全文获取类型
收费全文 | 650篇 |
免费 | 15篇 |
国内免费 | 7篇 |
专业分类
化学 | 386篇 |
晶体学 | 6篇 |
力学 | 19篇 |
数学 | 74篇 |
物理学 | 187篇 |
出版年
2022年 | 5篇 |
2021年 | 7篇 |
2020年 | 6篇 |
2019年 | 5篇 |
2017年 | 8篇 |
2016年 | 16篇 |
2015年 | 7篇 |
2014年 | 16篇 |
2013年 | 38篇 |
2012年 | 39篇 |
2011年 | 41篇 |
2010年 | 14篇 |
2009年 | 16篇 |
2008年 | 42篇 |
2007年 | 28篇 |
2006年 | 32篇 |
2005年 | 27篇 |
2004年 | 24篇 |
2003年 | 23篇 |
2002年 | 15篇 |
2001年 | 15篇 |
2000年 | 10篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 9篇 |
1995年 | 8篇 |
1994年 | 7篇 |
1993年 | 7篇 |
1992年 | 6篇 |
1991年 | 4篇 |
1990年 | 13篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 7篇 |
1986年 | 4篇 |
1985年 | 8篇 |
1984年 | 5篇 |
1983年 | 6篇 |
1982年 | 14篇 |
1981年 | 11篇 |
1980年 | 12篇 |
1979年 | 3篇 |
1978年 | 9篇 |
1977年 | 3篇 |
1976年 | 6篇 |
1975年 | 8篇 |
1974年 | 10篇 |
1973年 | 8篇 |
1970年 | 4篇 |
1969年 | 4篇 |
排序方式: 共有672条查询结果,搜索用时 421 毫秒
191.
A simple laboratory-made sheathless electrospray interface for coupling of capillary electrophoresis to ion-trap mass spectrometry (CE/MS) was developed. The interface was machined in-house and it was designed to be freely interchangeable with the commercially available ionization sources for the mass spectrometer. Sharpened fused-silica capillaries were coated with nickel by a simple electrodeless plating procedure and were used as all-in-one columns/emitters. The electrodeless plating produced a 2-5- micro m thick smooth nickel layer that lasted for more than 8 h of continuous electrospraying. The performance of the CE/MS interface was examined by using four cationic imipramine derivatives as test substances. Relative detection limits were calculated on the basis of the extracted ion electrophorograms and were in the range 6-130 nmol/L, corresponding to absolute detection limits in the range of 20-400 amol. The system was applied for analysis of impurities in an impure imipramine N-oxide preparation, and two of the impurities could be identified on the basis of online-MS(MS) spectra recorded in scan-dependent mode. 相似文献
192.
Instrumental analytical and bioenzymatic methods were used to differentiate between species of the Actinobacillus-Haemophilus-Pasteurella group. Long-chain fatty acids were analysed directly with gas chromatography (GC) without derivatization. GC of trifluoroacetylated whole-cell methanolysates was a rapid method for differentiation. Cellular sugars were more suitable for differentiation than fatty acids. D-Glycero-D-mannoheptose, the major localization of which was lipopolysaccharide, distinguished H. aphrophilus from A. actinomycetemcomitans, H. paraphrophilus, H. influenzae type b, P. haemolytica, P. multocida, and P. ureae. GC of single colonies, which is a new chemotaxonomic method, was preferable to GC of liquid-grown cells. Lysozyme-and EDTA-induced bacteriolysis and reduction of methylene blue by cellular hydrogenase served as additional criteria for differentiation. 相似文献
193.
J E Celis P Madsen H H Rasmussen H Leffers B Honoré B Gesser K Dejgaard E Olsen N Magnusson J Kiil 《Electrophoresis》1991,12(11):802-872
A two-dimensional (2-D) gel database of cellular proteins from noncultured, unfractionated normal human epidermal keratinocytes has been established. A total of 2651 [35S]methionine-labeled cellular proteins (1868 isoelectric focusing, 783 nonequilibrium pH gradient electrophoresis) were resolved and recorded using computer-aided 2-D gel electrophoresis. The protein numbers in this database differ from those reported in an earlier version due to changes in the scanning hardware (Celis et al., Electrophoresis 1990, 11, 242-254). Annotation categories reported include: "protein name" (listing 207 known proteins in alphabetical order), "basal cell markers", "differentiation markers", "proteins highly up-regulated in psoriatic skin", "microsequenced proteins" and "human autoantigens". For reference, we have also included 2-D gel (isoelectric focusing) patterns of cultured normal and psoriatic keratinocytes, melanocytes, fibroblasts, dermal microvascular endothelial cells, peripheral blood mononuclear cells and sweat duct cells. The keratinocyte 2-D gel protein database will be updated yearly in the November issue of Electrophoresis. 相似文献
194.
Olsen JV Haselmann KF Nielsen ML Budnik BA Nielsen PE Zubarev RA 《Rapid communications in mass spectrometry : RCM》2001,15(12):969-974
Electron capture dissociation (ECD) in Fourier transform ion cyclotron resonance mass spectrometry coupled with electrospray ionization enhances the sequence elucidation of peptide nucleic acids compared with conventional low-energy collisionally activated dissociation (CAD). Examples are shown where ECD produced complete or extensive sequence coverage in PNAs six to ten nucleobases long. However, facile base losses from the reduced species and low abundances of backbone ECD fragments presented a significant problem. This was rationalized through the lower degree of charge solvation on the backbone compared to polypeptides. Combination of both CAD and ECD data is advantageous, as these techniques produce cleavages at different sites. 相似文献
195.
The solid-phase synthesis of a small library of mimetics of the cyclic depsipeptide hapalosin is described. 3-Amino-4-hydroxy-5-nitrobenzoic acid was anchored through the anilino moiety to a backbone amide linker (BAL) handle support. Using chemoselective reactions and without the need for protecting group manipulations, the benzoic acid group was first amidated, then the aniline nitrogen was acylated, and finally the nitro group was reduced to an amine and acylated or reductively alkylated, to generate a 12-member library. 相似文献
196.
Olsen RA Liu L Ghaderi N Johns A Hatcher ME Mueller LJ 《Journal of the American Chemical Society》2003,125(33):10125-10132
Pyridine carboxamides are a class of medicinal agents with activity that includes the reduction of iron-induced renal damage, the regulation of nicotinamidase activity, and radio- and chemosensitization. Such pharmacological activities, and the prevalence of the carboxamide moiety and the importance of amide rotations in biology, motivate detailed investigation of energetics in these systems. In this study, we report the use of dynamic nuclear magnetic resonance to measure the amide rotational barriers in the pyridine carboxamides picolinamide and nicotinamide. The activation enthalpies and entropies of DeltaH++ = 12.9 +/- 0.3 kcal/mol and DeltaS++ = -7.7 +/- 0.9 cal/mol K for nicotinamide and DeltaH++ = 18.3 +/- 0.4 kcal/mol and DeltaS++ = +1.3 +/- 1.0 cal/mol K for picolinamide report a substantial energetic difference for these regioisomers. Ab initio calculations of the rotational barriers are in good agreement with the experimentally determined values and help partition the 5.4 kcal/mol enthalpy difference into its major contributions. Of principal importance are the variations in steric interactions in the ground states of picolinamide and nicotinamide, superior pi electron donation from the pyridine ring in the transition state of nicotinamide, and an intramolecular hydrogen bond in the ground state of picolinamide. 相似文献
197.
The impact of column inner diameter on chromatographic performance in temperature gradient liquid chromatography has been investigated in the present study. Columns with inner diameters of 0.32, 0.53, 3.2 and 4.6 mm were compared with respect to retention and efficiency characteristics using temperature gradients from 30 to 90 degrees C with temperature ramps of 1, 5, 10 and 20 degrees C min(-1). The columns were all of 15 cm length and were packed with 3 microm Hypersil ODS particles. Alkylbenzenes served as model compounds, and the mobile phase consisted of acetonitrile-water (50:50, v/v). The study revealed that the column ID is not a critical limiting factor when performing temperature programming in LC, at least for columns narrower than 4.6 mm inner diameter in the temperature interval 30-90 degrees C. The retention times for all components on all columns were highly comparable, with similar peak profiles without any signs of peak splitting. The use of mobile phase pre-heating when using the larger bore columns was avoided by starting the temperature gradients close to ambient. However, the relative apparent efficiency was inversely proportional to column inner diameter, making the capillary columns generally more functional towards temperature gradients than the larger bore columns with respect to chromatographic efficiency. In addition, the capillary columns possessed higher robustness towards temperature programming than the conventional columns. 相似文献
198.
Three cobalt(III) complexes of the macrocyclic tetraamine [3(5)]adamanzane (1,5,9,13-tetraazabicyclo[7.7.3]nonadecane) were isolated as salts. The X-ray crystal structures were solved for the compounds [Co([3(5)]adz)(CO(3))]AsF(6) (1b), [Co([3(5)]adz)(HCO(3))]ZnBr(4).H(2)O (2a), and [Co([3(5)]adz)(SO(4))]AsF(6).H(2)O (3a). The coordination geometry around the cobalt(III) ion is a distorted octahedron with the inorganic ligands at cis-positions. Complex 2 is the second example of a cobalt(III) complex for which the X-ray structure shows a chelate binding mode of the hydrogen carbonate entity. The pK(a) value of the [Co([3(5)]adz)(HCO(3))](2+) ion (2) was determined spectrophotometrically to be 0.27 (25 degrees C, I = 5.0 M). The protonation appears to occur at the noncoordinated carbonyl oxygen atom of the carbonate group, with hydrogen bonding to the crystal water molecule. Evidence is presented for this oxygen atom as the site of protonation in solution as well. In 5.0 M CF(3)SO(3)H a slow reaction of the carbonato complex, quantitatively yielding the [Co([3(5)]adz)(H(2)O)(2)](3+) ion, was observed. k(obs) = 7.9(1) x 10(-)(6) s(-)(1) at 25 degrees C. 相似文献
199.
Zhao Z Huskey DT Olsen KJ Nicovich JM McKee ML Wine PH 《Physical chemistry chemical physics : PCCP》2007,9(31):4383-4394
A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the reaction of atomic chlorine with pyridine (C(5)H(5)N) as a function of temperature (215-435 K) and pressure (25-250 Torr) in nitrogen bath gas. At T> or = 299 K, measured rate coefficients are pressure independent and a significant H/D kinetic isotope effect is observed, suggesting that hydrogen abstraction is the dominant reaction pathway. The following Arrhenius expression adequately describes all kinetic data at 299-435 K for C(5)H(5)N: k(1a) = (2.08 +/- 0.47) x 10(-11) exp[-(1410 +/- 80)/T] cm(3) molecule(-1) s(-1) (uncertainties are 2sigma, precision only). At 216 K < or =T< or = 270 K, measured rate coefficients are pressure dependent and are much faster than computed from the above Arrhenius expression for the H-abstraction pathway, suggesting that the dominant reaction pathway at low temperature is formation of a stable adduct. Over the ranges of temperature, pressure, and pyridine concentration investigated, the adduct undergoes dissociation on the time scale of our experiments (10(-5)-10(-2) s) and establishes an equilibrium with Cl and pyridine. Equilibrium constants for adduct formation and dissociation are determined from the forward and reverse rate coefficients. Second- and third-law analyses of the equilibrium data lead to the following thermochemical parameters for the addition reaction: Delta(r)H = -47.2 +/- 2.8 kJ mol(-1), Delta(r)H = -46.7 +/- 3.2 kJ mol(-1), and Delta(r)S = -98.7 +/- 6.5 J mol(-1) K(-1). The enthalpy changes derived from our data are in good agreement with ab initio calculations reported in the literature (which suggest that the adduct structure is planar and involves formation of an N-Cl sigma-bond). In conjunction with the well-known heats of formation of atomic chlorine and pyridine, the above Delta(r)H values lead to the following heats of formation for C(5)H(5)N-Cl at 298 K and 0 K: Delta(f)H = 216.0 +/- 4.1 kJ mol(-1), Delta(f)H = 233.4 +/- 4.6 kJ mol(-1). Addition of Cl to pyridine could be an important atmospheric loss process for pyridine if the C(5)H(5)N-Cl product is chemically degraded by processes that do not regenerate pyridine with high yield. 相似文献
200.
H. Olsen A. A. Michelson C. Leiss Ch. Fabry E. A. Wülfing und F. F. Martens 《Fresenius' Journal of Analytical Chemistry》1899,38(6):354-356
Ohne Zusammenfassung 相似文献