全文获取类型
收费全文 | 465篇 |
免费 | 6篇 |
国内免费 | 7篇 |
专业分类
化学 | 329篇 |
晶体学 | 3篇 |
力学 | 5篇 |
数学 | 49篇 |
物理学 | 92篇 |
出版年
2024年 | 1篇 |
2022年 | 2篇 |
2021年 | 3篇 |
2020年 | 4篇 |
2019年 | 4篇 |
2018年 | 2篇 |
2017年 | 1篇 |
2016年 | 7篇 |
2015年 | 6篇 |
2014年 | 14篇 |
2013年 | 33篇 |
2012年 | 20篇 |
2011年 | 27篇 |
2010年 | 5篇 |
2009年 | 15篇 |
2008年 | 33篇 |
2007年 | 33篇 |
2006年 | 31篇 |
2005年 | 29篇 |
2004年 | 27篇 |
2003年 | 30篇 |
2002年 | 19篇 |
2001年 | 4篇 |
2000年 | 8篇 |
1999年 | 8篇 |
1998年 | 7篇 |
1997年 | 8篇 |
1996年 | 6篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 1篇 |
1992年 | 3篇 |
1991年 | 7篇 |
1990年 | 8篇 |
1989年 | 5篇 |
1988年 | 9篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 7篇 |
1983年 | 2篇 |
1982年 | 6篇 |
1981年 | 8篇 |
1980年 | 6篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 5篇 |
1976年 | 5篇 |
1973年 | 4篇 |
1971年 | 1篇 |
1964年 | 1篇 |
排序方式: 共有478条查询结果,搜索用时 15 毫秒
81.
Chiral phosphine oxide successfully catalyzed the direct aldol-type reactions of cyclohexanone derivatives and benzaldehyde derivatives in high stereoselectivities. The reaction mechanism involves the in situ formation of trichlorosilyl enol ethers. The present reaction could be extended to the cross-aldol reactions between two aldehydes. 相似文献
82.
Cho J Furutachi H Fujinami S Tosha T Ohtsu H Ikeda O Suzuki A Nomura M Uruga T Tanida H Kawai T Tanaka K Kitagawa T Suzuki M 《Inorganic chemistry》2006,45(7):2873-2885
The reaction of [Ni2(OH)2(Me2-tpa)2]2+ (1) (Me2-tpa = bis(6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine) with H2O2 causes oxidation of a methylene group on the Me2-tpa ligand to give an N-dealkylated ligand and oxidation of a methyl group to afford a ligand-based carboxylate and an alkoxide as the final oxidation products. A series of sequential reaction intermediates produced in the oxidation pathways, a bis(mu-oxo)dinickel(III) ([Ni2(O)2(Me2-tpa)2]2+ (2)), a bis(mu-superoxo)dinickel(II) ([Ni2(O2)2(Me2-tpa)2]2+ (3)), a (mu-hydroxo)(mu-alkylperoxo)dinickel(II) ([Ni2(OH)(Me2-tpa)(Me-tpa-CH2OO)]2+ (4)), and a bis(mu-alkylperoxo)dinickel(II) ([Ni2(Me-tpa-CH2OO)2]2+ (5)), was isolated and characterized by various physicochemical measurements including X-ray crystallography, and their oxidation pathways were investigated. Reaction of 1 with H2O2 in methanol at -40 degrees C generates 2, which is extremely reactive with H2O2, producing 3. Complex 2 was isolated only from disproportionation of the superoxo ligands in 3 in the absence of H2O2 at -40 degrees C. Thermal decomposition of 2 under N2 generated an N-dealkylated ligand Me-dpa ((6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine) and a ligand-coupling dimer (Me-tpa-CH2)2. The formation of (Me-tpa-CH2)2 suggests that a ligand-based radical Me-tpa-CH2* is generated as a reaction intermediate, probably produced by H-atom abstraction by the oxo group. An isotope-labeling experiment revealed that intramolecular coupling occurs for the formation of the coupling dimer. The results indicate that the rebound of oxygen to Me-tpa-CH2* is slower than that observed for various high-valence bis(mu-oxo)dimetal complexes. In contrast, the decomposition of 2 and 3 in the presence of O2 gave carboxylate and alkoxide ligands, respectively (Me-tpa-COO- and Me-tpa-CH2O-), instead of (Me-tpa-CH2)2, indicating that the reaction of Me-tpa-CH2* with O2 is faster than the coupling of Me-tpa-CH2* to generate ligand-based peroxyl radical Me-tpa-CH2OO*. Although there is a possibility that the Me-tpa-CH2OO* species could undergo various reactions, one of the possible reactive intermediates, 4, was isolated from the decomposition of 3 under O2 at -20 degrees C. The alkylperoxo ligands in 4 and 5 can be converted to a ligand-based aldehyde by either homolysis or heterolysis of the O-O bond, and disproportionation of the aldehyde gives a carboxylate and an alkoxide via the Cannizzaro reaction. 相似文献
83.
A simple and sensitive method was developed for the determination of erythromycin A (EA), decladinosyl erythromycin A (dClEA) and erythromycin B (EB) in rat plasma and urine by high-performance liquid chromatography with electrogenerated chemiluminescence detection using Tris(2,2'-bipyridine)ruthenium(II). The recovery rates of EA, dClEA and EB were 97, 94 and 85% from rat plasma and 89, 83 and 93% from rat urine, respectively. The calibration curves were linear over the concentration ranges 0.05-5 microg/mL for plasma and 0.5-50 microg/mL for urine. The precision and accuracy for all analytes in rat plasma were < or =9.0 and -6.3-7.2%, and those in urine were < or =9.4% and -6.1-7.6%, respectively. This method proved to be a powerful tool for determination of EA, dClEA and EB concentrations in samples from rats. 相似文献
84.
Hiroaki Inoue Yuji Arai Tsunao Kishida Masaharu Shin-Ya Ryu Terauchi Shuji Nakagawa Masazumi Saito Shinji Tsuchida Atsuo Inoue Toshiharu Shirai Hiroyoshi Fujiwara Osam Mazda Toshikazu Kubo 《Ultrasonics》2014
The goal of this feasibility study was to examine whether sonoporation assisted transduction of siRNA could be used to ameliorate arthritis locally. If successful, such approach could provide an alternative treatment for the patients that have or gradually develop adverse response to chemical drugs. Tumor necrosis factor alpha (TNF-α) produced by synovial fibroblasts has an important role in the pathology of rheumatoid arthritis, inducing inflammation and bone destruction. In this study, we injected a mixture of microbubbles and siRNA targeting TNF-α (siTNF) into the articular joints of rats, and transduced siTNF into synovial tissue by exposure to a collimated ultrasound beam, applied through a probe 6 mm in diameter with an input frequency of 3.0 MHz, an output intensity of 2.0 W/cm2 (spatial average temporary peak; SATP), a pulse duty ratio of 50%, and a duration of 1 min. Sonoporation increased skin temperature from 26.8 °C to 27.3 °C, but there were no adverse effect such as burns. The mean level of TNF-α expression in siTNF-treated knee joints was 55% of those in controls. Delivery of siTNF into the knee joints every 3 days (i.e., 7, 10, 13, and 16 days after immunization) by in vivo sonoporation significantly reduced paw swelling on days 20–23 after immunization. Radiographic scores in the siTNF group were 56% of those in the CIA group and 61% of those in the siNeg group. Histological examination showed that the number of TNF-α positive cells was significantly lower in areas of pannus invasion into the ankle joints of siTNF- than of siNeg-treated rats. These results indicate that transduction of siTNF into articular synovium using sonoporation may be an effective local therapy for arthritis. 相似文献
85.
Tsuji M Gomi S Maeda Y Matsunaga M Hikino S Uto K Tsuji T Kawazumi H 《Langmuir : the ACS journal of surfaces and colloids》2012,28(24):8845-8861
Rapid sphere-to-prism (STP) transformation of silver was studied in aqueous AgNO(3)/NaBH(4)/polyvinylpyrrolidone (PVP)/trisodium citrate (Na(3)CA)/H(2)O(2) solutions by monitoring time-dependent surface plasmon resonance (SPR) bands in the UV-vis region, by examining transmission electron microscopic (TEM) images, and by analyzing emitted gases during fast reaction. Roles of PVP, Na(3)CA, and H(2)O(2) were studied without addition of a reagent, with different timing of each reagent's addition, and with addition of H(2)O(2) to mixtures of spheres and prisms. Results show that prisms can be prepared without addition of PVP, although it is useful to synthesize smaller monodispersed prisms. A new important role of citrate found in this study, besides a known role as a protecting agent of {111} facets of plates, is an assistive agent for shape-selective oxidative etching of Ag nanoparticles by H(2)O(2). The covering of Ag nanoparticles with carboxylate groups is necessary to initiate rapid STP transformation by premixing citrate before H(2)O(2) addition. Based on our data, rapid prism formation starts from the consumption of spherical Ag particles because of shape-selective oxidative etching by H(2)O(2). Oxidative etching of spherical particles by H(2)O(2) is faster than that of prisms. Therefore, spherical particles are selectively etched and dissolved, leaving only seeds of prisms to grow into triangular prisms. When pentagonal Ag nanorods and a mixture of cubes and bipyramids were used as sources of prisms, rod-to-prism (RTP), cube-to-prism (CTP), and bipyramid-to-prism (BTP) transformations were observed in Ag nanocrystals/NaBH(4)/PVP/Na(3)CA/H(2)O(2) solutions. Shape-selective oxidative etching of rods was confirmed using flag-type Ag nanostructures consisting of a triangular plate and a side rod. These data provide useful information for the size-controlled synthesis of triangular Ag prisms, from various Ag nanostructures and using a chemical reduction method, having surface plasmon resonance (SPR) bands at a desired wavelength. 相似文献
86.
Hiroshi Yabuno Hiroyuki Kaneko Masaharu Kuroda Takeshi Kobayashi 《Nonlinear dynamics》2008,52(1-2):137-149
A technique for dimensional reduction of nonlinear delay differential equations (DDEs) with time-periodic coefficients is
presented. The DDEs considered here have a canonical form with at most cubic nonlinearities and periodic coefficients. The
nonlinear terms are multiplied by a perturbation parameter. Perturbation expansion converts the nonlinear response problem
into solutions of a series of nonhomogeneous linear ordinary differential equations (ODEs) with time-periodic coefficients.
One set of linear nonhomogeneous ODEs is solved for each power of the perturbation parameter. Each ODE is solved by a Chebyshev
spectral collocation method. Thus we compute a finite approximation to the nonlinear infinite-dimensional map for the DDE.
The linear part of the map is the monodromy operator whose eigenvalues characterize stability. Dimensional reduction on the
map is then carried out. In the case of critical eigenvalues, this corresponds to center manifold reduction, while for the
noncritical case resonance conditions are derived. The accuracy of the nonlinear Chebyshev collocation map is demonstrated
by finding the solution of a nonlinear delayed Mathieu equation and then a milling model via the method of steps. Center manifold
reduction is illustrated via a single inverted pendulum including both a periodic retarded follower force and a nonlinear
restoring force. In this example, the amplitude of the limit cycle associated with a flip bifurcation is found analytically
and compared to that obtained from direct numerical simulation. The method of this paper is shown by example to be applicable
to systems with strong parametric excitations. 相似文献
87.
Toru Katsumata Masaharu Satoh Jun Wada Masashi Shiotsuki Fumio Sanda Toshio Masuda 《Macromolecular rapid communications》2006,27(15):1206-1211
Summary: 2,2,6,6‐Tetramethylpiperidine 1‐oxyl (TEMPO)‐containing N‐propargylamide HCCCH2NHCO‐4‐TEMPO ( 1 ), propargyl ester HCCCH2OCO‐4‐TEMPO ( 2 ), phenylacetylene derivative HCCC6H3‐3,4‐(CO2‐4‐TEMPO)2 ( 3 ), and norbornene diester monomers, NB‐2,3‐exo,exo‐(CH2OCO‐4‐TEMPO)2 ( 4 ), NB‐2,3‐endo,exo‐(COO‐4‐TEMPO)2 ( 5a ), NB‐2,3‐endo,endo‐(COO‐4‐TEMPO)2 ( 5b ) (NB = norbornene, TEMPO = 2,2,6,6‐tetramethyl‐1‐piperidinyloxyl) were synthesized and polymerized with rhodium and ruthenium catalysts. Monomers 2 , 5a , and 5b gave polymers with number‐average molecular weights of 47 000–185 000 in 59–100% yields, while 1 , 3 , and 4 gave polymers insoluble in common organic solvents in 88–100% yields. The capacities of cells fabricated with poly( 1 ), poly( 2 ), and poly( 3 ) were 67, 82, and 23 Ah · kg−1 based on the weight, respectively. The capacity of poly( 5a )‐based cell reached the theoretical value (109 Ah · kg−1) of the polymer.
88.
Prof. Takahisa Omata Aman Sharma Prof. Issei Suzuki Tomohiro Ishiyama Shinji Kohara Koji Ohara Prof. Madoka Ono Prof. Yang Ren Khurelbaatar Zagarzusem Prof. Masaya Fujioka Prof. Gaoyang Zhao Prof. Junji Nishii 《Chemphyschem》2022,23(3):e202100840
Anhydrous silicophosphoric acid glass with an approximate composition of H5Si2P9O29 was synthesized and its thermal and proton-conducting properties were characterized. Despite exhibiting a glass transition at 192 °C, the supercooled liquid could be handled as a solid up to 280 °C owing to its high viscosity. The glass and its melt exhibited proton conduction with a proton transport number of ∼1. Although covalent O−H bonds were weakened by relatively strong hydrogen bonding, the proton conductivity (4×10−4 S cm−1 at 276 °C) was considerably lower than that of phosphoric acid. The high viscosity of the melt was due to the tight cross-linking of phosphate ion chains by six-fold-coordinated Si atoms. The low proton conductivity was attributed to the trapping of positively charged proton carriers around anionic SiO6 units (expressed as (SiO6/2)2−) to compensate for the negative charges. 相似文献
89.
Halide ion conductivities of the complexes of cryptand[2.2.2] with alkali-metal halides or alkaline-earth metal halides were measured at 20–160°C. The halide ion conductivities of the complexes were found to be much higher than those of the crown ether complexes with alkali-metal halides or alkaline-earth metal halides. This is caused by the much weaker Coulomb attraction between metal-cation and halide ion in cryptand complexes than in crown ether complexes. 相似文献
90.