with a carbocation reaction center but are consistent with the corresponding correlation for acid-catalyzed dehydration of 3-substituted benzene-cis-1,2-dihydrodiols for which ρ = -6.9 and r = 0.43. Substituents at the 6- and 7-positions of the naphthalene rings by contrast are correlated by σ(+) with ρ = -3.2 for reaction of the 1-hydroxyl group and ρ = -2.7 for reaction of the 2-hydroxyl group. The unimpaired resonance implied by these substituent effects appears to be inconsistent with a previous explanation of the weak resonance of the 3-substituents in terms of imbalance of charge development and/or nonplanarity of the benzenium ring in the transition state. An alternative possibility is that the adjacent hydroxyl group interferes sterically with conjugation of +M substituents. "Hyperaromaticity" of the arenium ion intermediates does not appear to be a factor influencing this behavior. 相似文献