全文获取类型
收费全文 | 1711篇 |
免费 | 40篇 |
国内免费 | 13篇 |
专业分类
化学 | 1184篇 |
晶体学 | 29篇 |
力学 | 31篇 |
数学 | 123篇 |
物理学 | 397篇 |
出版年
2023年 | 13篇 |
2022年 | 19篇 |
2021年 | 18篇 |
2020年 | 16篇 |
2019年 | 21篇 |
2018年 | 12篇 |
2017年 | 12篇 |
2016年 | 28篇 |
2015年 | 33篇 |
2014年 | 38篇 |
2013年 | 108篇 |
2012年 | 92篇 |
2011年 | 84篇 |
2010年 | 54篇 |
2009年 | 54篇 |
2008年 | 88篇 |
2007年 | 121篇 |
2006年 | 93篇 |
2005年 | 94篇 |
2004年 | 79篇 |
2003年 | 80篇 |
2002年 | 75篇 |
2001年 | 40篇 |
2000年 | 27篇 |
1999年 | 37篇 |
1998年 | 14篇 |
1997年 | 19篇 |
1996年 | 22篇 |
1995年 | 16篇 |
1994年 | 16篇 |
1993年 | 19篇 |
1992年 | 18篇 |
1991年 | 14篇 |
1990年 | 13篇 |
1989年 | 16篇 |
1988年 | 9篇 |
1987年 | 13篇 |
1986年 | 14篇 |
1985年 | 25篇 |
1984年 | 31篇 |
1983年 | 19篇 |
1982年 | 18篇 |
1981年 | 20篇 |
1980年 | 15篇 |
1979年 | 21篇 |
1978年 | 13篇 |
1977年 | 10篇 |
1976年 | 10篇 |
1975年 | 8篇 |
1973年 | 11篇 |
排序方式: 共有1764条查询结果,搜索用时 0 毫秒
41.
Koga T Taguchi K Kobuke Y Kinoshita T Higuchi M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(5):1146-1156
The self-assembly of peptides and proteins into beta-sheet-rich high-order structures has attracted much attention as a result of the characteristic nanostructure of these assemblies and because of their association with neurodegenerative diseases. Here we report the structural and conformational properties of a peptide-conjugated graft copolymer, poly(gamma-methyl-L-glutamate) grafted polyallylamine (1) in a water-2,2,2-trifluoroethanol solution as a simple model for amyloid formation. Atomic force microscopy revealed that the globular peptide 1 self-assembles into nonbranching fibrils that are about 4 nm in height under certain conditions. These fibrils are rich in beta-sheets and, similar to authentic amyloid fibrils, bind the amyloidophilic dye Congo red. The secondary and quaternary structures of the peptide 1 can be controlled by manipulating the pH, solution composition, and salt concentration; this indicates that the three-dimensional packing arrangement of peptide chains is the key factor for such fibril formation. Furthermore, the addition of carboxylic acid-terminated poly(ethylene glycol), which interacts with both of amino groups of 1 and hydrophobic PMLG chains, was found to obviously inhibit the alpha-to-beta structural transition for non-assembled peptide 1 and to partially cause a beta-to-alpha structural transition against the 1-assembly in the beta-sheet form. These findings demonstrate that the amyloid fibril formation is not restricted to specific protein sequences but rather is a generic property of peptides. The ability to control the assembled structure of the peptide should provide useful information not only for understanding the amyloid fibril formation, but also for developing novel peptide-based material with well-defined nanostructures. 相似文献
42.
Minoo Jalili Moghaddam Shigeo Hozumi Yoshiaki Inaki Kiichi Takemoto 《Journal of polymer science. Part A, Polymer chemistry》1988,26(12):3297-3308
Polyamides containing thymine photodimer units in the main chain were synthesized, and their photolysis by ultraviolet irradiation below 260 nm were studied in film state. Photodimers of thymine derivatives were obtained by photochemical reaction of the carboxylic acid derivatives of thymine in aqueous solution irradiated above 270 nm. An attempt was made to resolve the isomers of the photodimers, and the two kinds of cis isomers [cis–syn(head to head), and cis–anti(head to tail)] were isolated successfully. The polyamides were prepared by condensation of the photodimers with diamine using an activated ester method. The photodissociation of the thymine photodimer in the polymer main chain caused the breakage of the polymer chains, leading to the production of oligomers and dimer compounds containing thymine bases at the ends of the molecule. The dissociation rate of the polymer did not depend on the kind of the thymine photodimer which was in the main chain of the polymer. 相似文献
43.
Yasuhiko Kawamura Kohji Akitomo Masaaki Oe Tokunaru Horie Masao Tsukayama 《Tetrahedron letters》1997,38(52):3610-8992
Upon irradiation (>340 nm) of a benzene solution of diazofluorene with di-p-tolyl- or di-p-anisyl disulfide, the corresponding 9,9′-bis(arylmercapto)bifluorenyl was afforded in moderate to good yield accompanied by formation of 9,9′-bis(arylmercapto)fluorene. The major reaction pathway is considered to be a disulfur ylide formation followed by two times of successive Stevens rearrangement or by concerted electron redistribution via [2,3]sigmatropic rearrangement. 相似文献
44.
A highly sensitive method for the determination of propafenone in plasma has been established using gas chromatography-mass spectrometry with the deuterium-labelled compound as an internal standard. Plasma levels as low as 1 ng/ml were measured using 0.5-ml plasma samples. Plasma protein binding of the drug in rats, dogs and humans in vitro and in vivo was determined by the proposed method. About 90% of the drug was bound to the plasma protein in all species in vitro (20-500 ng/ml) and 69-88% in rats, 90-95% in dogs and 77-89% in humans after oral administration of the drug at doses of 50 mg/kg, 5 mg/kg and 200 mg per person, respectively. 相似文献
45.
46.
The spectrophotometric determination of ammonium ion in water by flow-injection analysis with a membrane-separator and a pH indicator for detection is studied in detail. The relations derived facilitate the selection of appropriate solution compositions or the prediction of sensitivity. It is shown that 1.5×10?5 M bromocresol purple (pH 6.8) as acceptor solution gives the maximal sensitivity in the flow system with a laboratory-made separation unit. Application of ultrasonic radiation in the separation step and the use of different flow rates for the donor and acceptor streams may result in increased permeation of ammonia and a correspondingly high sensitivity. By modifying the acceptor solution so that the sensitivity is decreased, more concentrated samples such as urine can be analyzed by direct injection without prior dilution. In this procedure, the sample rate was 60 h?1 for ammonium concentration of more than 10?5 M and 30–40 h?1 for concentrations in the range 3×10?7?10?5 M. The detection limit was about 3×10?7 M. 相似文献
47.
Tsutsumi T Amakura Y Nakamura M Brown DJ Clark GC Sasaki K Toyoda M Maitani T 《The Analyst》2003,128(5):486-492
The chemical-activated luciferase expression (CALUX) assay is a reporter gene assay that detects dioxin-like compounds based on their ability to activate the aryl hydrocarbon receptor (AhR) and thus expression of the reporter gene. In this paper, the CALUX assay was examined for its application in the screening of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) in retail fish. The sample extracts were cleaned up on a sulfuric acid-silica gel column followed by an activated carbon column, and the AhR activity of the separated PCDD/F and dioxin-like PCB fractions was determined using the assay. The quantitative limit for 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) was 0.98 pg ml(-1) (0.19 pg assay(-1) in the standard curve, corresponding to 0.16 pg g(-1) of CALUX-based toxic equivalency (2,3,7,8-TCDD equivalents) in the tested sample. Recovery tests in which dioxins were added to fish samples resulted in acceptable recoveries (77-117%). The CALUX assay performed well in the analysis of dioxins in fish samples and a comparative study revealed a strong correlation between the CALUX assay and high-resolution gas chromatography-high-resolution mass spectrometry analysis for the determination of PCDD/Fs (r = 0.89) and dioxin-like PCBs (r = 0.91) in retail fish (n = 22). These data revealed that the CALUX assay would be a useful screening method for PCDD/Fs and dioxin-like PCBs in retail fish. 相似文献
48.
Kana Kobayashi-Taguchi Takashi Saitou Yoshiaki Kamei Akari Murakami Kanako Nishiyama Reina Aoki Erina Kusakabe Haruna Noda Michiko Yamashita Riko Kitazawa Takeshi Imamura Yasutsugu Takada 《Molecules (Basel, Switzerland)》2022,27(10)
Fibroadenomas (FAs) and phyllodes tumors (PTs) are major benign breast tumors, pathologically classified as fibroepithelial tumors. Although the clinical management of PTs differs from FAs, distinction by core needle biopsy diagnoses is still challenging. Here, a combined technique of label-free imaging with multi-photon microscopy and artificial intelligence was applied to detect quantitative signatures that differentiate fibroepithelial lesions. Multi-photon excited autofluorescence and second harmonic generation (SHG) signals were detected in tissue sections. A pixel-wise semantic segmentation method using a deep learning framework was used to separate epithelial and stromal regions automatically. The epithelial to stromal area ratio and the collagen SHG signal strength were investigated for their ability to distinguish fibroepithelial lesions. An image segmentation analysis with a pixel-wise semantic segmentation framework using a deep convolutional neural network showed the accurate separation of epithelial and stromal regions. A further investigation, to determine if scoring the epithelial to stromal area ratio and the SHG signal strength within the stromal area could be a marker for differentiating fibroepithelial tumors, showed accurate classification. Therefore, molecular and morphological changes, detected through the assistance of computational and label-free multi-photon imaging techniques, enable us to propose quantitative signatures for epithelial and stromal alterations in breast tissues. 相似文献
49.
Enantioselective copper-catalyzed 1,4-additions of dialkylzincs to enones were carried out in the presence of 1 mol % of Cu(OTf)2 and 2.5 mol % of an N,N,P-ligand possessing a tert-butyl group at the adjacent position of the nitrogen of pyridine to afford the corresponding 1,4-adducts in up to 98% ee. 相似文献
50.