全文获取类型
收费全文 | 601篇 |
免费 | 11篇 |
国内免费 | 2篇 |
专业分类
化学 | 418篇 |
晶体学 | 7篇 |
力学 | 9篇 |
数学 | 130篇 |
物理学 | 50篇 |
出版年
2022年 | 2篇 |
2021年 | 5篇 |
2020年 | 8篇 |
2019年 | 5篇 |
2018年 | 3篇 |
2017年 | 7篇 |
2016年 | 11篇 |
2015年 | 21篇 |
2014年 | 14篇 |
2013年 | 39篇 |
2012年 | 33篇 |
2011年 | 33篇 |
2010年 | 16篇 |
2009年 | 20篇 |
2008年 | 23篇 |
2007年 | 40篇 |
2006年 | 28篇 |
2005年 | 24篇 |
2004年 | 20篇 |
2003年 | 31篇 |
2002年 | 22篇 |
2001年 | 8篇 |
2000年 | 12篇 |
1999年 | 13篇 |
1998年 | 6篇 |
1997年 | 10篇 |
1996年 | 9篇 |
1995年 | 13篇 |
1994年 | 8篇 |
1993年 | 10篇 |
1992年 | 12篇 |
1991年 | 7篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 6篇 |
1987年 | 7篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 9篇 |
1981年 | 4篇 |
1980年 | 9篇 |
1979年 | 4篇 |
1978年 | 9篇 |
1977年 | 7篇 |
1976年 | 6篇 |
1975年 | 7篇 |
1974年 | 4篇 |
1973年 | 3篇 |
1966年 | 3篇 |
排序方式: 共有614条查询结果,搜索用时 15 毫秒
21.
Monique G.A. da Silva Ábner M. Nunes Simoni M.P. Meneghetti Mario R. Meneghetti 《Comptes Rendus Chimie》2013,16(7):640-650
Gold nanorods (AuNRs) were obtained via a wet chemistry technique, in aqueous medium, employing crystallisation seeds. The kinetics of formation, the aspect ratio, and the selectivity of the particles were evaluated according to the parameters of synthesis: the growth-driving agent, seed, and gold precursor concentrations. In 2–4 h, the rod particles attained the expected size and shape under kinetic control, and were stable for at least 2 days. In order to obtain good quality AuNRs in good yields, without enrichment, we suggest keeping the growth-driving agent/gold molar ratio, the AuI/seed ratio, and the concentration of the reagents in the final solution within specific ranges. For example, even if good molar ratios between the reagents are maintained, relatively highly concentrated reaction solutions lead to AuNRs with lower aspect ratios. The main properties of the prepared colloidal systems and the nanoparticles were evaluated by UV–vis spectroscopy and transmission electron microscopy, respectively. 相似文献
22.
Monique?SabatyEmail author Sandrine?Grosse Geraldine?Adryanczyk Séverine?Boiry Frédéric?Biaso Pascal?Arnoux David?Pignol 《BMC biochemistry》2013,14(1):28
Background
YedY, a molybdoenzyme belonging to the sulfite oxidase family, is found in most Gram-negative bacteria. It contains a twin-arginine signal sequence that is cleaved after its translocation into the periplasm. Despite a weak reductase activity with substrates such as dimethyl sulfoxide or trimethylamine N-oxide, its natural substrate and its role in the cell remain unknown. Although sequence conservation of the YedY family displays a strictly conserved hydrophobic C-terminal residue, all known studies on Escherichia coli YedY have been performed with an enzyme containing a 6 histidine-tag at the C-terminus which could hamper enzyme activity.Results
In this study, we demonstrate that the tag fused to the C-terminus of Rhodobacter sphaeroides YedY is detrimental to the enzyme’s reductase activity and results in an eight-fold decrease in catalytic efficiency. Nonetheless this C-terminal tag does not influence the properties of the molybdenum active site, as assayed by EPR spectroscopy. When a cleavable His-tag was fused to the N-terminus of the mature enzyme in the absence of the signal sequence, YedY was expressed and folded with its cofactor. However, when the signal sequence was added upstream of the N-ter tag, the amount of enzyme produced was approximately ten-fold higher.Conclusion
Our study thus underscores the risk of using a C-terminus tagged enzyme while studying YedY, and presents an alternative strategy to express signal sequence-containing enzymes with an N-terminal tag. It brings new insights into molybdoenzyme maturation in R. sphaeroides showing that for some enzymes, maturation can occur in the absence of the signal sequence but that its presence is required for high expression of active enzyme.23.
Ariana Borges Souza Monique Rodrigues Moreira Carly Henrique Gambeta Borges Marília Rodrigues Simão Jairo Kenupp Bastos João Paulo Barreto de Sousa Sérgio Ricardo Ambrosio Rodrigo Cassio Sola Veneziani 《Biomedical chromatography : BMC》2013,27(3):280-283
The Copaifera species (Leguminoseae) are popularly known as ‘copaíba’ or ‘copaíva’ and are grown in the states of Amazonas, Pará and Ceará in northern Brazil. The oleoresins obtained from these species have been extensively used owing to their pharmacological potential and their application in cosmetic and pharmaceutical preparations. In the present study, the development and validation of a novel, rapid and efficient RP‐HPLC methodology for the analysis of the diterpene (?)‐copalic acid (CA), pointed out as the only chemical marker of the Copaifera genus, are described. The regression equation (Y = 26,707x ? 29,498) was obtained with good linearity (r2 = 0.9993) and the limits of quantification and detection were 9.182 and 3.032 µg/mL, respectively. The precision and the accuracy of the method were adequate (lower than 4%). Finally, the validation parameters evaluated were satisfactorily met, so the developed method represents a suitable tool for application in the quality control of such natural products. Further studies aiming to develop analytical methodologies for each Copaifera species using a more representative number of chemical markers should be performed. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
24.
Pascal Gosselin Serge Masson Monique Saquet André Thuillier 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):103-104
Abstract A new synthesis of dithioesters, starting from phenylisothiocyanate is described (scheme I) and this method is convenient for the preparation of β-olefinic dithioesters (e. g. 1, scheme II). 相似文献
25.
PHOTOSENSITIZING PROPERTIES OF BACTERIOCHLOROPHYLLIN a and BACTERIOCHLORIN a, TWO DERIVATIVES OF BACTERIOCHLOROPHYLL a 总被引:2,自引:0,他引:2
Eva M. Beems Tom M. A. R. Dubbelman Johan Lugtenburg Jaap A. van Best Monique F. M. A. Smeets J. Pierre J. Boegheim 《Photochemistry and photobiology》1987,46(5):639-643
Abstract The photosensitizing properties of two water soluble derivatives of bacteriochlorophyll a , bacteriochlorophyllin a and bacteriochlorin a (lacking the central Mg-ion) were investigated and compared to those of hematoporphyrin derivatives. At physiological pH the oxygen consumption rate of histidine, tryptophan, dithiothreitol and guanosine upon illumination was 3 to 4 times higher when bacteriochlorin a was used as photosensitizer than when hematoporphyrin derivatives were used. Especially bacteriochlorin a proved to be an effective sensitizer for the killing of L929 cells. Because bacteriochlorin a has an absorption maximum at 765 nm in phosphate buffered saline (allowing a light penetration in tissue about ten times larger than at 630 nm) and a high molar absorption coefficient (32 000 M cm−1 ) it has promising possibilities for the application in photodynamic therapy. 相似文献
26.
Ren Traber Hans Hofmann Hans-Rudolf Loosli Monique Ponelle Albert von Wartburg 《Helvetica chimica acta》1987,70(1):13-36
Novel Cyclosporins from Tolypocladium inflatum. The Cyclosporins K–Z The fungus T. inflatum produces a plethora of oligopeptides, the cyclosporins, which exhibit remarkable biological activities. Cyclosporin A, the main metabolite, represents a potent immunosuppressant which opened new ways in the immunotherapy of bone marrow and organ transplantations. In addition to the already described cyclosporins A–I, we report now the isolation of the cyclosporins K–Z. The structural assignments of these novel congeners are based on chemical degradation, correlation reactions, mass spectra, and extensive analysis of 1H- and 13C-NMR spectra. All cyclosporins are cyclic undecapeptides differing from each other by minor variations in the amino-acid sequence. Comparison of the immunosuppressive and antifungal effects furnished new information concerning structure-activity relationships. 相似文献
27.
Monique Perrin Sylvain Lecocq 《Journal of inclusion phenomena and macrocyclic chemistry》1991,11(2):171-183
A cyclic pentamer was obtained fromp-(1,1,3,3-tetramethylbutyl) phenol. It crystallizes from a mixture of acetone and toluene at room temperature giving a 1 : 1 complex with toluene (compound A), whereas at 50°C the empty form (compound B) is obtained. Crystals of A are orthorhombic, space groupPna21,a = 20.083(2),b = 12.936(6),c = 28,423(1) Å,Z = 4, finalR value = 0.067. The empty form, B, is monoclinicP21/c,a = 18.695(2),b = 11.673(5),c = 35.100(4) Å, = 114.33(1),Z = 4, finalR value = 0.135. The macrocycle is in the cone conformation for both compounds; the toluene molecule lies in the cone as often found for calix[4]arenes. 相似文献
28.
Aresta M Tommasi I Quaranta E Fragale C Mascetti J Tranquille M Galan F Fouassier M 《Inorganic chemistry》1996,35(14):4254-4260
Extended labeling experiments have shown that formation of rhodium peroxocarbonate from CO(2) and [RhCl(eta(2)-O(2))(P)(3)] (P is PEt(2)Ph or PEtPh(2)) proceeds through O-O bond cleavage and CO(2) insertion. O-transfer to ancillary phosphine ligand to give R(3)P=O selectively (>85%) involves the Rh-linked O atom of the peroxo group of RhCl(CO(4))(P)(3). 相似文献
29.
Marcel Gielen Hassan Dalil Monique Biesemans Bernard Mahieu Dick de Vos Rudolph Willem 《应用有机金属化学》1999,13(7):515-520
Di‐n‐butyl‐, triphenyl and tri‐n‐butyltin derivatives of 3 S, 4 S ‐3‐[( R )‐1‐(tert‐butyldimethyl‐<?tw=103.5%>silyloxy)ethyl‐4‐[( R )‐1‐carboxyethyl]‐2‐azetidi<?tw>‐none were synthesized and characterized. Their antitumour activity was screened against seven tumoural cell lines of human origin. Copyright © 1999 John Wiley & Sons, Ltd. 相似文献