全文获取类型
收费全文 | 464篇 |
免费 | 11篇 |
专业分类
化学 | 352篇 |
晶体学 | 1篇 |
力学 | 2篇 |
数学 | 22篇 |
物理学 | 98篇 |
出版年
2023年 | 7篇 |
2021年 | 3篇 |
2020年 | 8篇 |
2019年 | 5篇 |
2018年 | 3篇 |
2016年 | 7篇 |
2015年 | 7篇 |
2014年 | 8篇 |
2013年 | 10篇 |
2012年 | 24篇 |
2011年 | 19篇 |
2010年 | 15篇 |
2009年 | 12篇 |
2008年 | 29篇 |
2007年 | 27篇 |
2006年 | 31篇 |
2005年 | 31篇 |
2004年 | 31篇 |
2003年 | 23篇 |
2002年 | 18篇 |
2001年 | 17篇 |
2000年 | 17篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1997年 | 5篇 |
1996年 | 8篇 |
1995年 | 5篇 |
1994年 | 4篇 |
1993年 | 9篇 |
1992年 | 8篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 8篇 |
1986年 | 5篇 |
1985年 | 8篇 |
1984年 | 4篇 |
1983年 | 5篇 |
1980年 | 2篇 |
1978年 | 2篇 |
1975年 | 2篇 |
1974年 | 3篇 |
1972年 | 2篇 |
1942年 | 2篇 |
1938年 | 2篇 |
1937年 | 2篇 |
1936年 | 2篇 |
1932年 | 2篇 |
1929年 | 2篇 |
1919年 | 2篇 |
排序方式: 共有475条查询结果,搜索用时 31 毫秒
61.
Versatile pathways for in situ polyolefin functionalization with heteroatoms: catalytic chain transfer 总被引:1,自引:0,他引:1
Chain-transfer processes represent highly effective chemical means to achieve selective, in situ d- and f-block-metal catalyzed functionalization of polyolefins. A diverse variety of electron-poor and electron-rich chain-transfer agents, including silanes, boranes, alanes, phosphines, and amines, effect efficient chain termination with concomitant carbon-heteroelement bond formation during single-site olefin-polymerization processes. High polymerization activities, control of polyolefin molecular weight and microstructure, and selective chain functionalization are all possible, with distinctly different mechanisms operative for the electron-poor and electron-rich reagents. A variety of metal centers (early transition metals, lanthanides, late transition metals) and single-site ancillary ligand arrays (metallocene, half-metallocene, non-metallocene) are able to mediate these selective chain-termination/functionalization processes. 相似文献
62.
Letizia JA Salata MR Tribout CM Facchetti A Ratner MA Marks TJ 《Journal of the American Chemical Society》2008,130(30):9679-9694
Electron transporting (n-channel) polymer semiconductors for field-effect transistors are rare. In this investigation, the synthesis and characterization of new electron-depleted N-alkyl-2,2'-bithiophene-3,3'-dicarboximide-based pi-conjugated homopolymers and copolymers containing the 2,2'-bithiophene unit are reported. A novel design approach is employed using computational modeling to identify favorable monomer properties such as core planarity, solubilizing substituent tailorability, and appropriate electron affinity with gratifying results. Monomeric model compounds are synthesized to confirm these properties, and a crystal structure reveals a short 3.43 A pi-pi stacking distance with favorable solubilizing substituent orientations. A family of 10 homopolymers and bithiophene copolymers is then synthesized via Yamamoto and Stille polymerizations, respectively. Two of these polymers are processable in common organic solvents: the homopolymer poly(N-(2-octyldodecyl)-2,2'-bithiophene-3,3'-dicarboximide) (P1) exhibits n-channel FET activity, and the copolymer poly(N-(2-octyldodecyl)-2,2':5',2':5',2'-quaterthiophene-3,3'-dicarboximide) (P2) exhibits air-stable p-channel FET operation. After annealing, P1 films exhibit a very high degree of crystallinity and an electron mobility > 0.01 cm (2) V(-1) s(-1) with a current on-off ratio of 10 (7), which is remarkably independent of film-deposition conditions. Extraordinarily, P1 films also exhibit terracing in AFM images with a step height matching the X-ray diffraction d spacing, a rare phenomenon for polymeric organic semiconductors. Another fascinating property of these materials is the air-stable p-channel FET performance of annealed P2 films, which exhibit a hole mobility of approximately 0.01 cm(2) V(-1) s(-1) and a current on-off ratio of 10(7). 相似文献
63.
Andriy Kuklya Sasho Joksimoski Klaus Kerpen Florian Uteschil Robert Marks Ursula Telgheder 《International Journal for Ion Mobility Spectrometry》2016,19(2-3):121-130
In this study the influence of aromatic dopant benzene on the sensitivity of GC-APPI-DMS to gasoline related aromatic compounds was investigated. This influence was investigated on example of four gasolin related fingerprints (toluene, ethylbenzene, o-xylene, and 1,2,4-trimethylbenzene), which were found in high relative abundance in the water-soluble gasoline fraction. The analysis of calibration curves slopes demonstrats that the GC-APPI-DMS sensitivity to gasoline fingerprints can be improved by up to seven times when benzene concentration in nitrogen carrier gas is less than 10 ppmv/v. The estimated detection limits (S/N?=?3) for the analyzed in this study compounds were found to be within the range of 33–105 μg L?1 at benzene concentration in the carrier gas of 2.27 ppmv/v (10 μL injection volume). These limits of detection may be reduced (at the cost of lower resolution) using the larger injection volumes. For example, increase of injection volume to 100 μL at benzene concentration in the carrier gas of 2.27 ppmv/v leads to reduction of LOD values for toluene, ethylbenzene, and o-xylene to 11.1, 13.3, and 5.3 μg L?1, respectively. 相似文献
64.
Single‐Face/All‐cis Arene Hydrogenation by a Supported Single‐Site d0 Organozirconium Catalyst
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Madelyn Marie Stalzer Dr. Christopher P. Nicholas Dr. Alak Bhattacharyya Dr. Alessandro Motta Dr. Massimiliano Delferro Prof. Tobin J. Marks 《Angewandte Chemie (International ed. in English)》2016,55(17):5263-5267
The single‐site supported organozirconium catalyst Cp*ZrBz2/ZrS (Cp*=Me5C5, Bz=benzyl, ZrS=sulfated zirconia) catalyzes the single‐face/all‐cis hydrogenation of a large series of alkylated and fused arene derivatives to the corresponding all‐cis‐cyclohexanes. Kinetic/mechanistic and DFT analysis argue that stereoselection involves rapid, sequential H2 delivery to a single catalyst‐bound arene face, versus any competing intramolecular arene π‐face interchange. 相似文献
65.
A series of "constrained geometry" organoactinide complexes, (CGC)An(NMe)2 (CGC = Me2Si(eta5-Me4C5)(tBuN); An = Th, 1; U, 2), has been prepared via efficient in situ, two-step protodeamination routes in good yields and high purity. Both 1 and 2 are quantitatively converted to the neutrally charged, solvent-free dichlorides (1-Cl2, 2-Cl2) and slightly more soluble diiodides (1-I2, 2-I2) with excess Me3Si-X (X = Cl, I) in non-coordinating solvents. The new complexes were characterized by NMR spectroscopy, elemental analysis, and (for 1 and 2) single-crystal X-ray diffraction, revealing substantially increased metal coordinative unsaturation vs the corresponding Me2SiCp' '2AnR2 (Cp' ' = eta5-Me4C5; An = Th, R = CH2(SiMe3), 3; An = U, R = CH2Ph, 4) and Cp'2AnR2 (Cp' = eta5-Me5C5 ; An = Th, R = CH2(SiMe3), 5; An = U, R = CH2(SiMe3), 6) complexes. Complexes 1-6 exhibit broad applicability for the intramolecular hydroamination of diverse C-C unsaturations, including terminal and internal aminoalkenes (primary and secondary amines), aminoalkynes (primary and secondary amines), aminoallenes, and aminodienes. Large turnover frequencies (Nt up to 3000 h-1) and high regioselectivities (>/=95%) are observed throughout, along with moderate to high diastereoselectivities (up to 90% trans ring closures). With several noteworthy exceptions, reactivity trends track relative 5f ionic radii and ancillary ligand coordinative unsaturation. Reactivity patterns and activation parameters are consistent with a reaction pathway proceeding via turnover-limiting C=C/CC insertion into the An-N sigma-bond. 相似文献
66.
Phan AT Kuryavyi V Burge S Neidle S Patel DJ 《Journal of the American Chemical Society》2007,129(14):4386-4392
The c-kit oncogene is an important target in the treatment of gastrointestinal tumors. A potential approach to inhibition of the expression of this gene involves selective stabilization of G-quadruplex structures that may be induced to form in the c-kit promoter region. Here we report on the structure of an unprecedented intramolecular G-quadruplex formed by a G-rich sequence in the c-kit promoter in K+ solution. The structure represents a new folding topology with several unique features. Most strikingly, an isolated guanine is involved in G-tetrad core formation, despite the presence of four three-guanine tracts. There are four loops: two single-residue double-chain-reversal loops, a two-residue loop, and a five-residue stem-loop, which contain base-pairing alignments. This unique structural scaffold provides a highly specific platform for the future design of ligands specifically targeted to the promoter DNA of c-kit. 相似文献
67.
Stabilisation of human telomeric quadruplex DNA and inhibition of telomerase by a platinum-phenanthroline complex 总被引:1,自引:0,他引:1
Two new mono-substituted phenanthroline ligands and their platinum(II) square planar complexes have been prepared; one of the complexes has been shown to induce a high degree of quadruplex DNA stabilisation and to inhibit telomerase. 相似文献
68.
M. J. Marks S. Munjal S. Namhata D. C. Scott F. Bosscher J. A. De Letter B. Klumperman 《Journal of polymer science. Part A, Polymer chemistry》2000,38(3):560-570
Randomly branched bisphenol A polycarbonates (PCs) were prepared by interfacial polymerization methods to explore the limits of gel‐free compositions available by the adjustment of various composition and process variables. A molecular weight distribution (MWD) model was devised to predict the MWD, G, and weight‐average molecular weight per arm (Mw /arm) values based on the composition variables. The amounts of the monomer, branching agent, and chain terminator must be adjusted such that the weight‐average functionality of the phenolic monomers (FOH ) was less than 2 to preclude gel formation in both the long‐ and short‐chain branched (SCB) PCs. Several series of SCB and long‐chain branched PCs were prepared, and those lacking gels showed molecular weights measured by gel permeation chromatography–UV and gel permeation chromatography–LS consistent with model calculations. In SCB PCs, the minimum Mw /arm that could be realized without gel formation depended on both composition (molecular weight, terminator type) and process (terminator addition point, coupling catalyst) variables. The minimum Mw /arm achieved in the low molecular weight series studied ranged from ∼3300 to ∼1000. The use of long chain alkyl phenol terminators gave branched PCs with lower glass‐transition temperatures but a higher gel‐free minimum Mw /arm. SCB PCs where Mw /arm was less than ∼Mc spontaneously cracked after compression molding, a result attributed to their lack of polymer chain entanglements. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 560–570, 2000 相似文献
69.
Beverly S Colley Melissa A Cavallin KC Biju David R Marks Debra A Fadool 《BMC neuroscience》2009,10(1):8
Background
Neurotrophins are important regulators of growth and regeneration, and acutely, they can modulate the activity of voltage-gated ion channels. Previously we have shown that acute brain-derived neurotrophic factor (BDNF) activation of neurotrophin receptor tyrosine kinase B (TrkB) suppresses the Shaker voltage-gated potassium channel (Kv1.3) via phosphorylation of multiple tyrosine residues in the N and C terminal aspects of the channel protein. It is not known how adaptor proteins, which lack catalytic activity, but interact with members of the neurotrophic signaling pathway, might scaffold with ion channels or modulate channel activity. 相似文献70.
Immunosensors are powerful analytical tools in clinical and veterinary diagnostics. This has led us to design a chemiluminescent immunosensor aimed at identifying anti-Brucella antibodies using optical fibers as the transducer. In order to develop the optimal transducer, to achieve an optimal chemical modification thereby allowing an optimal covalent binding of the protein receptor, several cleaning strategies and silane coupling agents were investigated. Brucella killed organisms were used as a model receptor for quantifying anti-Brucella IgG antibodies in a suspension compared to conventional colorimetric and chemiluminescent ELISA. A silane-benzophenone derivative was selected as the best performing silane coupling agent: the optical fiber immunosensor (OFIS) has showed the lowest limit of detection at 0.207 μg/ml, compared to 0.828 μg/ml and 0.414 μg/ml achieved by colorimetric and chemiluminescent ELISAs, respectively. These results, together with the additional advantages of rapidity, lower reagent volumes and moderate operating conditions, have set the grounds for further study in order to adapt this platform for on-site diagnostics of brucellosis disease markers. 相似文献