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121.
Emilio Aicart Huu Van Tra Lina Andreoli-Ball Donald Patterson 《Journal of solution chemistry》1994,23(11):1183-1201
Expansion coefficients , isothermal compressibilities, thermal pressure coefficients and heat capacities have been measured at 25°C for the cyclohexane+trans-decalin system. An S-shaped composition dependence, positivelnegative for highllow cyclohexane compositions is found for C
p
E
dV
E
/dT and the thermal expansion contribution to C
p
E
namely VT. The thermal motion contribution to C
p
E
, namely C
v
is close to zero. The positive excursion of these mixing quantities at high cyclohexane content is anomalous. Correspondingly, the mixing quantity-VT deviates strongly in this region from the predicted equality with H
E
. The literature and this work show that all these excess quantities behave similarly for cyclohexane mixed with cyclooctane, methylcyclohexane and some highly branched alkanes. The unusual composition dependence of the thermodynamic quantities is consistent with order occurring when any large alkane molecule of globular shape is added to cyclohexane. This is speculatively associated with an interference by the globular alkane with the relatively free rotation of cyclohexane molecules. 相似文献
122.
Johan Garssen Theresa L. Buckley Henk Van Loveren 《Photochemistry and photobiology》1998,68(2):205-210
The aim of this study was to investigate the possible role of sensory nerves in UV light-induced systemic immunomodulation. Contact hypersensitivity to the low molecular weight compound picrylchloride was used as a model for cellular immunity that can be suppressed by low (i.e. suberythemal) doses of UV light even after exposure at a distant locus (i.e. systemic immunosuppression). In sensory nerve-depleted mice, achieved by two subcutaneous injections with the neurotoxin capsaicin before the age of 4 weeks, UV light exposure failed to inhibit contact hypersensitivity responses to picrylchloride. This indicates that sensory nerves are at least partially involved in the induction of systemic immunosuppression by UV light. In order to analyze whether sensory neuropeptides, such as calcitonin gene-related peptide (CGRP) and tachykinins, are involved in UV light-induced systemic immunosuppression, mice were pretreated with selective antagonists prior to each UV light exposure. These experiments indicated that CGRP but not the tachykinins plays a crucial role in the UV light-induced systemic immunosuppression. 相似文献
123.
Haes AJ Zhao J Zou S Own CS Marks LD Schatz GC Van Duyne RP 《The journal of physical chemistry. B》2005,109(22):11158-11162
A novel method to produce solution-phase triangular silver nanoparticles is presented. Ag nanoparticles are prepared by nanosphere lithography and are subsequently released into solution. The resulting nanoparticles are asymmetrically functionalized to produce either single isolated nanoparticles or dimer pairs. The structural and optical properties of Ag nanoparticles have been characterized. Mie theory and the Discrete Dipole Approximation method (DDA) have been used to model and interpret the optical properties of the released Ag nanoparticles. 相似文献
124.
Gary H. Van Domeselaar Glen S. Kwon Lena C. Andrew David S. Wishart 《Colloids and surfaces. B, Biointerfaces》2003,30(4):323-334
This work describes a simple, versatile solid-phase peptide-synthesis (SPPS) method for preparing micelle-forming poly(ethylene oxide)-block-peptide block copolymers for drug delivery. To demonstrate its utility, this SPPS method was used to construct two series of micelle-forming block copolymers (one of constant core-composition and variable length; the other of constant core length and variable composition). The block copolymers were then used to study in detail the effect of size and composition on micellization. The various block copolymers were prepared by a combination of SPPS for the peptide block, followed by solution–phase conjugation of the peptide block with a proprionic acid derivative of poly(ethylene oxide) (PEO) to form the PEO-b-peptide block copolymer. The composition of each block component was characterized by mass spectrometry (MALDI and ES-MS). Block copolymer compositions were characterized by 1H NMR. All the block copolymers were found to form micelles as judged by transmission electron microscopy (TEM) and light scattering analysis. To demonstrate their potential as drug delivery systems, micelles prepared from one member of the PEO-b-peptide block copolymer series were physically loaded with the anticancer drug doxorubicin (DOX). Micelle static and dynamic stability were found to correlate strongly with micelle core length. In contrast, these same micellization properties appear to be a complex function of core composition, and no clear trends could be identified from among the set of compositionally varying, fixed length block copolymer micelles. We conclude that SPPS can be used to construct biocompatible block copolymers with well-defined core lengths and compositions, which in turn can be used to study and to tailor the behavior of block copolymer micelles. 相似文献
125.
Van Der Eycken E Appukkuttan P De Borggraeve W Dehaen W Dallinger D Kappe CO 《The Journal of organic chemistry》2002,67(22):7904-7907
Inter- and intramolecular hetero-Diels-Alder reactions in a series of functionalized 2(1H)-pyrazinones were investigated under controlled microwave irradiation. The cycloaddition reactions were efficiently performed in sealed tubes, utilizing either a combination of 1,2-dichloroethane and a thermally stable ionic liquid, or 1,2-dichlorobenzene as reaction medium. In all cases, a significant rate-enhancement using microwave flash heating as compared to thermal heating was observed. 相似文献
126.
Vanommeslaeghe K Van Alsenoy C De Proft F Martins JC Tourwé D Geerlings P 《Organic & biomolecular chemistry》2003,1(16):2951-2957
Histone deacetylase (HDAC) inhibitors have recently attracted considerable interest because of their therapeutic potential for the treatment of cell proliferative diseases. An X-ray structure of a very potent inhibitor, Trichostatin A (TSA), bound to HDLP (an HDAC analogue isolated from Aquifex aeolicus), is available. From this structure, an active site model (322 atoms), relevant for the binding of TSA and structural analogues, has been derived, and TSA has been minimized in this active site at HF 3-21G* level. The resulting conformation is in excellent accordance with the X-ray structure, and indicates a deprotonation of the hydroxamic acid in TSA by His 131. Also, a water molecule was minimized in the active site. In addition to a similar deprotonation, in accordance with a possible catalytic mechanism of HDAC as proposed by Finnin et al. (M. S. Finnin, J. R. Donigian, A. Cohen, V. M. Richon, R. A. Rifkind and P. A. Marks, Nature, 1999, 401, 188-193), a displacement of the resulting OH- ion in the active site was observed. Based on these results, the difference in energy of binding between TSA and water was calculated. The resulting value is realistic in respect to experimental binding affinities. Furthermore, the mechanism of action of the His 131-Asp 166 charge relay system was investigated. Although the Asp residue in this motif is known to substantially increase the basicity of the His residue, no proton transfer from His 131 to Asp 166 was observed on binding of TSA or water. However, in the empty protonated active site, this proton transfer does occur. 相似文献
127.
A. Van Baalen C.J. Groenenboom H.J. De Liefde Meijer 《Journal of organometallic chemistry》1974,74(2):245-253
The synthesis and the properties of the complexes Cp2TaCl2, Cp2M(allyl), Cp2M(1-methylallyl) and Cp2M(2-methylallyl) with M Nb, Ta are described. The complex Cp2TaCl2 has one unpaired electron per tantalum atom, while the allyl complexes are diamagnetic. The IR and PMR spectra indicate that the allyl group is π-bonded to the metal. The mass spectra of the complexes are discussed; the thermal stability of the Cp2Nb- and Cp2Ta-(allyl) complexes was investigated by differential thermal analysis. The properties of the niobium and tantalum complexes are compared with those of the corresponding titanium complexes. 相似文献
128.
The molecular electric dipole moments are reported for the series of tin-substituted tetracarbonyl cobalt compounds RnYm?nSn{Co(CO)4}4?m (m = 1–3; n ? m; R = alkyl, phenyl; Y = halogen). The effect of the substituents at the tin atom on the nature of the CoSn bond is established on calculating the (CO)4CoSn group dipole moments. It is shown that the charge transfer in the CoSn bond is mainly determined by the inductive properties of the ligands attached to tin. 相似文献
129.
Ehsan A. H. Gomaa H. Schut A. Van Veen M. Mohsen U. Fromm P. Morshuis 《Journal of Radioanalytical and Nuclear Chemistry》1996,211(1):77-83
Using the positron annihilation lifetime technique, the annihilation parameters have been measured for epoxy and high density polyethylene (HDPE) as a function of AC electric field strength and the exposure time. The lifetime spectra have been resolved into three components, the longest component (I33) is attributed to the pick-off annihilation of o-Ps in the amorphous regions. The intermediate one (I22) is due to the annihilation of free positrons, while the shorter component (I11) stems from self annihilation of p-Ps. In HDPE, the o-Ps parameters 3 andI
3 are measured as a function of electric field strengths in the range from 10 to 100 kV/cm exposed for 24 hours. A decrease inI
3 of 8% is observed from zero to 50 kV/cm followed by an increase of the same order from 50 to 100 kV/cm. By investigating the effect of the exposure time from 2 to 24 hours at 16 and 50 kV/cm, the effect is confirmed and is attributed to the inhibition of o-Ps formation at lower field strength. In epoxy, the effect or exposure time onI
3 at 166 and 133 kV/cm shows a similar behavior as in HDPE. At 133 kV/cmI
3 decreases by only 2.5%. On the other hand, the changes in 3 occur at short exposure times. Again at large times the saturation is obtained. These effects are attributed to the expansion of free volume (increase of 3) competing at longer exposure times with other phenomena, such as liberation of free radicals, which reduce the o-Ps intensityI
3 through the conversion to p-Ps. The reactions between o-Ps and free radicals might also lead to free positrons, which could explain the increase ofI
2 and the decrease of 3 at longer exposure times. 相似文献
130.