全文获取类型
收费全文 | 6346篇 |
免费 | 140篇 |
国内免费 | 44篇 |
专业分类
化学 | 4651篇 |
晶体学 | 66篇 |
力学 | 143篇 |
数学 | 722篇 |
物理学 | 948篇 |
出版年
2023年 | 26篇 |
2022年 | 48篇 |
2021年 | 52篇 |
2020年 | 78篇 |
2019年 | 96篇 |
2018年 | 68篇 |
2017年 | 48篇 |
2016年 | 129篇 |
2015年 | 108篇 |
2014年 | 120篇 |
2013年 | 310篇 |
2012年 | 373篇 |
2011年 | 462篇 |
2010年 | 220篇 |
2009年 | 194篇 |
2008年 | 401篇 |
2007年 | 451篇 |
2006年 | 445篇 |
2005年 | 435篇 |
2004年 | 398篇 |
2003年 | 316篇 |
2002年 | 280篇 |
2001年 | 98篇 |
2000年 | 73篇 |
1999年 | 73篇 |
1998年 | 79篇 |
1997年 | 56篇 |
1996年 | 84篇 |
1995年 | 63篇 |
1994年 | 59篇 |
1993年 | 44篇 |
1992年 | 44篇 |
1991年 | 48篇 |
1990年 | 44篇 |
1989年 | 36篇 |
1988年 | 39篇 |
1987年 | 35篇 |
1986年 | 32篇 |
1985年 | 53篇 |
1984年 | 54篇 |
1983年 | 49篇 |
1982年 | 47篇 |
1981年 | 49篇 |
1980年 | 44篇 |
1979年 | 44篇 |
1978年 | 49篇 |
1977年 | 40篇 |
1976年 | 38篇 |
1975年 | 24篇 |
1974年 | 25篇 |
排序方式: 共有6530条查询结果,搜索用时 15 毫秒
151.
Crystal engineering of novel cocrystals of a triazole drug with 1,4-dicarboxylic acids 总被引:4,自引:0,他引:4
Remenar JF Morissette SL Peterson ML Moulton B MacPhee JM Guzmán HR Almarsson O 《Journal of the American Chemical Society》2003,125(28):8456-8457
Cocrystals of the poorly soluble antifungal drug cis-itraconazole (1) with 1,4-dicarboxylic acids have been prepared. The crystal structure of the succinic acid cocrystal with 1 was determined to be a trimer by single-crystal X-ray. The trimer is comprised of two molecules of 1 oriented in antiparallel fashion to form a pocket with a triazole at either end. The extended succinic acid molecule fills the pocket, bridging the triazole groups through hydrogen-bonding interactions rather than interacting with the more basic piperazine nitrogens. The solubility and dissolution rate of some of the cocrystals are approximately the same as those of the amorphous drug in the commercial formulation and are much higher than those for the crystalline free base. The results suggest that cocrystals of drug molecules have the possibility of achieving the higher oral bioavailability common for amorphous forms of water-insoluble drugs while maintaining the long-term chemical and physical stability that crystal forms provide. 相似文献
152.
Lee S Stackow R Trevithick-Sutton C Foote CS Barrett AG Hoffman BM 《Photochemistry and photobiology》2003,77(1):18-21
We report the quantum yields for singlet oxygen production by a series of porphyrazines (pz) of the form M[pz(An;B4-n)] (Scheme 1), where the peripheral substituent A is [S-R]2 with R = (CH2CH2O)3H, B is a fused alpha,alpha'-dialkoxybenzo group and M = 2H, Mg or Zn. These compounds show intense near-IR absorbance/emission (longest wavelength emission, approximately 830 nm). Their solubilities vary with R, whereas their optical properties do not. We show that singlet oxygen sensitization by these luminescent compounds can be "tuned" from essentially off to on by varying n and selection among M = 2H, Mg or Zn. The quantum yields vary ca 60-fold within the set of compounds studied, from phidelta = 0.007 for compound 3 to phidelta = approximately 0.4 for compound 11. 相似文献
153.
Ring-opening/ring-closing metathesis on cyclobutene-containing substrates with angular oxygen functionality provides a stereospecific introduction of 1,5-bis-dienes required for an anion-accelerated oxy-Cope rearrangement. The reaction sequence offers generally a stereocontrolled preparation of a variety of medium ring-containing bicyclic ring systems, while rearrangement to the bicyclo[7,3,0]dodecane (9-5) system leads to a mixture of olefin isomers. 相似文献
154.
Horgan A Saunders B Vincent B Heenan RK 《Journal of colloid and interface science》2003,262(2):548-559
A series of water-soluble, amphiphilic graft copolymers has been prepared by free-radical copolymerization of methoxypoly(ethylene glycol) macromonomers, with either methyl methacrylate or butyl methacrylate as the comonomers, in water/ethanol solvent mixtures. Lower molecular weight copolymers were obtained by increasing the concentration of the initiator, azobisisobutyronitrile (AIBN), used in the polymerization reaction. However, the route used also led to the formation of significant quantities of tetramethylsuccinodinitrile, a toxic byproduct resulting from the cage reaction of AIBN. Static fluorescence measurements using pyrene as a probe, along with 1H NMR experiments, showed that the graft copolymers form aggregates in water at very low concentrations (approximately 0.01 g l(-1)) with the pendant hydrophilic graft chains forming a stabilizing shell around the hydrophobic backbone. An increase in the hydrophile-lipophile balance of the graft copolymers was found to lead to smaller aggregates with lower aggregation numbers and highly swollen hydrophilic shells, as revealed by small angle neutron scattering (SANS). 相似文献
155.
156.
Functionalized pyridylboronic acids and their Suzuki cross-coupling reactions to yield novel heteroarylpyridines 总被引:1,自引:0,他引:1
Parry PR Wang C Batsanov AS Bryce MR Tarbit B 《The Journal of organic chemistry》2002,67(21):7541-7543
2-Bromo-5-pyridylboronic acid 2a, 2-chloro-5-pyridylboronic acid 2b, 2-methoxy-5-pyridylboronic acid 2c, and 5-chloro-2-methoxy-4-pyridylboronic acid 4 have been synthesized and shown to undergo palladium-catalyzed cross-coupling reactions with heteroaryl bromides to yield novel heteroarylpyridine derivatives. The X-ray crystal structures of 2a and 2b have been obtained. 相似文献
157.
Grossman RB Hattori K Parkin S Patrick BO Varner MA 《Journal of the American Chemical Society》2002,124(46):13686-13687
A cage-shaped N,N'-diacylaminal crystallizes from some aromatic solvents as "supramolecular chair cyclohexanes", squat cylindrical hexamers with approximate D3d symmetry containing two arene molecules, and from other aromatic and nonaromatic solvents as infinite tapes. A homologous diacylaminal crystallizes only as an infinite tape. The hexamers represent the first examples of cyclic hexamers held together by %@mt;sys@%%@bold@%R%@rsf@%%@sx@%2%@be@%2%@sxx@%%@fn;(;vis;full;auto@%8%@fnx;);vis;full@%-type%@mx@% hydrogen bonds in which the hydrogen-bonded atoms are not coplanar. The diacylaminal represents a new supramolecular synthon, one perhaps more suited to the design of three-dimensional architectures. 相似文献
158.
Nucleation and growth of germanium nanowires seeded by organic monolayer-coated gold nanocrystals 总被引:9,自引:0,他引:9
Germanium nanowires, ranging from 10 to 150 nm in diameter, were grown several micrometers in length in cyclohexane heated and pressurized above its critical point. Alkanethiol-protected gold nanocrystals, either 2.5 or 6.5 nm in diameter, were used to seed wire formation. Growth proceeded through a solution-liquid-solid mechanism at growth temperatures ranging from 300 to 450 degrees C. At temperatures exceeding 500 degrees C, large Ge particulates formed due to unfavorable growth kinetics. Temperature, the nature of the precursor, precursor concentration, and the Au:Ge ratio were determining factors in nanowire morphology. The Ge nanowires were characterized using a range of techniques, including XPS, XRD, high-resolution TEM and SEM, nanometer-scale EDS mapping, and DTA. 相似文献
159.
Krzystek J Pardi LA Brunel LC Goldberg DP Hoffman BM Licoccia S Telser J 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2002,58(6):1113-1127
High-field and -frequency electron paramagnetic resonance (HFEPR) spectroscopy has been used to study three complexes of high spin Manganese(III), 3d4, S = 2. The complexes studied were tetraphenylporphyrinatomanganese(III) chloride (MnTPPCI), phthalocyanatomanganese(III) chloride (MnPcCl), and (8,12-diethyl-2,3,7,13,17,18-hexamethylcorrolato)manganese(III) (MnCor). We demonstrate the ability to obtain both field-oriented (single-crystal like) spectra and true powder pattern HFEPR spectra of solid samples. The latter are obtained by immobilizing the powder, either in an n-eicosane mull or KBr pellet. We can also obtain frozen solution HFEPR spectra with good signal-to-noise, and yielding the expected true powder pattern. Frozen solution spectra are described for MnTPPCl in 2:3 (v/v) toluene/CH2Cl2 solution and for MnCor in neat pyridine (py) solution. All of the HFEPR spectra have been fully analyzed using spectral simulation software and a complete set of spin Hamiltonian parameters has been determined for each complex in each medium. Both porphyrinic complexes (MnTPPCl and MnPcCl) are rigorously axial systems, with similar axial zero-field splitting (zfs): D approximately -2.3 cm(-1), and g values quite close to 2.00. In contrast, the corrole complex, MnCor, exhibits slightly larger magnitude, rhombic zfs: D approximtely -2.6 cm(-1), absolute value(E) approximately 0.015 cm(-1), also with g values quite close to 2.00. These results are discussed in terms of the molecular structures of these complexes and their electronic structure. We propose that there is a significant mixing of the triplet (S = 1) excited state with the quintet (S= 2) ground state in Mn(III) complexes with porphyrinic ligands, which is even more pronounced for corroles. 相似文献
160.
Warren J. Oldham Brian L. Scott Kent D. Abney Wayne H. Smith David A. Costa 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(3):m139-m140
In the title complex, [UCl(C2H6OS)7]Cl3, the uranium metal center is coordinated in a distorted bicapped trigonal prism geometry by seven O atoms from dimethyl sulfoxide ligands and by a terminal chloride ligand. Charge balance is maintained by three outer‐sphere chloride ions per uranium(IV) metal center. Principle bond lengths include U—O 2.391 (2)–2.315 (2) Å, U—Cl 2.7207 (9) Å, and average S—O 1.540 (5) Å. 相似文献