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21.
Luke Geever Ciaran Cooney Declan Devine Sinead Devery Michael Nugent Clement Higginbotham 《Macromolecular Symposia》2008,266(1):53-58
Summary: PVP/PNIPAAm copolymers exhibit a temperature sensitive nature that makes them an attractive candidate for controlled drug delivery devices. Diclofenac sodium was added to the monomeric mixture, which included an initiator and crosslinking agent (where appropriate), prior to UV photopolymerisation. It was found that the xerogels retained similar properties as the original samples (not containing drug) at lower levels of drug integration. In all cases, drug dissolution analysis showed that the active agent was released at a slower rate at temperatures above the Lower Critical Solution Temperature (LCST). Interestingly, the drug release trends were almost identical for both the physically and chemically crosslinked hydrogels, when the decrease in transition temperature caused by the incorporated crosslinking agent is taken into consideration. It is believed that both types of copolymers reached a constant maximum swollen weight at a set of temperatures above their transition temperatures. When this swollen plateau is attained, the hydrophilic-hydrophobic interactions are balanced, thus the gel does not swell or shrink further and the drug diffuses out at a constant rate. 相似文献
22.
Brands KM Payack JF Rosen JD Nelson TD Candelario A Huffman MA Zhao MM Li J Craig B Song ZJ Tschaen DM Hansen K Devine PN Pye PJ Rossen K Dormer PG Reamer RA Welch CJ Mathre DJ Tsou NN McNamara JM Reider PJ 《Journal of the American Chemical Society》2003,125(8):2129-2135
An efficient stereoselective synthesis of the orally active NK(1) receptor antagonist Aprepitant is described. A direct condensation of N-benzyl ethanolamine with glyoxylic acid yielded a 2-hydroxy-1,4-oxazin-3-one which was activated as the corresponding trifluoroacetate. A Lewis acid mediated coupling with enantiopure (R)-1-(3,5-bis(trifluoromethyl)phenyl)ethan-1-ol afforded a 1:1 mixture of acetal diastereomers which was converted into a single isomer via a novel crystallization-induced asymmetric transformation. The resulting 1,4-oxazin-3-one was converted via a unique and highly stereoselective one-pot process to the desired alpha-(fluorophenyl)morpholine derivative. Interesting and unexpected [1,2]-Wittig and [1,3]-sigmatropic rearrangements were identified during the optimization of these key steps. In the final step, a triazolinone side chain was appended to the morpholine core. The targeted clinical candidate was thus obtained in 55% overall yield over the longest linear sequence. 相似文献
23.
The purpose of this study was to elucidate the mechanism whereby a protective animal colloid acts to prevent agglomeration of solvated nitrocellulose spheres during the manufacture of small arms propellant. To accomplish this, glycine and several glycine-containing peptides were incorporated into cast films of nitrocellulose and studied by means of infrared spectroscopy and X-ray photoelectron spectroscopy. Also, each of the amino acids and peptides were studied by means of infrared spectroscopy in water solution with suspended di-n-butyl phthalate present. The resulting interactions are described. 相似文献
24.
We show that the dynamics of Fermi-Pasta-Ulam recurrence is associated with a nonlinear phase shift between initial and final states that are otherwise identical, after a full growth-return cycle. The properties of this phase shift are studied for the particular case of the self-focussing nonlinear Schrödinger equation, and we describe the magnitude of the phase shift in terms of the system parameters. This phase shift, accumulated during the nonlinear recurrence cycle, is a previously-unremarked feature of the Fermi-Pasta-Ulam problem, and we anticipate its wide significance as an essential feature of related dynamics in other systems. 相似文献
25.
Cronin B Nix MG Devine AL Dixon RN Ashfold MN 《Physical chemistry chemical physics : PCCP》2006,8(5):599-612
The photodissociation dynamics of 2,5-dimethylpyrrole (2,5-DMP) has been investigated following excitation at 193.3 nm and at many near ultraviolet (UV) wavelengths in the range 244 < lambda(phot) < 282 nm using H Rydberg atom photofragment translational spectroscopy (PTS). Complementary UV absorption and, at the longest excitation wavelengths, one photon resonant multiphoton ionisation spectra of 2,5-DMP are reported also; analysis of the latter highlights the role of methyl torsional motions in promoting the parent absorption. The deduced fragmentation dynamics show parallels with that reported recently (B. Cronin, M. G. D. Nix, R. H. Qadiri and M. N. R. Ashfold, Phys. Chem. Chem. Phys., 2004, 6, 5031) for the bare pyrrole molecule. Excitation at the longer wavelengths leads to (vibronically induced) population of the 1(1)A(2)(pisigma*) excited state of 2,5-DMP, but once lambda(phot) decreases to approximately 250 nm stronger, dipole allowed transitions start to become apparent in the parent absorption. All total kinetic energy release (TKER) spectra of the H + 2,5-dimethylpyrrolyl (2,5-DMPyl) fragments measured at lambda(phot)> or=244 nm show a structured fast component, many of which are dominated by a peak with TKER approximately 5100 cm(-1); analysis of this structure reveals lambda(phot) dependent population of selected vibrational levels of 2,5-DMPyl, and enables determination of the N-H bond strength in 2,5-DMP: D(0) = 30 530 +/- 100 cm(-1). Two classes of behaviour are proposed to account for details of the observed energy partitioning. Both assume that N-H bond fission involves passage over (or tunnelling through) a small exit channel barrier on the 1(1)A(2) potential energy surface, but differ according to the vibrational energy content of the photo-prepared molecules. Specific parent out-of-plane skeletal modes that promote the 1(1)A(2)-X(1)A(1) absorption appear to evolve adiabatically into the corresponding vibrations of the 2,5-DMPyl products. Methyl torsions can also promote the 1(1)A(2)<-- X(1)A(1) absorption in 2,5-DMP, and provide a means of populating a much higher density of excited vibrational levels than in pyrrole. Such excited levels are deduced to dissociate by redistributing the minimum amount of internal energy necessary to overcome the exit channel barrier in the N-H dissociation coordinate. Coupling with the ground state surface via a conical intersection at extended N-H bond lengths is proposed as a further mechanism for modest translational --> vibrational energy transfer within the separating products. The parent absorption cross-section increases considerably at wavelengths approximately 250 nm, and PTS spectra recorded at lambda(phot)< or = 254 nm display a second, unstructured, peak at lower TKER. As in pyrrole, this slower component is attributed to H atoms from the unimolecular decay of highly vibrationally excited ground state molecules formed via radiationless decay from photo-excited states lying above the 1(1)A(2) state. 相似文献
26.
Limanto J Desmond RA Gauthier DR Devine PN Reamer RA Volante RP 《Organic letters》2003,5(13):2271-2274
Nucleophilic displacement of readily available alpha,alpha-dibromoketones with excess morpholine gave the corresponding ketoaminals, which upon condensation with aminoguanidine in MeOH in the presence of AcOH afforded 5-substituted-3-amino-1,2,4-triazines in >95% regioselectivity and 45-76% isolated yield. [reaction: see text] 相似文献
27.
28.
1‐Acetylirrüno‐3‐methyl‐1H‐isochromene‐4‐carbonitrile, 1 , reacts with glycine ethyl ester under basic conditions to give an imidazo[2,1‐a]isoquinoline derivative, while reaction with hydrazine hydrate in 1,4‐dioxane, with further chemistry, provides access to [1,2,4]triazolo[5,1‐a]isoquinoline, [1,2,4]triazolo[3,4‐a]isoquinoline and tetrazolo[5,1‐a]isoquinoline analogs. Benzene ring nitration and radical bromination of substituent methyl groups were investigated in the four tricycles, with some different positional reactivities being found. Two bromomethyl derivatives so produced were oxidised; ethyl 2‐bromomethyl‐6‐cyano‐5‐methylimidazo[2,1‐a]isoquinoline‐3‐carboxylate gave the anticipated ethyl 6‐cyano‐2‐formyl‐5‐methylimidazo[2,1‐a]isoquinoline‐3‐carboxylate (which reacted further with hydrazine to form a new system, 8,9‐dihydro‐6‐methyl‐8‐oxopyridazino[4′,5′:4,5]imidazo[2,1‐a]isoquinoline‐5‐carbonitrile), while 5‐bromomethyl‐2‐methyl[1,2,4]triazolo[5,1‐a]isoquinoline‐6‐carbonitrile unexpectedly gave directly another new system, 5,6‐dihydro‐5‐hydroxy‐2‐methyl‐7H‐pyrrolo[3,4‐c][1,2,4]triazolo[5,1‐a]isoquinolin‐7‐one. 相似文献
29.
Gauthier DR Limanto J Devine PN Desmond RA Szumigala RH Foster BS Volante RP 《The Journal of organic chemistry》2005,70(15):5938-5945
A convergent, practical, and efficient synthesis of 2',6-difluoro-5'-[3-(1-hydroxy-1-methylethyl)imidazo[1,2-b][1,2,4]triazin-7-yl]biphenyl-2-carbonitrile (1), an orally active GABA(A) alpha(2/3)-selective agonist, is described. The seven-step, chromatography-free synthesis was demonstrated on a multi-kilogram scale and utilized biaryl bromide 6 and imidazotriazine 22 as key intermediates. Biaryl bromide 6 was prepared via a highly selective aromatic bromination. The regioselective condensation of aminotriazine 15 with chloroacetaldehyde provided the desired imidazotriazine intermediate 22. A highly regioselective palladium-catalyzed arylation in the final step highlights the efficiency of the route. 相似文献
30.