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181.
Near-infrared and ultraviolet spectra of water-NaCl-benzene mixtures have been measured in the 473-573 K and 100-400 bar range and 373-498 K and 50-300 bar range, respectively. Concentrations of water in the benzene-rich phase and benzene in the water-rich phase were estimated from integrated intensities of the absorption bands. It is found that addition of NaCl in the aqueous phase suppresses transfer of water into the benzene-rich phase, and the relative decrease in water solubility in benzene exhibits good correlation with an increase in density of the aqueous NaCl solution relative to that of neat water. The salting-out constant for the water-NaCl-benzene system, which is estimated from a relative decrease in benzene solubility in the aqueous phase by addition of sodium chloride, increases significantly with increasing temperature. It is suggested that the effect of sodium chloride on the water-benzene mutual solubilities can be explained by ion-induced electrostriction of the aqueous phase. 相似文献
182.
C. G. Overberger Yotaro Morishima 《Journal of polymer science. Part A, Polymer chemistry》1980,18(5):1433-1446
Preparation and optical properties of linear polyethylenimine (PEI) containing L -(?)-N-[(?)-2-(thymin-1-yl) propionyl] prolyl group as grafting pendant, [P-(?)Pro-(?)T], and its related monomer and dimer model compounds are described. Hypochromic effects and circular dichroism of these compounds were compared with those of PEI containing (?)-2-(thymin-1-yl) propionyl group as grafting pendant, [P-(?)T], which has no L -proline ring as a spacing group. P-(?)Pro-(?)T showed no exciton coupling of B2u π-π* transition although it showed large hypochromicity in neutral aqueous solution, implying that the stacking of the bases has no screw sense. 相似文献
183.
Hashidzume A Watanabe S Morishima Y 《Langmuir : the ACS journal of surfaces and colloids》2007,23(4):2191-2197
The binding of a nonionic surfactant, Triton X-100 (TX), to amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and N-dodecylmethacrylamide (C12) (p(A/C12(x)), where x denotes the mol % content of C12) was investigated by frontal analysis continuous capillary electrophoresis (FACCE) combined with dynamic light scattering focusing on the effect of the hydrophobe content on the binding in a wide range of x (5-60 mol %). From binding isotherms obtained from FACCE data, the binding was found to be cooperative in the whole range of x. Furthermore, a significant change in the binding behavior, i.e., cooperativity, was found to occur in a relatively narrow range of x (38-50 mol %), which is attributable to a change in the self-association behavior of p(A/C12(x)) in this x range. 相似文献
184.
The structure of a jet-cooled 1-naphthol (1-NpOH) dimer was investigated by using resonant-enhanced two-photon ionization (R2PI) and ion-detected infrared (IR) dip spectroscopy. A geometrical optimization and a frequency calculation in (1-NpOH)2 were also performed at the MP2/cc-pVDZ level. Stable isomers in the MP2/cc-pVDZ calculation were classified into a structure dominated only by the pi-pi interaction and structures formed by cooperation between the pi-pi interaction and hydrogen bonding. On the basis of a comparison between the observed and calculated IR spectra, the geometry of (1-NpOH)2 was concluded to be a pi-pi stacking structure supported by hydrogen bonding. 相似文献
185.
Murahashi S Nakae T Terai H Komiya N 《Journal of the American Chemical Society》2008,130(33):11005-11012
Ruthenium-catalyzed oxidative cyanation of tertiary amines with molecular oxygen in the presence of sodium cyanide and acetic acid gives the corresponding alpha-aminonitriles, which are highly useful intermediates for organic synthesis. The reaction is the first demonstration of direct sp(3) C-H bond activation alpha to nitrogen followed by carbon-carbon bond formation under aerobic oxidation conditions. The catalytic oxidation seems to proceed by (i) alpha-C-H activation of tertiary amines by the ruthenium catalyst to give an iminium ion/ruthenium hydride intermediate, (ii) reaction with molecular oxygen to give an iminium ion/ruthenium hydroperoxide, (iii) reaction with HCN to give the alpha-aminonitrile product, H2O2, and Ru species, (iv) generation of oxoruthenium species from the reaction of Ru species with H2O2, and (v) reaction of oxoruthenium species with tertiary amines to give alpha-aminonitriles. On the basis of the last two pathways, a new type of ruthenium-catalyzed oxidative cyanation of tertiary amines with H2O2 to give alpha-aminonitriles was established. The alpha-aminonitriles thus obtained can be readily converted to alpha-amino acids, diamines, and various nitrogen-containing heterocyclic compounds. 相似文献
186.
M. Mizusaki Y. Morishima B.B. Raju F.M. Winnik 《The European physical journal. E, Soft matter》2001,5(1):105-115
Steady-state fluorescence spectroscopy and isothermal titration calorimetry (ITC) have been used to study the aggregation
in aqueous solutions of poly-(2-acrylamido)-2-methylpropanesulfonic acids, sodium salt mono-endcapped with either N,N-di-n-octadecyl or N-4-[(1-pyrenyl)butyl]-N-n-octadecyl which were prepared by free radical polymerization of 2-(acrylamido)-2-methylpropane sulfonic acid (AMPS) initiated
with the azo compounds, 4,4'-azobis{cyano-N,N-di-n-octadecyl}pentanamide and 4,4'-azobis{cyano-N,N-[4-(1-pyrenyl)butyl]-n-octadecyl}pentanamide, respectively. Both techniques indicate the occurrence of multimolecular aggregates in solutions of
the polymers in water and in 0.2 M NaCl. The concentration range for aggregation is about 1-14 mmol AMPS l-1 (0.5-2.7 g l-1) in 0.2 M NaCl and the enthalpy of micellization, estimated from ITC data, is ∼100 J [mol AMPS]-1. The accessibility of the chromophores to neutral molecules and to cationic species was assessed by quenching of fluorescence
with nitromethane and thallium nitrate, respectively. The association of the mono-endcapped polymers is compared to that of
PAMPS derivatives carrying hydrophobic groups randomly attached along the chain.
Received 7 August 2000 and Received in final form 26 October 2000 相似文献
187.
Hiroshi Watanabe Ming-Long Yao Kunihiro Osaki Toshiyuki Shikata Hirokazu Niwa Yotaro Morishima 《Rheologica Acta》1999,38(1):2-13
Nonlinear rheology was examined for concentrated suspensions of spherical silica particles (with radius of 40 nm) in viscous
media, 2.27/1 (wt/wt) ethylene glycol/glycerol mixture and pure ethylene glycol. The particles were randomly and isotropically
dispersed in the media in the quiescent state, and their effective volume fraction φeff ranged from 0.36 to 0.59. For small strains, the particles exhibited linear relaxation of the Brownian stress σB due to their diffusion. For large step strains γ, the nonlinear relaxation modulus G(t,γ) exhibited strong damping and obeyed the time-strain separability. This damping was related to γ-insensitivity of strain-induced
anisotropy in the particle distribution that resulted in decreases of σB/γ. The damping became stronger for larger φeff. This φeff dependence was related to a hard-core volume effect, i.e., strain-induced collision of the particles that is enhanced for
larger φeff. Under steady/transient shear flow, the particles exhibited thinning and thickening at low and high γ˙, respectively. The thinning behavior was well described by a BKZ constitutive equation using the G(t,γ) data and attributable to decreases of a Brownian contribution, σB/γ˙. The thickening behavior, not described by this equation, was related to dynamic clustering of the particles and corresponding
enhancement of the hydrodynamic stress at high γ˙. In this thickening regime, the viscosity growth η+ after start-up of flow was scaled with a strain γ˙t. Specifically, critical strains γd and γs for the onset of thickening and achievement of the steadily thickened state were independent of γ˙ but decreased with increasing φeff. This φeff dependence was again related to the hard-core volume effect, flow-induced collision of the particles enhanced for larger
φeff.
Received: 26 June 1998 Accepted: 9 December 1998 相似文献
188.
Shin‐Ichi Yusa Mikiharu Kamachi Yotaro Morishima 《Journal of polymer science. Part A, Polymer chemistry》1999,37(1):47-58
A copolymer of cholesteryl 6‐(methacryloyloxy)hexanoate and a small amount of (1‐pyrenylmethyl) 6‐(methacryloyloxy)hexanoate (Py‐C5‐MA) was prepared by free radical copolymerization. A copolymer of 1‐eicosanylmethacrylate and a small amount of Py‐C5‐MA was also prepared as a reference copolymer. A wide‐angle X‐ray diffraction pattern for an n‐hexane solution of the cholesterol(Chol)‐containing copolymer showed a peak corresponding to a spacing of 5.3 Å. In n‐hexane, the hydrodynamic radius (Rh) for the Chol‐containing copolymer (Mw = 7.8 × 104) was 8.1 nm, while that of the eicosanyl‐containing copolymer (Mw = 4.9 × 104) was 9.6 nm, Rh for the former being smaller than that for the latter, although Mw for the former was higher than that of the latter. 1H‐NMR spectra of the Chol‐containing polymer in n‐hexane‐d14 indicated a strong restriction of local motions of pendant Chol groups. Fluorescence spectra of the Chol‐containing copolymer in n‐hexane indicated that each pyrene group was isolated from others. In n‐hexane/benzene mixed solutions of the Chol‐containing polymer, the ratio of the intensity of the excimer relative to the monomer emission decreased with increasing the ratio of n‐hexane in the mixed solvent. Electron transfer from N,N‐dimethylaniline to singlet‐excited pyrene chromophores was suppressed in the Chol‐containing copolymer in n‐hexane. The pyrene chromophores exhibited a long triplet lifetime in n‐hexane. These observations led us to conclude that Chol groups formed stacks in n‐hexane, and that the pyrene chromophores were trapped in the Chol stacks, leading to the “protection” of pyrene from the bulk phase. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 47–58, 1999 相似文献
189.
190.