全文获取类型
收费全文 | 587篇 |
免费 | 3篇 |
国内免费 | 1篇 |
专业分类
化学 | 453篇 |
晶体学 | 2篇 |
力学 | 4篇 |
数学 | 78篇 |
物理学 | 54篇 |
出版年
2018年 | 6篇 |
2017年 | 5篇 |
2016年 | 8篇 |
2015年 | 5篇 |
2013年 | 16篇 |
2012年 | 6篇 |
2011年 | 17篇 |
2010年 | 7篇 |
2009年 | 12篇 |
2008年 | 14篇 |
2007年 | 12篇 |
2006年 | 17篇 |
2005年 | 8篇 |
2004年 | 19篇 |
2003年 | 9篇 |
2002年 | 13篇 |
2000年 | 7篇 |
1999年 | 6篇 |
1944年 | 9篇 |
1943年 | 7篇 |
1928年 | 6篇 |
1919年 | 5篇 |
1916年 | 7篇 |
1915年 | 8篇 |
1913年 | 5篇 |
1911年 | 8篇 |
1910年 | 12篇 |
1909年 | 10篇 |
1908年 | 7篇 |
1907年 | 8篇 |
1905年 | 5篇 |
1904年 | 6篇 |
1902年 | 5篇 |
1901年 | 8篇 |
1900年 | 12篇 |
1899年 | 6篇 |
1898年 | 11篇 |
1897年 | 6篇 |
1895年 | 7篇 |
1894年 | 5篇 |
1892年 | 11篇 |
1891年 | 12篇 |
1890年 | 9篇 |
1889年 | 6篇 |
1888年 | 6篇 |
1883年 | 5篇 |
1882年 | 10篇 |
1870年 | 8篇 |
1869年 | 5篇 |
1866年 | 7篇 |
排序方式: 共有591条查询结果,搜索用时 15 毫秒
581.
Powell N Dudley E Morishita M Bogdanova T Tronko M Thomas G 《Rapid communications in mass spectrometry : RCM》2004,18(19):2249-2254
Data derived from analysis of single nucleotide polymorphisms (SNPs) are being applied in many diverse fields, from medical studies of disease mechanisms and individual drug response, to population genetics for tracking migration and mixing of ancestral groups and also in forensic science for the identification of human remains and identification of individuals from bodily samples. All these applications have in common the need to generate data for multiple loci from large numbers of samples. Matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS) is a promising platform for the generation of such data and we present a simple, flexible and robust technique for SNP determination. We demonstrate these features by typing two SNPs (Q276P and R326Q) in the human phosphatase gene PTPrj, which has been implicated in the aetiology of colon, lung, breast and thyroid cancers. A nucleotide depletion primer extension assay using no commercial kits or dideoxyNTPs was used to genotype a panel of DNAs derived from thyroid cancer patients and normal volunteers. The results obtained were in perfect agreement with those generated via restriction fragment length polymorphism analysis. No significant association was noted between possession of either allelic variant and a disease state, but the technique was validated as simple, flexible and appropriate for application in this context. Furthermore, it was highly cost-effective and required minimal optimisation, rendering it ideal for this type of pilot study. 相似文献
582.
We analyze the multiple-quantum dynamics governed by a new homonuclear recoupling strategy effecting an average dipolar Hamiltonian comprising three-spin triple-quantum operators (e.g., S(p)+S(q)+S(r)+) under magic-angle spinning conditions. Analytical expressions are presented for polarization transfer processes in systems of three and four coupled spins-1/2 subject to triple-quantum filtration (3QF), and high-order multiple-quantum excitation is investigated numerically in moderately large clusters, comprising up to seven spins. This recoupling approach gives highly efficient excitation of triple-quantum coherences: ideally, up to 67% of the initial polarization may be recovered by 3QF in three-spin systems in polycrystalline powders. Two homonuclear 2D correlation strategies are demonstrated experimentally on powders of uniformly 13C-labeled alanine and tyrosine: the first correlates the single-quantum spectrum in the first dimension with the corresponding 3QF spectrum along the other. The second protocol correlates triple-quantum coherences with their corresponding single-quantum coherences within triplets of coupled spins. 相似文献
583.
The synthesis of the germination self-inhibitor (-)-Gloeosporone is reported. The embedded 1,7-diol motif in the product is constructed by an ironcarbonyl tether controlled Mukaiyama aldol reaction. The key step in the synthesis is the reductive removal of the ligating iron species by treatment of an acetoxycomplex 6 with lithium naphthalenide. 相似文献
584.
Andrews DM Barnes MC Dowle MD Hind SL Johnson MR Jones PS Mills G Patikis A Pateman TJ Redfern TJ Robinson JE Slater MJ Trivedi N 《Organic letters》2003,5(24):4631-4634
[reaction: see text] In this, the second of two Letters, the optimization of the pyrrolidine-5,5-trans-lactam template (exemplified by 1a) as a mechanism-based inhibitor of hepatitis C NS3/4A protease is described. "Right Box" analysis of cassette dosing screening pharmacokinetic data was used to rapidly categorize the compounds. GW0014 (compound 4d) emerged as the compound displaying an optimal balance of biochemical and replicon potency, along with low i.v. clearance in the dog. 相似文献
585.
Ruud W. Busker Gerard M. J. Beijersbergen van Henegouwen Ed. P. van Ballegooie Wendie Vasbinder 《Photochemistry and photobiology》1988,48(5):683-688
Abstract— Allergic reactions to the widely applied urinary tract disinfectant nitrofurantoin (NFT) often concern the skin. They are probably mediated by a NFT-protein adduct. which has been suggested to result from incomplete nitro-reduction during metabolism. In this study it was investigated whether photoactivation of NFT in rats, upon exposure to UV-A, leads to formation of adducts between the drug and biomacromolecules. Rats were given p.o. doses of [14 C]-NFT, and some were exposed to UV-A. More irreversible binding was found in skin of the back (both in dermis and in epidermis). tail, ears, eyes, plasma proteins, and spleen of light-exposed rats compared to those kept in the dark. This photobinding increased (up to ∼0.6 nmol/mg protein =∼25 nmol/g tissue) with dose and light-intensity. When rats were kept at 32°C, instead of 22°C during NFT/UV-A treatment, even more irreversible binding was observed; this is probably caused by an increased dermal blood flow. Under these conditions, irreversibly bound radioactivity was even found in kidney, lung and liver. Irreversible binding in these inner organs is explained by systemic distribution of radioactivity, photobound to plasma proteins. Photodecomposition of NFT in the skin, followed by reaction of photoproducts with (cellular) biomacromolecules may explain some of the skin rashes and other (allergic) reactions reported for this drug. 相似文献
586.
587.
Jason Stafford Ed Walsh Vanessa Egan 《International Journal of Heat and Fluid Flow》2011,32(6):1160-1172
Scaled versions of fan designs are often chosen to address thermal management issues in space constrained applications. Using velocity field and local heat transfer measurement techniques, the thermal performance characteristics of a range of geometrically scaled centrifugal fan designs have been investigated. Complex fluid flow structures and surface heat transfer trends due to centrifugal fans were found to be common over a wide range of fan aspect ratios (blade height to fan diameter). The limiting aspect ratio for heat transfer enhancement was 0.3, as larger aspect ratios were shown to result in a reduction in overall thermal performance. Over the range of fans examined, the low profile centrifugal designs produced significant enhancement in thermal performance when compared to that predicted using classical laminar flow theory. The limiting non-dimensional distance from the fan, where this enhancement is no longer apparent, has also been determined. Using the fundamental information inferred from local velocity field and heat transfer measurements, selection criteria can be determined for both low and high power practical applications where space restrictions exist. 相似文献
588.
Carrara Vda S Serra LZ Cardozo-Filho L Cunha EF Torres-Santos EC Cortez DA 《Molecules (Basel, Switzerland)》2011,17(1):15-33
Piper amalago L. leaves were extracted with supercritical carbon dioxide and compressed propane under different conditions, and with chloroform by the conventional maceration method. These methods were compared for the pyrrolidine alkaloid content. Supercritical carbon dioxide (SFE-CO?) at 313 K and 12.55 MPa showed the highest selectivity for the main compound (600.53 mg/g of extract). A gradient high-performance liquid chromatography (HPLC) method was developed and validated to quantify the alkaloid N-[7-(3',4'-methylenedioxyphenyl)-2(Z),4(Z)-heptadienoyl]pyrrolidine in the extracts. The HPLC method showed linearity, precision and accuracy, allowing the quantitative analysis of the alkaloid in all the samples. All the extracts were tested against the promastigote and intracellular amastigote forms of Leishmania amazonensis. The antileishmanial activity was evaluated in terms of inhibitory concentration for 50% of protozoa (IC??). The cytotoxicity was also evaluated against J774A1 macrophages, and the cytotoxic concentrations for 50% of macrophages were obtained (CC??). The SFE-CO? (313 K; 12.55 MPa) extract showed the highest antileishmanial activity with the following IC?? values of 16 and 7 μg/mL against the promastigotes and intracellular amastigotes forms, respectively. The extract showed low cytotoxicity with a CC?? value of 93 μg/mL. 相似文献
589.
Kyle AF Jakubec P Cockfield DM Cleator E Skidmore J Dixon DJ 《Chemical communications (Cambridge, England)》2011,47(36):10037-10039
A highly diastereoselective bifunctional organocatalyst controlled Michael addition, a nitro-Mannich/lactamization cascade, a furan N-acyliminium cyclisation, a sequential alkyne RCM/syn-reduction and an alkene RCM has allowed a 19 step, highly stereoselective synthesis of (-)-nakadomarin A. 相似文献
590.
The preparation and reactions of optically and chemically stable (S)-4-hydroxy-1,3-dioxolane 3 as a 2-hydroxy aldehyde equivalent were explored. Hydroxydioxolane 3 was prepared by reduction of ketodioxolane 2 which was obtained from (S)-2-hydroxycarboxylic acid 1. The reactions of 3 with triethyl phosphonoacetate and organometallic reagents were carried out. These and other conversions gave synthetically and biologically useful products in moderate to good chemical and moderate stereochemical yields. 相似文献