全文获取类型
收费全文 | 3105篇 |
免费 | 107篇 |
国内免费 | 6篇 |
专业分类
化学 | 2277篇 |
晶体学 | 8篇 |
力学 | 65篇 |
数学 | 485篇 |
物理学 | 383篇 |
出版年
2022年 | 26篇 |
2021年 | 19篇 |
2020年 | 45篇 |
2019年 | 45篇 |
2018年 | 32篇 |
2017年 | 28篇 |
2016年 | 73篇 |
2015年 | 68篇 |
2014年 | 93篇 |
2013年 | 134篇 |
2012年 | 140篇 |
2011年 | 184篇 |
2010年 | 94篇 |
2009年 | 84篇 |
2008年 | 139篇 |
2007年 | 159篇 |
2006年 | 143篇 |
2005年 | 148篇 |
2004年 | 142篇 |
2003年 | 93篇 |
2002年 | 95篇 |
2001年 | 61篇 |
2000年 | 55篇 |
1999年 | 57篇 |
1998年 | 46篇 |
1997年 | 63篇 |
1996年 | 54篇 |
1995年 | 37篇 |
1994年 | 49篇 |
1993年 | 44篇 |
1992年 | 29篇 |
1991年 | 32篇 |
1990年 | 33篇 |
1989年 | 32篇 |
1988年 | 32篇 |
1987年 | 33篇 |
1986年 | 46篇 |
1985年 | 48篇 |
1984年 | 51篇 |
1983年 | 40篇 |
1982年 | 48篇 |
1981年 | 26篇 |
1980年 | 37篇 |
1979年 | 40篇 |
1978年 | 30篇 |
1977年 | 36篇 |
1976年 | 26篇 |
1973年 | 18篇 |
1972年 | 20篇 |
1971年 | 21篇 |
排序方式: 共有3218条查询结果,搜索用时 15 毫秒
141.
Viktor Reshetnikov Steffen Daum Dr. Christina Janko Weronika Karawacka Dr. Rainer Tietze Prof. Dr. Christoph Alexiou Dr. Solomiya Paryzhak Dr. Tetiana Dumych Prof. Dr. Rostyslav Bilyy Dr. Philipp Tripal Dr. Benjamin Schmid Dr. Ralf Palmisano Prof. Dr. Andriy Mokhir 《Angewandte Chemie (International ed. in English)》2018,57(37):11943-11946
Mitochondrial membrane potential is more negative in cancer cells than in normal cells, allowing cancer targeting by delocalized lipophilic cations (DLCs). However, as the difference is rather small, these drugs affect also normal cells. Now a concept of pro‐DLCs is proposed based on an N‐alkylaminoferrocene structure. These prodrugs are activated by the reaction with reactive oxygen species (ROS) forming ferrocenium‐based DLCs. Since ROS are overproduced in cancer, the high‐efficiency cancer‐cell‐specific targeting of mitochondria could be achieved as demonstrated by fluorescence microscopy in combination with two fluorogenic pro‐DLCs in vitro and in vivo. We prepared a conjugate of another pro‐DLC with a clinically approved drug carboplatin and confirmed that its accumulation in mitochondria was higher than that of the free drug. This was reflected in the substantially higher anticancer effect of the conjugate. 相似文献
142.
Rainer Strommer Wolfgang Strauss Helmut Emmert Reinhard Sailer Rudolf Steiner Eva Reisinger Ernst Haslinger Hans W. Schramm 《Monatshefte für Chemie / Chemical Monthly》2001,132(3):387-392
Summary. Selenium dioxide oxidation allows the selective introduction of a hydroxyl group at position 6 of the steroid skeleton of
the antihormone (11β, 17β)-11-(4-dimethylamino-phenyl)-17-hydroxyl-17-(1-propynyl)-estra-4,9-dien-3-one (mifepristone, RU
486) and leads in a one-step procedure to two diastereomeric oxidation products. Their structure (6α- and 6β-hydroxy-mifepristone)
was determined by NMR spectroscopy. The antiprogestinic activity of the oxidation products is comparable to that of mifepristone.
Received August 25, 2000. Accepted (revised) October 24, 2000 相似文献
143.
Karsten Haas J. Feldmann Rainer Wennrich Hans-Joachim Stärk 《Analytical and bioanalytical chemistry》2001,370(5):587-596
The analytical performance of an axial inductively-coupled-plasma time-of-flight mass spectrometer (ICP–TOFMS) as a detector
for fast transient chromatographic signals resulting from the coupling to capillary gas chromatography (CGC) was investigated.
A cryotrapping GC–ICP–TOFMS method for the determination of volatile metal(loid) compounds (VOMs) in gases was used and the
suitability of the TOF mass analyzer for multi-elemental speciation analysis and multi-isotope ratio determinations was studied
in terms of accuracy and precision. Isotope ratios 118Sn/120Sn and 121Sb/123Sb have been determined in in-house gas standard atmospheres in Tedlar bags at two different levels (100 pg and 1 ng) for
different elemental species (SnH4, MeSnH3, Me2SnH2, Me3SnH, BuSnH3, SbH3, and MeSbH2). A limitation arising from counting statistics in both detection modes could be shown. A solution containing rhodium (10
ng mL–1) and cadmium (40 ng mL–1) was introduced simultaneously to the GC outlet. Rhodium acts as a continuous internal standard and Cd is used for mass-bias
correction (by measuring the 111Cd/113Cd ratio). The detection system in both pulse counting and analog mode was examined. The best attainable precision was established
for Me2SnH2 (analog mode, 12 replicates, 1 ng, RSD 0.34%, accuracy 0.31%) whereas most other species ranged between 0.4 and 0.5% RSD
if higher concentrations were used. The limitations of the pulse counting system are clearly seen, with peak heights of more
than 2000 counts reaching saturation (for an integration time of 100 ms), which reduces the accuracy of isotope ratio determinations.
A dozen VOM could be detected in an aged landfill gas sample; several unidentified Sn compounds were present. Although their
isotope ratios are within the confidence value of the standards, it is not yet clear if the acquired precision is good enough
to identify isotopic fractionation of metal(loid)s through biovolatilization processes. With the precision achieved, the combination
of cryotrapping GC and ICP–TOFMS is a powerful tool for monitoring volatile multi-element species in multi-tracer experiments
and isotope dilution methodology.
Received: 23 November 2000 / Revised: 19 February 2001 / Accepted: 24 February 2001 相似文献
144.
Vasyl I. Zaremba Ihor R. Muts Yaroslav M. Kalychak Rolf-Dieter Hoffmann Rainer Pttgen 《Journal of solid state chemistry》2001,160(2):415
The title compound was synthesized by reacting the elements in an arc-melting apparatus under purified argon and subsequent annealing at 870 K. Ca3Ni8In4 was investigated using X-ray diffraction on both powders and single crystals: P63mc, a=898.9(1) pm, c=752.2(2) pm, wR2=0.0591, 327 F2 values, and 35 parameters. This structure is an ordered, noncentrosymmetric variant of the BaLi4 type. The nickel and indium atoms build a complex three-dimensional [Ni8In4] polyanion in which the calcium atoms fill distorted hexagonal channels. To a first approximation the formula may be written as (3 Ca2+)6+ [Ni8In4]6−. Within the polyanion the Ni1, Ni3, and Ni4 atoms form one-dimensional cluster units which extend in the c direction while the Ni2 atoms have only indium neighbors in a distorted tetrahedral coordination. The Ni–Ni distances in the cluster range from 241 to 266 pm. The cluster units are surrounded and interconnected by indium atoms. The group– subgroup relation from centrosymmetric BaLi4 to noncentrosymmetric Ca3Ni8In4 is presented. Chemical bonding in Ca3Ni8In4 and the structural relation with Lu3Co7.77Sn4, Ca3Au6.61Ga4.39, and Co2Al5 is briefly discussed. 相似文献
145.
Polymerisation of methyl methacrylate in the presence of two catalytic chain transfer agents has been investigated. Several factors were examined to see how they would affect the chain transfer process. Oxygen and initiator impurities added to the system were found to be detrimental. The transfer process was highly intolerant of initiator impurities, but was able to endure a large excess of oxygen. The temperature dependencies of the chain transfer process were determined for cobaloxime boron fluoride (COBF) and cobalt(meso‐Ph4‐porphyrin) (CoP). The results showed that a study of MW, or ktr would be a better gauge of the catalyst activity. Activation energies were determined at two concentrations of initiator and it was discovered that the transfer process has a dependence on the initiator concentration. A mechanism for this dependency is proposed that involves a reduction in the active catalyst concentration. As a result, the measured values for Ctr, and ktr, must be apparent values. An additional consequence of the initiator dependence is that the MW of the polymer products will be directly dependent on the concentration of the initiator. 相似文献
146.
147.
Crystal Structure,Magnetism, 89Y Solid State NMR,and 121Sb Mössbauer Spectroscopic Investigations of YIrSb 下载免费PDF全文
Christopher Benndorf Lukas Heletta Theresa Block Hellmut Eckert Rainer Pöttgen 《无机化学与普通化学杂志》2017,643(4):294-298
The ternary antimonide YIrSb was synthesized from the binary precursor YIr and elemental antimony by a diffusion controlled solid‐state reaction. Single crystals were obtained by a flux technique with elemental bismuth as an inert solvent. The YIrSb structure (TiNiSi type, space group Pnma) was refined from single‐crystal X‐ray diffractometer data: a = 711.06(9), b = 447.74(5), c = 784.20(8) pm, wR2 = 0.0455, 535 F2 values, 20 variables. 89Y solid state MAS NMR and 121Sb Mössbauer spectra show single resonance lines in agreement with single‐crystal X‐ray data. YIrSb is a Pauli paramagnet. 相似文献
148.
The complex [C5H5RhH(C2H4)PMe3]BF4 (I) reacts with NaF and NaCN by deprotonation to give C5H5Rh(PMe3)C2H4 but with NaCl, NaBr and NaI the ethylrhodium compounds C5H5RhC2H5(PMe3)X (II–IV) are obtained. The reactions of I with CO and PPri3 yield the BF4 salts of the cations [C5H5RhH(CO)PMe3]+ and [C5H5RhH(PPri3)PMe3]+ (V, VI), respectively, from which the uncharged complexes C5H5Rh(CO)PMe3 (VII) and C5H5Rh(PPRi3)PMe3 (VIII) are prepared. The carbonyl compound VII is also accessible either from C5H5Rh(CO)2 and PMe3 or from C5H5Rh(PMe3)2 and CO. The reaction of I with ethylene leads to the BF4 salt of the cation [C5H5RhC2H5(PMe3)C2H4]+ (X) which on treatment with PMe3 forms the complex [C5H5RhC2H5(PMe3)C2H4PMe3]BF4 (XI). The compound [C5H5RhH(C2H4)PPri3]BF4 (XII) reacts with NaI by insertion to yield C5H5RhC2H5(PPri3)I (XIII) whereas with PPri3 the salt [C5H5RhH(PPri3)2]BF4 (XIV) is produced. The bis(triisopropylphosphine) complex C5H5Rh(PPri3)2 (XVI) is obtained from XIV and NaH. 相似文献
149.
150.