全文获取类型
收费全文 | 957篇 |
免费 | 55篇 |
国内免费 | 4篇 |
专业分类
化学 | 804篇 |
晶体学 | 8篇 |
力学 | 12篇 |
数学 | 28篇 |
物理学 | 164篇 |
出版年
2023年 | 10篇 |
2022年 | 12篇 |
2021年 | 14篇 |
2020年 | 23篇 |
2019年 | 25篇 |
2018年 | 14篇 |
2017年 | 9篇 |
2016年 | 31篇 |
2015年 | 22篇 |
2014年 | 22篇 |
2013年 | 60篇 |
2012年 | 76篇 |
2011年 | 77篇 |
2010年 | 30篇 |
2009年 | 57篇 |
2008年 | 64篇 |
2007年 | 65篇 |
2006年 | 54篇 |
2005年 | 82篇 |
2004年 | 55篇 |
2003年 | 45篇 |
2002年 | 40篇 |
2001年 | 7篇 |
2000年 | 14篇 |
1999年 | 15篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 7篇 |
1995年 | 6篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 5篇 |
1991年 | 2篇 |
1990年 | 8篇 |
1988年 | 7篇 |
1987年 | 3篇 |
1986年 | 6篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 6篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1971年 | 2篇 |
1968年 | 1篇 |
1962年 | 1篇 |
排序方式: 共有1016条查询结果,搜索用时 15 毫秒
151.
A possible deduction is proposed of channel length distribution in one-dimensional porous materials from the kinetic data
obtained in isothermal thermogravimetry (TG). The method utilizes the absorption/desorption of small molecules into one-dimensional
nano-channel. In the surface-controlled absorption/desorption, the second derivative with respect to time is directly proportional
to the channel-length distribution function. Even in the diffusion-controlled case, the second derivative with respect to
the square root of time gives rough information on the distribution function. 相似文献
152.
Dy J Ogawa K Kamada K Ohta K Kobuke Y 《Chemical communications (Cambridge, England)》2008,(29):3411-3413
Butadiyne-porphyrin dimer arrays, which were generated by complementary coordination of the central zinc atom to imidazolyl followed by metathesis, were elongated stepwise and their 2PA properties were explored. 相似文献
153.
154.
Taichi Mitsumoto Dr. Yuya Ashida Dr. Kazuya Arashiba Dr. Shogo Kuriyama Akihito Egi Prof. Dr. Hiromasa Tanaka Prof. Dr. Kazunari Yoshizawa Prof. Dr. Yoshiaki Nishibayashi 《Angewandte Chemie (International ed. in English)》2023,62(43):e202306631
We newly designed and prepared a novel molybdenum complex bearing a 4-[3,5-bis(trifluoromethyl)phenyl]pyridine-based PNP-type pincer ligand, based on the bond dissociation free energies (BDFEs) of the N−H bonds in molybdenum-imide complexes bearing various substituted pyridine-based PNP-type pincer ligands. The complex worked as an excellent catalyst toward ammonia formation from the reaction of an atmospheric pressure of dinitrogen with samarium diiodide as a reductant and water as a proton source under ambient reaction conditions, where up to 3580 equivalents of ammonia were formed based on the molybdenum atom of the catalyst. The catalytic activity was significantly improved by one order of magnitude larger than that observed when using the complex before modification. 相似文献
155.
Dr. Jin Su Dr. Tohru Tsuruoka Dr. Takuji Tsujita Dr. Yuu Inatomi Dr. Kazuya Terabe 《Angewandte Chemie (International ed. in English)》2023,62(9):e202217203
Solid-state batteries (SSBs) that use solid electrolytes instead of flammable liquid electrolytes have the potential to generate higher specific capacity and offer better safety. Magnesium (Mg) based SSBs with Mg metal anodes are considered to be one of the most promising energy storage candidates, because it gives high theoretical volumetric capacities of 3830 mAh cm−3. Here, we demonstrate an atomic layer deposition (ALD) process with a double nitrogen plasma process that successfully produces nitrogen-incorporated magnesium phosphorus oxynitride (MgPON) solid-state electrolyte (SSE) thin films at a low deposition temperature of 125 °C. The ALD MgPON SSEs exhibit an ionic conductivity of 0.36 and 1.2 μS cm−1 at 450 and 500 °C, respectively. The proposed ALD strategy shows the ability of conformal deposition nitrogen-doped SSEs on pattered substrates and is attractive for using nitride ion-conducing films as protective or wetting interlayers in solid-state Mg and Li batteries. 相似文献
156.
Interaction of wheat germ agglutinin with an N-acetylglucosamine-carrying telomer brush accumulated on a colloidal gold monolayer 总被引:1,自引:0,他引:1
A disulfide-carrying telomer with many pendent N-acetylglucosamine (GlcNAc) residues (Cys-PMHGlcNAc) was obtained by photo-polymerization of 1-(6'-methacryloylaminohexyl)-2-N-acetoamido-2-deoxy d-glucopyranoside) (MHGlcNAc) using a benzyl N,N-diethyldithiocarbamoyl (BDC) derivative that shows abilities of initiation, transfer, and termination (iniferter). The disulfide-carrying telomer was accumulated on a monolayer of colloidal Au on a glass substrate, and the interaction of wheat germ agglutinin (WGA) with GlcNAc residue at the polymer brush-solution interface was examined by using the localized surface plasmon resonance (LSPR) technique. For comparison, an amphiphile carrying many pendent GlcNAc residues was also prepared with MHGlcNAc and a lipophilic radical initiator and was incorporated in a phospholipid liposome to examine interaction of the GlcNAc residue with WGA on the liposome surface using turbidity measurements. Both the colloidal gold optical device and the liposome showed a concentration-dependent specific binding of WGA, and the GlcNAc-carrying liposome had a detection limit of 100 nM for WGA, whereas that of the colloidal gold device was 10nM. The sugar-carrying telomer-coated device examined here is not only useful as a simple biosensor chip but is also expected to expand our knowledge of bio-related phenomena at the liquid-telomer brush interfaces on a colloidal Au. 相似文献
157.
Hiraka K Kanehisa M Tamai M Asayama S Nagaoka S Oyaizu K Yuasa M Kawakami H 《Colloids and surfaces. B, Biointerfaces》2008,67(1):54-58
We prepared an anticancer drug based on a pH-sensitive liposome retaining Fe-porphyrin as an SOD mimic. The liposomes contained cationic/anionic lipid combinations and were composed of Fe-porphyrin, 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine, dimethylditetradecylammonium bromide, sodium oleate, and Tween-80. The Fe-porphyrin was released from the liposome at low pH, and the cytotoxicity for cancer cells by the liposome depended on the acidic environments of the endosomes in the cells. Furthermore, although the liposome exhibited an excellent anticancer effect on a gastric cancer cell line, the SOD activity of Fe-porphyrin was shown to have a significant influence on the cytotoxicity toward cancer cells. These findings suggest that the pH-sensitive liposome retaining the Fe-porphyrin as an SOD mimic promises to be a novel anticancer drug for endosomal escape. 相似文献
158.
The accelerating effect of Sc(3+) on the electron-transfer (ET) reduction of the p-benzoquinone derivative 1-(p-tolylsulfinyl)-2,5-benzoquinone (TolSQ) by 10,10'-dimethyl-9,9'-biacridine ((AcrH)(2)) at 233 K changes to a decelerating effect with increasing reaction temperature; the observed second-order rate constant k(et) decreases with increasing Sc(3+) concentration at high concentrations of Sc(3+) at 298 K. At 263 K the k(et) value remains constant with increasing Sc(3+) concentration. Such a remarkable difference with regard to dependence of k(et) on [Sc(3+)] between low and high temperatures results from the difference in relative activity of two ET pathways that depend on temperature, one of which affords 1:1 complex TolSQ*(-)-Sc(3+), and the other 1:2 complex TolSQ*(-)-(Sc(3+))(2) with additional binding of Sc(3+) to TolSQ*(-)-Sc(3+). The formation of TolSQ*(-)-Sc(3+) and TolSQ*(-)-(Sc(3+))(2) complexes was confirmed by EPR spectroscopy in the ET reduction of TolSQ in the presence of low and high concentrations of Sc(3+), respectively. The effects of metal ions on other ET reactions of quinones to afford 1:1 and 1:2 complexes between semiquinone radical anions and metal ions are also reported. The ET pathway affording the 1:2 complexes has smaller activation enthalpies DeltaH( not equal) and more negative activation entropies DeltaS( not equal) because of stronger binding of metal ions and more restricted geometries of the ET transition states as compared with the ET pathway to afford the 1:1 complexes. 相似文献
159.
Kikukawa Y Yamaguchi S Tsuchida K Nakagawa Y Uehara K Yamaguchi K Mizuno N 《Journal of the American Chemical Society》2008,130(16):5472-5478
The di- and tetranuclear metal sandwich-type silicotungstates of Cs10[(gamma-SiW10O36)2{Zr(H2O)}2(mu-OH)2] x 18 H2O (Zr2, monoclinic, C2/c (No. 15), a = 25.3315(8) A, b = 22.6699(7) A, c = 18.5533(6) A, beta = 123.9000(12) degrees, V = 8843.3(5) A(3), Z = 4), Cs10[(gamma-SiW10O36)2{Hf(H2O)}2(mu-OH)2] x 17 H2O (Hf2, monoclinic, space group C2/c (No. 15), a = 25.3847(16) A, b = 22.6121(14) A, c = 18.8703(11) A, beta = 124.046(3) degrees, V = 8974.9(9) A(3), Z = 4), Cs8[(gamma-SiW10O36)2{Zr(H2O)}4(mu4-O)(mu-OH)6] x 26 H2O (Zr4, tetragonal, P4(1)2(1)2 (No. 92), a = 12.67370(10) A, c = 61.6213(8) A, V = 9897.78(17) A(3), Z = 4), and Cs8[(gamma-SiW10O36)2{Hf(H2O)}4(mu4-O)(mu-OH)6] x 23 H2O (Hf4, tetragonal, P4(1)2(1)2 (No. 92), a = 12.68130(10) A, c = 61.5483(9) A, V = 9897.91(18) A(3), Z = 4) were obtained as single crystals suitable for X-ray crystallographic analyses by the reaction of a dilacunary gamma-Keggin silicotungstate K8[gamma-SiW10O36] with ZrOCl2 x 8 H2O or HfOCl2 x 8 H2O. These dimeric polyoxometalates consisted of two [gamma-SiW10O36](8-) units sandwiching metal-oxygen clusters such as [M2(mu-OH)2](6+) and [M4(mu4-O)(mu-OH)6](8+) (M = Zr or Hf). The dinuclear zirconium and hafnium complexes Zr2 and Hf2 were isostructural. The equatorially placed two metal atoms in Zr2 and Hf2 were linked by two mu-OH ligands and each metal was bound to four oxygen atoms of two [gamma-SiW10O36](8-) units. The tertanuclear zirconium and hafnium complexes Zr4 and Hf4 were isostructural and consisted of the adamantanoid cages with a tetracoordinated oxygen atom in the middle, [M4(mu4-O)(mu-OH)6](8+) (M = Zr or Hf). Each metal atom in Zr4 and Hf4 was linked by three mu-OH ligands and bound to two oxygen atoms of the [gamma-SiW10O36](8-) unit. The tetra-nuclear zirconium and hafnium complexes showed catalytic activity for the intramolecular cyclization of (+)-citronellal to isopulegols without formation of byproducts resulting from etherification and dehydration. A lacunary silicotungstate [gamma-SiW10O34(H2O)2](4-) was inactive, and the isomer ratio of isopulegols in the presence of MOCl2 x 8 H2O (M = Zr or Hf) were much different from that in the presence of tetranuclear complexes, suggesting that the [M4(mu4-O)(mu-OH)6](8+) core incorporated into the POM frameworks acts as an active site for the present cyclization. On the other hand, the reaction hardly proceeded in the presence of dinuclear zirconium and hafnium complexes under the same conditions. The much less activity is possibly explained by the steric repulsion from the POM frameworks in the dinuclear complexes. 相似文献
160.
Semiquinone radical anion of 1-(p-tolylsulfinyl)-2,5-benzoquinone (TolSQ(*-)) forms a strong hydrogen bond with protonated histidine (TolSQ(*-)/His x 2 H(+)), which was successfully detected by electron spin resonance. Strong hydrogen bonding between TolSQ(*-) and His x 2 H(+) results in acceleration of electron transfer (ET) from ferrocenes [R2Fc, R = C5H5, C5H4(n-Bu), C5H4Me] to TolSQ, when the one-electron reduction potential of TolSQ is largely shifted to the positive direction in the presence of His x 2 H(+). The rates of His x 2 H(+)-promoted ET from R2Fc to TolSQ exhibit deuterium kinetic isotope effects due to partial dissociation of the N-H bond in His x 2 H(+) at the transition state, when His x 2 H(+) is replaced by the deuterated compound (His x 2 D(+)-d6). The observed deuterium kinetic isotope effect (kH/kD) decreases continuously with increasing the driving force of ET to approach kH/kD = 1.0. On the other hand, His x 2 H(+) also promotes a hydride reduction of TolSQ by an NADH analogue, 9,10-dihydro-10-methylacridine (AcrH2). The hydride reduction proceeds via the one-step hydride-transfer pathway. In such a case, a large deuterium kinetic isotope effect is observed in the rate of the hydride transfer, when AcrH2 is replaced by the dideuterated compound (AcrD2). In sharp contrast to this, no deuterium kinetic isotope effect is observed, when His x 2 H(+) is replaced by His x 2 D(+)-d6. On the other hand, direct protonation of TolSQ and 9,10-phenanthrenequinone (PQ) also results in efficient reductions of TolSQH(+) and PQH(+) by AcrH2, respectively. In this case, however, the hydride-transfer reactions occur via the ET pathway, that is, ET from AcrH2 to TolSQH(+) and PQH(+) occurs in preference to direct hydride transfer from AcrH2 to TolSQH(+) and PQH(+), respectively. The AcrH2(*+) produced by the ET oxidation of AcrH2 by TolSQH(+) and PQH(+) was directly detected by using a stopped-flow technique. 相似文献