全文获取类型
收费全文 | 42626篇 |
免费 | 16244篇 |
国内免费 | 485篇 |
专业分类
化学 | 54881篇 |
晶体学 | 62篇 |
力学 | 1252篇 |
综合类 | 5篇 |
数学 | 1446篇 |
物理学 | 1709篇 |
出版年
2024年 | 427篇 |
2023年 | 4265篇 |
2022年 | 1514篇 |
2021年 | 2545篇 |
2020年 | 4787篇 |
2019年 | 2334篇 |
2018年 | 2460篇 |
2017年 | 701篇 |
2016年 | 5666篇 |
2015年 | 5645篇 |
2014年 | 5086篇 |
2013年 | 5263篇 |
2012年 | 3359篇 |
2011年 | 1287篇 |
2010年 | 3475篇 |
2009年 | 3463篇 |
2008年 | 1162篇 |
2007年 | 859篇 |
2006年 | 275篇 |
2005年 | 176篇 |
2004年 | 169篇 |
2003年 | 127篇 |
2002年 | 93篇 |
2001年 | 78篇 |
2000年 | 85篇 |
1999年 | 107篇 |
1997年 | 98篇 |
1996年 | 116篇 |
1995年 | 138篇 |
1994年 | 109篇 |
1993年 | 219篇 |
1992年 | 96篇 |
1991年 | 81篇 |
1988年 | 93篇 |
1987年 | 89篇 |
1982年 | 77篇 |
1981年 | 86篇 |
1980年 | 104篇 |
1979年 | 94篇 |
1978年 | 96篇 |
1977年 | 163篇 |
1976年 | 182篇 |
1975年 | 186篇 |
1974年 | 195篇 |
1973年 | 111篇 |
1972年 | 153篇 |
1971年 | 122篇 |
1970年 | 207篇 |
1969年 | 125篇 |
1968年 | 133篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
992.
Chensheng Ma Dr. Wai Ming Kwok Dr. Hui‐Ying An Xiangguo Guan Dr. Michael Yunyi Fu Patrick H. Toy Dr. David Lee Phillips Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(17):5102-5118
3′,5′‐Dimethoxybenzoin (DMB) is a bichromophoric system that has widespread application as a highly efficient photoremovable protecting group (PRPG) for the release of diverse functional groups. The photodeprotection of DMB phototriggers is remarkably clean, and is accompanied by the formation of a biologically benign cyclization product, 3′,5′‐dimethoxybenzofuran (DMBF). The underlying mechanism of the DMB deprotection and cyclization has, however, until now remained unclear. Femtosecond transient absorption (fs‐TA) spectroscopy and nanosecond time‐resolved resonance Raman (ns‐TR3) spectroscopy were employed to detect the transient species directly, and examine the dynamic transformations involved in the primary photoreactions for DMB diethyl phosphate (DMBDP) in acetonitrile (CH3CN). To assess the electronic character and the role played by the individual sub‐chromophore, that is, the benzoyl, and the di‐meta‐methoxybenzylic moieties, for the DMBDP deprotection, comparative fs‐TA measurements were also carried out for the reference compounds diethyl phosphate acetophenone (DPAP), and 3′,5′‐dimethoxybenzylic diethyl phosphate (DMBnDP) in the same solvent. Comparison of the fs‐TA spectra reveals that the photoexcited DMBDP exhibits distinctly different spectral character and dynamic evolution from those of the reference compounds. This fact, combined with the related steady‐state spectral and density functional theoretical results, strongly suggests the presence in DMBDP of a significant interaction between the two sub‐chromophores, and that this interaction plays a governing role in determining the nature of the photoexcitation and the reaction channel of the subsequent photophysical and photochemical transformations. The ns‐TR3 results and their correlation with the fs‐TA spectra and dynamics provide evidence for a novel concerted deprotection–cyclization mechanism for DMBDP in CH3CN. By monitoring the direct generation of the transient DMBF product, the cyclization time constant was determined unequivocally to be ≈1 ns. This indicates that there is little relevance for the long‐lived intermediates (>10 ns) in giving the DMBF product, and excludes the stepwise mechanism proposed in the literature as the major pathway for the DMB cyclization reaction. This work provides important new insights into the origin of the 3′,5′‐dimethoxy substitution effect for the DMB photodeprotection. It also helps to clarify the many different views presented in previous mechanistic studies of the DMB PRPGs. In addition to this, our fs‐TA results on the reference compound DMBnDP in CH3CN provide the first direct observation (to the best of our knowledge) showing the predominance of a prompt (≈2 ps) heterolytic bond cleavage after photoexcitation of meta‐methoxybenzylic compounds. This provides insight into the long‐term controversies about the photoinitiated dissociation mode of related substituted benzylic compounds. 相似文献
993.
Heqing Jiang Dr. Fangyi Liang Oliver Czuprat Konstantin Efimov Armin Feldhoff Dr. Steffen Schirrmeister Dr. Thomas Schiestel Dr. Haihui Wang Prof. Jürgen Caro Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(26):7898-7903
A porous perovskite BaCoxFeyZr0.9?x?yPd0.1O3?δ (BCFZ‐Pd) coating was deposited onto the outer surface of a BaCoxFeyZr1?x?yO3?δ (BCFZ) perovskite hollow‐fiber membrane. The surface morphology of the modified BCFZ fiber was characterized by scanning electron microscopy (SEM), indicating the formation of a BCFZ‐Pd porous layer on the outer surface of a dense BCFZ hollow‐fiber membrane. The oxygen permeation flux of the BCFZ membrane with a BCFZ‐Pd porous layer increased 3.5 times more than that of the blank BCFZ membrane when feeding reactive CH4 onto the permeation side of the membrane. The blank BCFZ membrane and surface‐modified BCFZ membrane were used as reactors to shift the equilibrium of thermal water dissociation for hydrogen production because they allow the selective removal of the produced oxygen from the water dissociation system. It was found that the hydrogen production rate increased from 0.7 to 2.1 mL H2 min?1 cm?2 at 950 °C after depositing a BCFZ‐Pd porous layer onto the BCFZ membrane. 相似文献
994.
Su‐Kyung Lee Kyong‐Soon Shin Dr. Dong‐Youn Noh Prof. Dr. Olivier Jeannin Dr. Frédéric Barrière Dr. Jean‐François Bergamini Dr. Marc Fourmigué Dr. 《化学:亚洲杂志》2010,5(1):169-176
The redox‐active and chelating diphosphine, 3,4‐dimethyl‐3′,4′‐bis(diphenylphosphino)‐tetrathiafulvalene, denoted as P2 , is engaged in a series of platinum complexes, [(P2)Pt(dithiolene)], with different dithiolate ligands, such as 1,2‐benzenedithiolate (bdt), 1,3‐dithiole‐2‐thione‐4,5‐dithiolate (dmit), and 5,6‐dihydro‐1,4‐dithiin‐2,3‐dithiolate (dddt). The complexes are structurally characterized by X‐ray diffraction, together with a model compound derived from bis(diphenylphosphino)ethane, namely, [(dppe)Pt(dddt)] . Four successive reversible electron‐transfer processes are found for the [(P2)Pt(dddt)] complex, associated with the two covalently linked but electronically uncoupled electrophores, that is, the TTF core and the platinum dithiolene moiety. The assignments of the different redox processes to either one or the other electrophore is made thanks to the electrochemical properties of the model compound [(dppe)Pt(dddt)] lacking the TTF redox core, and with the help of theoretical calculations (DFT) to understand the nature and energy of the frontier orbitals of the [(P2)Pt(dithiolene)] complexes in their different oxidation states. The first oxidation of the highly electron‐rich [(P2)Pt(dddt)] complex can be unambiguously assigned to the redox process affecting the Pt(dddt) moiety rather than the TTF core, a rare example in the coordination chemistry of tetrathiafulvalenes acting as ligands. 相似文献
995.
Kun Jiang Zhi‐Jun Jia Shi Chen Li Wu Ying‐Chun Chen Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(9):2852-2856
An efficient tandem reaction for the asymmetric synthesis of six‐membered spirocyclic oxindoles has been successfully developed through a formal [2+2+2] annulation strategy. The amine‐catalysed stereoselective Michael addition of aliphatic aldehydes to electron‐deficient olefinic oxindole motifs gave chiral C3 components, which were further combined with diverse electrophiles (activated olefins or imines) to afford spirocyclic oxindoles with versatile molecular complexity (up to six contiguous stereogenic centres, high diastereo‐ and enantioselectivities). 相似文献
996.
Andrzej Rajca Prof. Velavan Kathirvelu Dr. Sandip K. Roy Dr. Maren Pink Dr. Suchada Rajca Dr. Santanu Sarkar Sandra S. Eaton Prof. Gareth R. Eaton Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(19):5778-5782
Site‐directed spin labeling and EPR spectroscopy offer accurate, sensitive tools for the characterization of structure and function of macromolecules and their assemblies. A new rigid spin label, spirocyclohexyl nitroxide α‐amino acid and its N‐(9‐fluorenylmethoxycarbonyl) derivative, have been synthesized, which exhibit slow enough spin‐echo dephasing to permit accurate distance measurements by pulsed EPR spectroscopy at temperatures up to 125 K in 1:1 water/glycerol and at higher temperatures in matrices with higher glass transition temperatures. Distance measurements in the liquid nitrogen temperature range are less expensive than those that require liquid helium, which will greatly facilitate applications of pulsed EPR spectroscopy to the study of structure and conformation of peptides and proteins. 相似文献
997.
Lili Zhu Xiaodan Chen Qihua Zhao Zhongshu Li Xiangyang Zhang Baiwang Sun Prof. Dr. 《无机化学与普通化学杂志》2010,636(8):1441-1443
The novel heterospin complex [Ni2(PhCOO)4(NITpPy)2]·2CH3CN ( 1 ) was synthesized by the reaction of nickel benzoate and 2‐(4‐pyridyl)‐4,4,5,5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide (NITpPy) in acetonitrile and dichloromethane solutions. The X‐ray structure determination shows that complex 1 consists of a symmetrical dimeric NiII benzoate paddle‐wheel core and pyridyl nitrogen atoms of radical ligands at the apical position, in addition, the temperature (2–300K) dependent magnetic susceptibility measurements indicate that 1 has antiferromagnetic behavior. 相似文献
998.
B. Liu Y. F. Wang J. Wang J. Gao R. Xu Y. M. Kong L. Q. Zhang X. D. Zhang 《Journal of Structural Chemistry》2009,50(5):880-886
The title complexes, K2[EuIII(dtpa)(H2O)]·5H2O (H5dtpa = diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid), Na2[TbIII(Httha)]·6H2O (H6ttha = triethylenetetramine-N,N,N′,N′,N″,N″-hexaacetic acid), were prepared, and their compositions and structures were determined
by elemental analyses and single-crystal X-ray diffraction techniques. The crystal of K2[EuIII(dtpa)(H2O)]·5H2O belongs to triclinic crystal system and $
P\bar 1
$
P\bar 1
space group. The crystal data are as follows: a = 8.3540(17), b = 10.147(2), c = 15.059(3) α = 84.63(3)?, β = 82.02(3)°, γ = 83.96(3)°, V = 1253.1(4)?3, Z = 2, R = 0.0325 and wR = 0.1013 for 4407 observed reflections with I ≥ 2σ(I). The [EuIII(dtpa)(H2O)]2− has a nine-coordinate pseudo-monocapped square antiprismatic structure, in which the nine coordinate atoms, three N and six
O are from one dtpa ligand and one water molecule. The crystal of the Na2[TbIII(Httha)]·6H2O belongs to monoclinic system and P21/c space group. The crystal data are as follows: a = 10.3976(10), b = 12.7908(13), c = 23.199(2) ? = 90.914(2)°, V = 3084.9(5)?3, Z = 4, R = 0.0309 and wR = 0.0704 for 5429 observed reflections with I ≥ 2σ(I). In the [TbIII(Httha)]2−, the Tb3+ ion is nine-coordinated yielding a pseudo-monocapped square antiprismatic conformation, in which the ttha ligand coordinates
to the central Tb3+ ion with four N atoms and five O atoms. There is a free non-coordinate carboxyl group (−CH2COOH) that can be modified by some biological molecules having target function. 相似文献
999.
A facile Pd-catalyzed sequential reaction has been developed for the synthesis of δ-carbolines from 2-iodoanilines and N-tosyl-enynamines. This protocol involves Larock heteroannulation/elimination/electrocyclization/oxidative aromatization cascade sequences and allows access to multisubstituted δ-carbolines in moderate to good yields. 相似文献
1000.
Wu H Yuan J Bai Y Pan G Wang H Kong J Fan X Liu H 《Dalton transactions (Cambridge, England : 2003)》2012,41(29):8829-8838
A V-shaped ligand bis(2-benzimidazol-2-ylmethyl)benzylamine L(1) with its two derivatives bis(N-methylbenzimidazol-2-ylmethyl)benzylamine L(2) and bis(N-benzylbenzimidazol-2-ylmethyl)benzylamine L(3) have been prepared. Reaction of these shape-specific designed ligands with Ag(pic) (pic = picrate) afforded three novel complexes, namely, [Ag(2)L(1)(2)](pic)(2)1, [Ag(2)L(2)(2)](pic)(2)·2DMF 2 and [AgL(3)(pic)] 3. The ligands and complexes were characterized on the basis of elemental analysis, UV-Vis, IR, NMR spectroscopy and X-ray crystallography. Complex 1 is a dinuclear metallacycle with a 2-fold rotational symmetry in which two syn-conformational L(1) ligands are connected by two linearly coordinated Ag(I) atoms. Due to the strong interaction between two adjacent Ag(I) atoms, the coordination mode of the central Ag(I) atom can be described as T-shaped. Complex 2 consists of a centrosymmetric dinuclear pore canal structure assembled from two nearly linearly coordinated Ag(I) atoms and two L(2) ligands. The structure of complex 3 adopts a four-coordinate environment for AgN(2)O(2), with the counterion participating in an eight-shaped geometry. In order to explore the relationship between the structure and biological properties, the DNA-binding properties have been investigated by viscosity measurements, electronic absorption, and fluorescence. The results suggest that the ligands and complexes bind to DNA in an intercalation mode, and their binding affinities for DNA are also different. Moreover, the three Ag(I) complexes also exhibited potential antioxidant properties in vitro studies. 相似文献