全文获取类型
收费全文 | 2886篇 |
免费 | 81篇 |
国内免费 | 19篇 |
专业分类
化学 | 2150篇 |
晶体学 | 23篇 |
力学 | 66篇 |
综合类 | 1篇 |
数学 | 192篇 |
物理学 | 554篇 |
出版年
2022年 | 29篇 |
2021年 | 33篇 |
2020年 | 45篇 |
2019年 | 41篇 |
2018年 | 30篇 |
2017年 | 26篇 |
2016年 | 77篇 |
2015年 | 65篇 |
2014年 | 65篇 |
2013年 | 132篇 |
2012年 | 147篇 |
2011年 | 152篇 |
2010年 | 102篇 |
2009年 | 93篇 |
2008年 | 168篇 |
2007年 | 175篇 |
2006年 | 155篇 |
2005年 | 163篇 |
2004年 | 138篇 |
2003年 | 115篇 |
2002年 | 121篇 |
2001年 | 64篇 |
2000年 | 54篇 |
1999年 | 51篇 |
1998年 | 34篇 |
1997年 | 19篇 |
1996年 | 30篇 |
1995年 | 26篇 |
1994年 | 17篇 |
1993年 | 26篇 |
1992年 | 40篇 |
1991年 | 30篇 |
1990年 | 19篇 |
1989年 | 22篇 |
1988年 | 30篇 |
1987年 | 18篇 |
1985年 | 36篇 |
1984年 | 33篇 |
1983年 | 16篇 |
1982年 | 32篇 |
1981年 | 27篇 |
1980年 | 20篇 |
1979年 | 32篇 |
1978年 | 19篇 |
1977年 | 32篇 |
1976年 | 25篇 |
1975年 | 18篇 |
1974年 | 16篇 |
1973年 | 18篇 |
1969年 | 15篇 |
排序方式: 共有2986条查询结果,搜索用时 0 毫秒
81.
Hattori S Ohkubo K Urano Y Sunahara H Nagano T Wada Y Tkachenko NV Lemmetyinen H Fukuzumi S 《The journal of physical chemistry. B》2005,109(32):15368-15375
Boron dipyrromethene (BODIPY), which is commonly used as an energy absorbing and transferring antenna molecule, has been modified to contain an electron donor moiety, 8-(2,4,5-trimethoxyphenyl)-4,4-difluoro-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (MEOPHBDP). The photoinduced electron transfer from a 2,4,5-trimethoxyphenyl moiety to a BODIPY moiety of MEOPHBDP in acetonitrile was observed by femtosecond laser flash photolysis measurements. The lifetime of the charge-separated state of MEOPHBDP was 59 ps at 298 K. The dye-sensitized solar cells (DSSC) were prepared using MEOPHBDP with carboxylic acid (MEOPHBDP-COOH) and a reference BODIPY dye having no electron donor moiety. The photovoltaic measurements were performed using a standard two-electrode system consisting of a working electrode and a Pt sputtered electrode in methoxyacetonitrile containing 0.5 M iodide and 0.05 M I(2). The photoelectrochemical properties of DSSC with MEOPHBDP are compared with those with a reference BODIPY dye. 相似文献
82.
83.
We revealed that in ATX-S10.Na(II)(13,17-bis (1-carboxypropionyl) carbamoylethyl-8-etheny-2-hydroxy-3-hydroxyiminoethylidene-2,7,12,18-tetraethyl porphyrin sodium)-mediated photodynamic therapy using 667 nm nanosecond-pulsed light excitation at a peak intensity of 2.0 MW/cm(2), phototoxicity increased with decreasing pulse repetition rate in the range of 5-30 Hz for A549 cell cultures. To examine the relation between the reaction mechanism and measured phototoxicity, we carefully measured the kinetics of photochemical oxygen consumption and photobleaching during irradiation of ATX-S10.Na(II)-sensitized A549 monolayer cultures. Measurements of oxygen consumption with a microelectrode, which was performed just above the cells, showed that there was no significant difference between the magnitudes of decrease in oxygen at the three repetition rates at the same cumulative fluence. Loss of ATX-S10.Na(II) fluorescence intensity also exhibited little repetition rate dependence when compared at the same cumulative fluence. We investigated the correlation between oxygen consumption and photobleaching during irradiation and obtained "fluorescence-oxygen diagrams." The diagrams showed dynamic changes between oxygen-dependent and oxygen-independent photobleaching at the higher repetition rates of 10 and 30 Hz, whereas such change was not clearly seen over the whole irradiation time at 5 Hz. These results suggest that the reduced phototoxicity at high repetition rates might be due to an oxygen-independent reaction. We presumed that the change in the reaction mechanism was associated with the local concentrations of the photosensitizer and oxygen in cells during irradiation. 相似文献
84.
A fully functionalized ABCD ring moiety of gambierol, a marine polycyclic ether toxin, was synthesized by the use of the oxiranyl anion strategy and reductive cycloetherification of a beta,delta-dihydroxy ketone. 相似文献
85.
Hiroki FurutaToyohisa Takase Hisafumi HayashiRyoji Noyori Yuji Mori 《Tetrahedron》2003,59(49):9767-9777
An efficient method has been developed for the synthesis of trans-fused tetrahydropyrans with angular methyl groups adjacent to the ring oxygen. The procedure involves the coupling reaction of a sulfonyl-stabilized oxiranyl anion with an appropriate triflate followed by 6-endo cyclization, and is effective for the construction of 6/6- and 6/7/6-cyclic ether ring systems with sterically congested 1,3-diaxial methyl groups. 相似文献
86.
A stereocontrolled linear synthesis of the ABCDEF-ring system of yessotoxin and adriatoxin, diarrhetic shellfish toxins, is described. Iterative application of a tetrahydropyran synthesis by reaction of the alkylation of a sulfonyl-stabilized oxiranyl anion followed by 6-endo cyclization of a 4,5-epoxy alcohol led to the synthesis of the trans-fused hexacyclic ether system, and the seven-membered E ring was constructed by ring expansion reaction. 相似文献
87.
To investigate quantitatively the anion effect on the extraction-ability and -selectivity of benzo-18-crown-6 (B18C6) for alkali metal ions, the constants for overall extraction into various diluents having low dielectric constants (K(ex)) and aqueous ion-pair formation (K(MLA)) of B18C6-sodium and potassium perchlorate 1:1:1 complexes (MLA) were determined at 25 degrees C. The K(ex) value was analyzed by the four fundamental equilibrium constants. The K(MLA) values were determined by applying our established method to this perchlorate extraction system. The K(M(B18C6)A) value of the perchlorate is much larger for K(+) than for Na(+), and is much smaller than that of the picrate. The K(M(B18C6)A) value makes a minor contribution to the magnitude of K(ex) for the perchlorate system, but a major contribution to that for the picrate one. The distribution behavior of the B18C6 1:1:1 complexes with the alkali metal perchlorates follows the regular solution theory. For the diluent with a high dipole moment, however, the 1:1:1 complexes somewhat undergo the dipole-dipole interaction. B18C6 always shows very high extraction selectivity for KClO(4) over NaClO(4), which is determined mostly by the much greater log/(log K(MLA)) value for K(+) than for Na(+). The extraction-ability and -selectivity of B18C6 for Na(+) and K(+) ions with a perchlorate ion were compared with those with a picrate ion in terms of the fundamental equilibrium constants. The K(+) extraction-selectivity of B18C6 over Na(+) for the perchlorate system is superior to that for the picrate one, which is caused largely by the greater log/(log K(K(B18C6)A))-log/(log K(Na(B18C6)A)) value for the perchlorate than for the picrate. The perchlorate system is recommended for extraction separation of K(+) from Na(+). 相似文献
88.
Hattori S Wada Y Yanagida S Fukuzumi S 《Journal of the American Chemical Society》2005,127(26):9648-9654
The electron self-exchange rate constants of blue copper model complexes, [(-)-sparteine-N,N'](maleonitriledithiolato-S,S')copper ([Cu(SP)(mmt)])(0/)(-), bis(2,9-dimethy-1,10-phenanthroline)copper ([Cu(dmp)(2)](2+/+)), and bis(1,10-phenanthroline)copper ([Cu(phen)(2)](2+/+)) have been determined from the rate constants of electron transfer from a homologous series of ferrocene derivatives to the copper(II) complexes in light of the Marcus theory of electron transfer. The resulting electron self-exchange rate constant increases in the order: [Cu(phen)(2)](2+/+) < [Cu(SP)(mmt)](0/)(-) < [Cu(dmp)(2)](2+/+), in agreement with the order of the smaller structural change between the copper(II) and copper(I) complexes due to the distorted tetragonal geometry. The dye-sensitized solar cells (DSSC) were constructed using the copper complexes as redox couples to compare the photoelectrochemical responses with those using the conventional I(3)(-)/I(-) couple. The light energy conversion efficiency (eta) values under illumination of simulated solar light irradiation (100 mW/cm(2)) of DSSCs using [Cu(phen)(2)](2+/+), [Cu(dmp)(2)](2+/+), and [Cu(SP)(mmt)](0/)(-) were recorded as 0.1%, 1.4%, and 1.3%, respectively. The maximum eta value (2.2%) was obtained for a DSSC using the [Cu(dmp)(2)](2+/+) redox couple under the light irradiation of 20 mW/cm(2) intensity, where a higher open-circuit voltage of the cell was attained as compared to that of the conventional I(3)(-)/I(-) couple. 相似文献
89.
Secondary structural changes of chymotrypsinogen A,-chymotrypsin, and their isolated polypeptides Cys1-Leu13, Ile16-Tyr146, and Ala149-Asn245were examined in aqueous solutions of sodium dodecyl sulfate (SDS), urea, and guanidine hydrochloride (residue numbers from chymotrypsinogen). After the fragmentation by the cleavage of disulfide bridges in-chymotrypsin, the helical structure was formed in the isolated polypeptide 16–146 where the helical segments do not exist in the protein state. The polypeptide 149–245, where the helical segments of the parent protein are originally located, contained no helices. The polypeptide 1–13 was almost disordered. The three polypeptides, chymotrypsinogen,-chymotrypsin and the polypeptide 16–146, clearly showed differences in the stabilities of helical structures in solutions of urea and guanidine hydrochloride. The addition of SDS accelerated the formation of helical structures in each polypeptide except for 1–13. 相似文献
90.
Shoichi Katsuta Tokutaro Kimura Yoshihiro Kudo Ryozo Nakagawa Yasuyuki Takeda Mikio Ouchi 《Journal of inclusion phenomena and macrocyclic chemistry》1998,31(2):89-98
The overall extraction constants (Kex) of uni- andbivalent metal picrates with 15-(2,5-dioxahexyl)-15-methyl-16-crown-5(L16C5) were determined between benzene and water at 25°C. TheKex values were analyzed into the constituent equilibriumconstants, i.e., the extraction constant of picric acid, the distributionconstant of the crown ether, the stability constant of the metalion–crown ether complex in water, and the ion-pair extraction constantof the complex cation with the picrate anion. The Kex valuedecreases in the orders Ag+ > Na+ >Tl+ > K+ > Li+ andPb2+ > Ba2+ > Sr2+ for theuni- and bivalent metals, respectively, which are the same as those observedfor 16C5. The extraction selectivity was found to be governed by theselectivity of the ion-pair extraction of the L16C5–metal picratecomplex rather than by that of the complex formation in water. Theextraction ability of L16C5 is smaller for all the metals than that of 16C5,which is mostly attributed to the higher lipophilicity of L16C5. Differencesin the extraction selectivity between L16C5 and 16C5 were observed for thebivalent metals but little for the univalent metals. The side-arm effect onthe extraction selectivity was interpreted on the basis of the negativecorrelation between the effect on the complex stability constant in waterand that on the ion-pair extraction constant. 相似文献