全文获取类型
收费全文 | 4133篇 |
免费 | 77篇 |
国内免费 | 11篇 |
专业分类
化学 | 3010篇 |
晶体学 | 8篇 |
力学 | 58篇 |
数学 | 719篇 |
物理学 | 426篇 |
出版年
2020年 | 26篇 |
2019年 | 27篇 |
2016年 | 55篇 |
2015年 | 65篇 |
2014年 | 58篇 |
2013年 | 153篇 |
2012年 | 120篇 |
2011年 | 156篇 |
2010年 | 98篇 |
2009年 | 101篇 |
2008年 | 123篇 |
2007年 | 127篇 |
2006年 | 148篇 |
2005年 | 137篇 |
2004年 | 165篇 |
2003年 | 117篇 |
2002年 | 125篇 |
2001年 | 69篇 |
2000年 | 67篇 |
1999年 | 68篇 |
1998年 | 53篇 |
1997年 | 63篇 |
1996年 | 67篇 |
1995年 | 64篇 |
1994年 | 66篇 |
1993年 | 59篇 |
1992年 | 72篇 |
1991年 | 50篇 |
1990年 | 45篇 |
1989年 | 48篇 |
1988年 | 57篇 |
1987年 | 42篇 |
1986年 | 63篇 |
1985年 | 66篇 |
1984年 | 84篇 |
1983年 | 63篇 |
1982年 | 64篇 |
1981年 | 82篇 |
1980年 | 84篇 |
1979年 | 69篇 |
1978年 | 87篇 |
1977年 | 60篇 |
1976年 | 71篇 |
1975年 | 55篇 |
1974年 | 53篇 |
1973年 | 61篇 |
1972年 | 42篇 |
1971年 | 40篇 |
1970年 | 38篇 |
1968年 | 25篇 |
排序方式: 共有4221条查询结果,搜索用时 15 毫秒
31.
Brunsveld L Watzke A Durek T Alexandrov K Goody RS Waldmann H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(9):2756-2772
Prenylated proteins with non-native functionalities are generally very difficult to obtain by recombinant or enzymatic means. The semisynthesis of preparative amounts of prenylated Rab guanosine triphosphatases (GTPases) from recombinant proteins and synthetic prenylated peptides depends largely on the availability of functionalised prenylated peptides corresponding to the proteins' native structure or modifications thereof. Here, we describe and compare solution-phase and solid-phase strategies for the generation of peptides corresponding to the prenylated C terminus of Rab7 GTPase. The solid-phase with utilisation of a hydrazide linker emerges as the more favourable approach. It allows a fast and practical synthesis of pure peptides and gives a high degree of flexibility in their modification. To facilitate the analysis of semisynthetic proteins, the synthesised peptides were equipped with a fluorescent group. Using the described approach, we introduced fluorophores at several different positions of the Rab7 C terminus. The position of the incorporated fluorescent groups in the peptides did not influence the protein-ligation reaction, as the generated peptides could be ligated onto thioester-tagged Rab7. However, it was found that the positioning of the fluorescent group had an influence on the functionality of the Rab7 proteins; analysis of the interaction of the semisynthetic Rab7 proteins with REP (Rab escort protein) and GDI (guanosine diphosphate dissociation inhibitor) molecules revealed that modification of the peptide side chains or of the C-terminal isoprenoid did not significantly interfere with complex formation. However, functionalisation of the C terminus was found to have an adverse effect on complex formation and stability, possibly reflecting low structural flexibility of the Rab GDI/REP molecules in the vicinity of the lipid-binding site. 相似文献
32.
Herbert Puderbach Hans Jürgen Ghausen 《Spectrochimica Acta Part B: Atomic Spectroscopy》1984,39(12):1547-1551
Results of examinations with TEM, SEM, EDX, ISS, SIMS and AES on sulphuric acid anodized films on aluminium are reported. Important technical information about the 20-μm thick coatings were obtained by monolayer and depth analysis. The fine structure of the oxide film and its modifications during a sealing process are discussed. Possibilities to prevent sealing smut on the surface are shown. The metal distribution inside the films which are coloured electrolytically with metal salts, is investigated. 相似文献
33.
An optical biosensor for the determination of hydrogen peroxide based on immobilized horseradish peroxidase is described. The fluorescence of the dimeric product of the enzyme catalysed oxidation of homovanillic acid is utilized to determine the concentration of H2O2. The membrane-bound enzyme is attached to a bifurcated fibre bundle permitting excitation and detection of the fluorescence by a fluorometer. The response of the sensor is linear from 1 to 130 M hydrogen peroxide; the coefficient of variation is 3%. The sensor is stable for more than 10 weeks. The operating pH for maximal sensor response is 8.15. This allows the sensor to be used in combination with oxidase reactions producing hydrogen peroxide, as is demonstrated with a co-immobilized lactate oxidase-horseradish peroxidase optode for the determination of L-lactate. The fluorescence intensity of this sensor depends linearly on the concentration of lactate between 3 and 200 M and a throughput of 10 samples per hour is possible. The precision is in the same range as that of the monoenzyme optode. The lifetime of the bienzyme sensor for lactate is considerably shorter than that of the peroxidase sensor; it is limited by the stability of the immobilized lactate oxidase enzyme. The sensor has been applied to the determination of lactate in control serum. 相似文献
34.
35.
Organoboranes, readily available via the hydroboration of unsaturated organic compounds, exhibit a remarkable versatility
in their reactions. The boron atom in these organoboranes can be readily converted into a wide variety of organic groups under
very mild conditions, providing simple versatile syntheses of organic compounds. Exploration of these substitution reactions
reveal that, with rare exceptions, the organoboranes transfer the alkyl group to other elements of synthetic interest with
complete retention of stereochemistry. Recently we have discovered a method of synthesizing essentially optically pure organoborane
intermediates. These optically active alkyl groups attached to boron can also be transferred with complete retention of optical
activity. Consequently, it is now possible to achieve by a rational synthesis the preparation of almost any optically active
compound with a chiral center, either R- or S-, in essentially 100% enantiomeric excess. 相似文献
36.
Roesky HW Murugavel R Walawalkar MG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(2):324-331
Metal hydroxides represent a very interesting and highly useful class of compounds that have been known to chemists for a very long time. While alkali and alkaline earth metal hydroxides (s‐block) are commonplace chemicals in terms of their abundance and their use in a chemical laboratory as bases, the interest in Brønsted acidic molecular terminal hydroxides of p‐block elements, such as aluminum and silicon, has been of recent origin, with respect to the variety of applications these compounds can offer both in materials science and catalysis. Moreover, these systems are environmentally friendly, relative to the metal halides, owing to their ‐OH functionality (resembling that of water). Design and conceptualization of the corresponding terminal thiols, selenols, and tellurols (M? SH, M? SeH, and M? TeH) offer even more challenging problems to synthetic inorganic chemists. This concept summarizes some of the recent strategies developed to stabilize these otherwise very unstable species. The successful preparation of a number of silicon trihydroxides a few years back resulted in the generation of several model compounds for metal–silicates. The recent synthesis of unusual aluminum compounds such as RAl(OH)2, RAl(SH)2, and RAl(SeH)2 with terminal EH (E=O, Se, or Se) groups is likely to change the ways in which some of the well‐known catalytic conversions are being carried out. The need for very flexible and innovative synthetic strategies to achieve these unusual compounds is emphasized in this concept. 相似文献
37.
The ring-oven technique is a special type of spot analysis. In this review, papers published since 1976 are discussed. The aspects dealt with include developments in the technique and its use, the identification and determination of inorganic ions, organic substances, enzymatic analysis, applications to air and water samples, and combinations with other techniques. 相似文献
38.
Indole lactones 8 and 14 were synthesized as a means of functionalizing the 1-isopropyl substituent of the indole nucleus. Lactone 8 , upon reduction with diisobutylaluminum hydride, produces lactol 9 which behaves like a masked hydroxy aldehyde and undergoes a Horner-Emmons reaction with triethyl phosphonoacteate to give α,β-unsaturated ester 3 which possesses a hydroxyl group on the 1-isopropyl moiety. 相似文献
39.
Gert Brandl Fritz Kastner Rainer Fritsch Herbert Zinner Albrecht Mannschreck 《Monatshefte für Chemie / Chemical Monthly》1992,123(11):1059-1069
Summary A procedure is described which serves to measure circular dichrograms () on line during stops of flow in liquid chromatography. Since the concentration of substrate in the spectrometer cell during the stop is not known, the differential absorption coefficients are calculated from the experimental differential absorbances A by means of UV absorption (i. e. photomultiplier voltage) data. Verifications of the procedure are obtained by its application to three substrates (Table 1), the () spectra of which were known. The present on-line technique is compared with a corresponding off-line method.The N,N-dimethylthiobenzamides1 and2 as well as the 9,10-phenanthrenequinone7 consist of interconvertible enantiomers because their planar states are destabilized by steric overcrowding of groups. The unknown dichrograms () of1, 2 and7 are obtained (Figs. 2 and 4) and discussed with reference to the helicities of these molecules.In memory of the late Professor Dr. Dr. h. c. Günther Snatzke. 相似文献
40.
S. Korhammer Rolf Herzig Peter Schramel Jorma Kumpulainen Bernd Markert Herbert Muntau Philippe Quevauviller 《Accreditation and quality assurance》2000,5(6):238-242
Cabbage is frequently used in environmental monitoring and food control, and, hence, cabbage reference materials (RMs) are
required for ensuring quality assurance. A cabbage RM was prepared in view of certification of specific elements from the
"black list" of high toxicological interest and nutritive importance. All tasks of the RM production (production of the plant
material, cutting and freeze-drying, determination of the residual water content, preparation of the RM, homogeneity testing,
stability testing, certification measurements) are described in detail.
Received: 12 November 1999 / Accepted: 29 January 2000 相似文献