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261.
Tadashi Arai Katsuhiro Takahashi Akinori Kubo Shinsuke Nakahara Sadao Sato Kimie Aiba Chihiro Tamura 《Tetrahedron letters》1979,20(25):2355-2358
The structure of saframycin C(3) has been established by an X-ray crystallographic analysis; this result allows the assignment of structure to the closely related saframycin B(2) by 13C NMR spectroscopy. 相似文献
262.
Suzuki Y Sazaki G Matsui T Nakajima K Tamura K 《The journal of physical chemistry. B》2005,109(8):3222-3226
The growth and dissolution rates of glucose isomerase crystals ({1 0 1} face) were measured in situ at 0.1 and 100 MPa. From these data, we determined that the solubilities at 25 degrees C were C(e) = 3.1 +/- 0.9 and 2.6 +/- 0.5 mg mL(-1) at 0.1 and 100 MPa, respectively. At the same supersaturation of sigma = 2.5 (sigma identical with ln(C/C(e)), C = the concentration of glucose isomerase, C(e) = the solubility) and temperature (T = 25 degrees C), the growth rate under 100 MPa was 7.6 times larger than that under 0.1 MPa. This result shows, for the first time, a kinetic acceleration of the growth rates of protein crystals with increasing pressure. The growth rates vs sigma data fitted well with a two-dimensional nucleation growth model of a polynucleation type. The fitting results indicate that the acceleration is mainly due to the decrease in the molecular surface energy of the glucose isomerase crystal with pressure. 相似文献
263.
Hayashi T Nakashima Y Ito K Ikegami T Aritome I Aoyagi K Ando T Hisaeda Y 《Inorganic chemistry》2003,42(23):7345-7347
The synthesis of the first fluorine-containing iron porphycenes, 2,7,12,17-tetraethyl-3,6,13,16-tetrakis(trifluoromethyl)porphycenatoiron(III) chloride [FePc(EtioCF(3))]Cl and its micro-oxo dimer [FePc(EtioCF(3))](2)O and their characterizations are reported. The crystal structure of [FePc(EtioCF(3))](2)O displays a severe saddled distortion of the porphycene framework due to the steric and electronic effects of the CF(3) substituents. The oxidation and reduction potentials for the micro-oxo dimer are significantly more positive compared to those observed for the reference micro-oxo dimer of the iron porphycenes and porphyrins having no electron-withdrawing substituent. Moreover, the (1)H and (19)F NMR spectra of [FePc(EtioCF(3))](2)O demonstrated that the micro-oxo dimer is readily converted into the monomeric ferrous complex in pyridine-d(5) through autoreduction for 1 day, although the reduction of the reference iron porphycenes and porphyrins are not observed in pyridine. These results indicate that the trifluoromethylated iron porphycene is a highly electron-deficient complex with a pyrrolic macrocycle ligand. 相似文献
264.
265.
Morino K Maeda K Okamoto Y Yashima E Sato T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(22):5112-5120
The temperature dependence of the helical conformations for the homopolymers of phenylacetylene derivatives bearing an optically active substituent, such as the (R)-((1-phenylethyl)carbamoyl)oxy and (R)-((1-(1-naphthyl)ethyl)carbamoyl)oxy groups at the phenyl group, and their copolymers with achiral phenylacetylenes were investigated in solution using circular dichroism (CD) and absorption spectroscopies. The magnitude of the induced CD (ICD) of the optically active homopolymers increased with decreasing temperature and was accompanied by a blueshift in their absorption maxima. On the other hand, the copolymers with achiral phenylacetylenes exhibited interesting ICD changes with temperature, depending on the bulkiness of the achiral comonomers. The copolymers with a less bulky phenylacetylene had a very intense ICD at low temperatures, the ICD pattern was almost opposite to those of the chiral homopolymers, while the copolymers with the most bulky phenylacetylene bearing a tert-butyldiphenylsiloxy group at the para position showed an ICD change similar to that of the optically active homopolymers. However, the copolymers with the phenylacetylene bearing a tert-butyldimethylsiloxy group with intermediate bulkiness at the para position showed no ICD change with temperature. These results indicate that the prevailing helix-sense of the chiral-achiral random copolymers of the phenylacetylenes is determined by a delicate interaction between the chiral and achiral side chains. The thermodynamic stability parameters for the helical conformations of the homopolymers and copolymers of the phenylacetylenes were estimated from the temperature dependence of the ICDs. 相似文献
266.
Heavy metal immobilization in aqueous solution using calcium phosphate and calcium hydrogen phosphates 总被引:1,自引:0,他引:1
Sugiyama S Ichii T Fujisawa M Kawashiro K Tomida T Shigemoto N Hayashi H 《Journal of colloid and interface science》2003,259(2):408-410
This study examines the possibilities for removing heavy metal cations from water with calcium phosphate, calcium hydrogen phosphate, and calcium dihydrogen phosphate at 293 K. It was reported that immobilization of aqueous heavy metal cations, which is known to be one of the characteristic properties of calcium hydroxyapatite, proceeded favorably with these phosphates. Calcium phosphate, calcium hydrogen phosphate, and calcium dihydrogen phosphate could favorably remove Pb2+ from aqueous solution. Calcium hydrogen phosphate also removed aqueous Cu2+, Co2+, and Cd2+, whereas these cations were not immobilized by calcium phosphate and calcium dihydrogen phosphate. A contribution of the dissolution-precipitation mechanism to immobilization with these phosphates is suggested. 相似文献
267.
Maeda K Morino K Okamoto Y Sato T Yashima E 《Journal of the American Chemical Society》2004,126(13):4329-4342
Cis-transoidal poly((4-carboxyphenyl)acetylene) (poly-1) is an optically inactive polymer but forms an induced one-handed helical structure upon complexation with optically active amines such as (R)-(1-(1-naphthyl)ethyl)amine ((R)-2) in DMSO. The complexes show a characteristic induced circular dichroism (ICD) in the UV-visible region of the polymer backbone. Moreover, the macromolecular helicity of poly-1 induced by (R)-2 can be "memorized" even after complete replacement of (R)-2 by various achiral amines. We now report fully detailed studies on the mechanism of the helicity induction and memory of the helical chirality of poly-1 by means of UV-visible, CD, and infrared spectroscopies. We have found that a one-handed helix is cooperatively induced on poly-1 upon the ion pair formation of the carboxy groups of poly-1 with optically active amines and that the bulkiness of the chiral amines plays a crucial role for inducing an excess of a single-handed helix. On the other hand, the free ion formation was found to be essential for the macromolecular helicity memory of poly-1 after the replacement of the chiral amine by achiral amines, since the intramolecular electrostatic repulsion between the neighboring carboxylate ions of poly-1 significantly contributes to reduce the atropisomerization process of poly-1. On the basis of the mechanism of helicity induction and the memory of the helical chirality drawn from the present studies, we succeeded in creating an almost perfect memory of the induced macromolecular helicity of poly-1 with (R)-2 by using 2-aminoethanol as an achiral chaperoning molecule to assist in maintaining the memory of helical chirality. 相似文献
268.
Sohda KY Minematsu T Hashimoto T Suzumura K Funatsu M Suzuki K Imai H Usui T Kamimura H 《Chemical & pharmaceutical bulletin》2004,52(11):1322-1325
Zonampanel monohydrate (YM872) has a potent and selective antagonistic effect on the glutamate receptor subtype, alpha-amino-3-hydroxy-5-methylisoxazole-4-propionic acid (AMPA) receptor. Metabolic fingerprinting in rat urine after a single intravenous administration of (14)C-labeled YM872 ((14)C-YM872) revealed the presence of two metabolites, R1 and R2. The two metabolites were semi-purified by preparative HPLC from rat urine after a single intravenous administration of non-labeled YM872, and their structures were elucidated by various instrumental analyses involving LC-NMR. The results showed that R1 and R2 have a hydroxyamino group and an amino group at the C-7 position of the quinoxalinedione skeleton, respectively. Therefore, the proposed metabolic pathway of YM872 in rats involves the reduction of the nitro group to a hydroxyamino group and then subsequent reduction to an amino group. 相似文献
269.
[reaction: see text] Sialyltransferases (STs) are involved in the biosynthesis of glycoconjugates with important biological activities. Most STs utilize cytidine-5'-monophospho-N-acetylneuraminic acid (CMP-Neu5Ac) as a common donor substrate. A bisubstrate analogue containing the donor substrate (CMP-Neu5Ac mimic) and the acceptor substrate (galactose) was synthesized. Four donor analogues having the partial structure of the bisubstrate analogue were also synthesized to support study of the structure-activity relationship. Each analogue contains an ethylene group in place of the exocyclic anomeric oxygen of CMP-Neu5Ac. The bisubstrate analogue exhibited only weak inhibitory activity to rat recombinant alpha-2,3- and alpha-2,6-ST (IC(50) = 1.3, 2.4 mM). Conversion of the C-1 carboxylate of the Neu5Ac moiety to carboxyamide, hydroxymethyl, or methylene phosphate each resulted in a reduction in inhibitory activity. Among the synthesized analogues, cytidin-5'-yl sialylethylphosphonate (4) was the most potent inhibitor against rat recombinant alpha-2,3- and alpha-2,6-ST (IC(50) = 0.047, 0.34 mM). 相似文献
270.
Wang X Adachi S Iwai H Takatsuki H Fujita K Kubo M Oku A Harada T 《The Journal of organic chemistry》2003,68(26):10046-10057
allo-Threonine-derived O-aroyl-B-phenyl-N-tosyl-1,3,2-oxazaborolidin-5-ones 1g,n catalyze the asymmetric Mukaiyama-Michael reaction of acyclic enones with a trimethylsilyl ketene S,O-acetal in high enantioselectivity. A range of alkenyl methyl ketones is successfully employed as Michael acceptors affording ee values of 85-90% by using 10 mol % of the catalyst. The use of 2,6-diisopropylphenol and tert-butyl methyl ether as additives is found to be essential to achieve high enantioselectivity in these reactions. The effects of the additives are discussed in terms of the retardation of an Si(+)-catalyzed racemic pathway, which seriously deteriorates the enantioselectivity of asymmetric Mukaiyama-Michael reactions. A working model for asymmetric induction is proposed based on correlation between catalyst structures and enantioselectivities. 相似文献