全文获取类型
收费全文 | 1975篇 |
免费 | 84篇 |
国内免费 | 17篇 |
专业分类
化学 | 1385篇 |
晶体学 | 17篇 |
力学 | 44篇 |
数学 | 356篇 |
物理学 | 274篇 |
出版年
2023年 | 18篇 |
2022年 | 9篇 |
2021年 | 18篇 |
2020年 | 34篇 |
2019年 | 33篇 |
2018年 | 32篇 |
2017年 | 31篇 |
2016年 | 62篇 |
2015年 | 58篇 |
2014年 | 52篇 |
2013年 | 120篇 |
2012年 | 135篇 |
2011年 | 128篇 |
2010年 | 67篇 |
2009年 | 79篇 |
2008年 | 128篇 |
2007年 | 148篇 |
2006年 | 143篇 |
2005年 | 104篇 |
2004年 | 94篇 |
2003年 | 72篇 |
2002年 | 85篇 |
2001年 | 46篇 |
2000年 | 49篇 |
1999年 | 28篇 |
1998年 | 23篇 |
1997年 | 24篇 |
1996年 | 33篇 |
1995年 | 19篇 |
1994年 | 25篇 |
1993年 | 17篇 |
1992年 | 16篇 |
1991年 | 16篇 |
1990年 | 13篇 |
1989年 | 11篇 |
1988年 | 10篇 |
1987年 | 8篇 |
1986年 | 3篇 |
1985年 | 17篇 |
1984年 | 9篇 |
1982年 | 5篇 |
1980年 | 5篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 5篇 |
1974年 | 5篇 |
1973年 | 4篇 |
1971年 | 5篇 |
1962年 | 3篇 |
排序方式: 共有2076条查询结果,搜索用时 15 毫秒
41.
Spectrofluorimetric methods to determine cisatracurium and mivacurium are proposed and applied to the determination of both substances in human serum and to the determination of mivacurium in pharmaceuticals. The fluorimetric methods allow the determination of 5-500 ng ml(-1) of mivacurium in aqueous solutions and 5-500 ng ml(-1) of cisatracurium in water-acetonitrile solutions, both containing acetic acid-sodium acetate buffer (pH 5.5) with lambda(exc)=230 nm and lambda(em)=324 nm. 相似文献
42.
Limited flexibility of lactose detected from residual dipolar couplings using molecular dynamics simulations and steric alignment methods 总被引:1,自引:0,他引:1
Martín-Pastor M Canales A Corzana F Asensio JL Jiménez-Barbero J 《Journal of the American Chemical Society》2005,127(10):3589-3595
The conformational flexibility of lactose in solution has been investigated by residual dipolar couplings (RDCs). One-bond carbon-proton and proton-proton coupling constants have been measured in two oriented media and interpreted in combination with molecular dynamics simulations (MD). Two different approaches, known as PALES (Zweckstetter et al., J. Am. Chem. Soc. 2000, 122, 3791-3792) and TRAMITE (Azurmendi et al., J. Am. Chem. Soc. 2002, 124, 2426-2427), have been used to determine the alignment tensor from a shape-induced alignment model with the oriented medium. The steric alignment of the structures from several MD trajectories has provided ensemble averaged RDCs that have been compared with the experimental ones. The obtained results reveal the almost exclusive presence of a major low energy region defined as syn-phi/syn-psi (> 97%), for which sampling occurs in a dynamic manner. This result satisfactorily agrees with that determined by standard NOE-based methods. 相似文献
43.
The thermodynamic functions Gibbs energy, enthalpy and entropy of solution, mixing and solvation of acetaminophen in propylene
glycol (PG) + ethanol (EtOH) cosolvent mixtures were evaluated from solubility data measured at several temperatures, using
the van't Hoff and Gibbs equations. The solubility was greater at 50% m/m of PG at 20.0^C, while it was greater at 80% of
PG at 40.0 ^C where m/m refers to mass percent. The solvation of this drug is appreciably greater in the mixtures than in
the pure solvents. By means of an enthalpy–entropy compensation analysis, complex behavior was found for the solution. From
0 up to 20% of PG and from 60 up to 100% of PG the solution process is enthalpy driven, whereas from 20 up to 60% of PG it
is entropy driven. These facts can be explained in terms of a decrease in the energy required for cavity formation in the
solvent for mixtures containing 20–60% of PG. 相似文献
44.
Mineral content and botanical origin of Spanish honeys 总被引:2,自引:0,他引:2
Fernández-Torres R Pérez-Bernal JL Bello-López MA Callejón-Mochón M Jiménez-Sánchez JC Guiraúm-Pérez A 《Talanta》2005,65(3):686-691
Eleven elements (Zn, P, B, Mn, Mg, Cu, Ca, Ba, Sr, Na and K) were determined by inductively plasma coupled spectrometry in 40 honey samples from different places of Spain and four different botanical origins: Eucalyptus (Eucalyptus sp.), Heather (Erica sp.), Orange-blossom (Citrus sinensis) and Rosemary (Rosmarinus officinalis). K, Ca and P show the higher levels with average concentrations ranged between 434.1-1935 mg kg−1 for K; 42.59-341.0 mg kg−1 for Ca and 51.17-154.3 mg kg−1 for P. Levels of Cu (0.531-2.117 mg kg−1), Ba (0.106-1.264 mg kg−1) and Sr (0.257-1.462 mg kg−1) are the lowest in all honey samples. Zn (1.332-7.825 mg kg−1), Mn (0.133-9.471 mg kg−1), Mg (13.26-74.38 mg kg−1) and Na (11.69-218.5 mg kg−1) concentrations were found strongly dependent on the kind of botanical origin.Results were submitted to pattern recognition procedures, unsupervised methods such as cluster and principal components analysis and supervised learning methods like linear discriminant analysis in order to evaluate the existence of data patterns and the possibility of differentiation of Spanish honeys from different botanical origins according to their mineral content. Cluster analysis shows four clusters corresponding to the four botanical origins of honey and PCA explained 71% of the variance with the first two PC variables. The best-grouped honeys were those from heather; eucalyptus honeys formed a more dispersed group and finally orange-blossom and rosemary honeys formed a less distinguishable group. 相似文献
45.
Graeme B Bolger Angela McCahill Stephen J Yarwood Michael R Steele Jim Warwicker Miles D Houslay 《BMC biochemistry》2002,3(1):24-11
Background
The cyclic AMP specific phosphodiesterase, PDE4D5 interacts with the β-propeller protein RACK1 to form a signaling scaffold complex in cells. Two-hybrid analysis of truncation and mutant constructs of the unique N-terminal region of the cAMP-specific phosphodiesterase, PDE4D5 were used to define a domain conferring interaction with the signaling scaffold protein, RACK1. 相似文献46.
Jiménez-Hernández ME Orellana G Montero F Portolés MT 《Photochemistry and photobiology》2000,72(1):28-34
The capability of the new luminescent probe (dibenzo[h,j] dipyrido[3,2-a:2',3'-c]phenazine)bis(2,2'-bipyridine)ruthenium(II) dication, (RB2Z), to discriminate live and dead cells has been tested on rat hepatocytes and mouse lymphocytes. RB2Z-stained cells were analyzed using flow cytometry, fluorescence (confocal) microscopy and time-resolved luminescence measurements. The established viability probes propidium iodide (PI) and SYTOX green (SG) were used as controls. The intense luminescence of RB2Z at 606 nm is localized in the nucleus of nonviable cells. Viability measurements by flow cytometry and fluorescence microscopy using RB2Z as dead-cell marker yield the same results as PI and SG. The luminescence lifetime of RB2Z also displays sensitivity to cell viability (0.45 and 0.82 microsecond in presence of fully viable and dead cells, respectively). This ruthenium complex is photostable under laser sources and its 200 nm Stokes shift facilitates multicolor labeling experiments in flow cytometry and fluorescence microscopy. Unlike the currently available probes, the long-lived excited state of RB2Z also allows assays based on luminescence decay measurements. 相似文献
47.
1,3-Cyclopentanedione bis(4-methylthiosemicarbazone) monohydrochloride produces colored solutions with chlorate ions in strongly acid medium. The yellow color obtained has been used to propose a spectrophotometric method of C103? determination in the concentration range 0.5–6.0 ppm (molar absorptivity 1.26 × 104 liters mol?1 cm?1 at a wavelength of 397 nm). 相似文献
48.
Giampaolo Primofiore Anna Maria Marini Federico Da Settimo Silvia Salerno Daniele Bertini Lisa Dalla Via Sebastiano Marciani Magno 《Journal of heterocyclic chemistry》2003,40(5):783-788
The synthesis of new planar derivatives characterized by the presence of a pyridothiopyranopyrazole or pyridothiopyranopyrimidine nucleus, carrying a substituted aryl group, is reported. The novel 1,4‐dihydropyrido[3′,2′:5,6]thiopyrano[4,3‐c]pyrazole derivatives were obtained by condensation of 2,3‐dihydro‐3‐hydroxymethylenethiopyrano[2,3‐b]pyridin‐4(4H)‐ones with appropriate hydrazines. The preparation of 2‐substituted pyrido[3′,2′:5,6]thiopyrano[4,3‐d]pyrimidines was accomplished from the intermediate 2,3‐dihy‐dro‐3‐dimethylaminomethylenethiopyrano[2,3‐b]pyridin‐4(4H)‐ones by reaction with the appropriate binucleophile amidines. The antiproliferative activity of some new products was tested by an in vitro assay on human tumour cell lines (HL‐60 and HeLa), but none of them showed any significant effects in the tests performed. Accordingly, linear flow dichroism measurements indicated their inability to form a molecular complex with DNA. 相似文献
49.
Gierczak T Jiménez E Riffault V Burkholder JB Ravishankara AR 《The journal of physical chemistry. A》2005,109(4):586-596
Rate coefficients for the gas-phase thermal decomposition of HO(2)NO(2) (peroxynitric acid, PNA) are reported at temperatures between 331 and 350 K at total pressures of 25 and 50 Torr of N(2). Rate coefficients were determined by measuring the steady-state OH concentration in a mixture of known concentrations of HO(2)NO(2) and NO. The measured thermal decomposition rate coefficients k(-)(1)(T,P) are used in combination with previously published rate coefficient data for the HO(2)NO(2) formation reaction to yield a standard enthalpy for reaction 1 of Delta(r)H degrees (298K) = -24.0 +/- 0.5 kcal mol(-1) (uncertainties are 2sigma values and include estimated systematic errors). A HO(2)NO(2) standard heat of formation, Delta(f)H degrees (298K)(HO(2)NO(2)), of -12.6 +/- 1.0 kcal mol(-1) was calculated from this value. Some of the previously reported data on the thermal decomposition of HO(2)NO(2) have been reanalyzed and shown to be in good agreement with our reported value. 相似文献
50.
Stephen B. Colbran Brian H. Robinson Jim Simpson 《Journal of organometallic chemistry》1984,265(2):199-204
The nitrosyl clusters PPN[YCCo3(CO)7(NO)] (Y = Me, Ph, COOH, (C5H5)Fe(C5H4)) have been prepared in high yield from the reaction of YCCo3(CO)9 with PPN(NO2) in THF, acetone or acetonitrile. Spectroscopic evidence indicates the structure of the nitrosyl anions is derived from that of YCCo3(CO)9 by the replacement of two CO ligands on one cobalt atom by a linear, terminal nitrosyl group. The nitrosyl metallates are extremely sensitive to oxidation and attempts to protonate the anions resulted in the reformation of the parent YCCo3(CO)9, molecules. The oxidative electrochemistry of the ferrocene complex, PPN[(C5H5)Fe(C5H4CCo3(CO)7(NO)] is also discussed. 相似文献