全文获取类型
收费全文 | 441篇 |
免费 | 22篇 |
国内免费 | 2篇 |
专业分类
化学 | 344篇 |
晶体学 | 2篇 |
力学 | 14篇 |
数学 | 83篇 |
物理学 | 22篇 |
出版年
2023年 | 1篇 |
2022年 | 8篇 |
2021年 | 9篇 |
2020年 | 12篇 |
2019年 | 14篇 |
2018年 | 5篇 |
2017年 | 5篇 |
2016年 | 23篇 |
2015年 | 18篇 |
2014年 | 29篇 |
2013年 | 18篇 |
2012年 | 25篇 |
2011年 | 32篇 |
2010年 | 20篇 |
2009年 | 17篇 |
2008年 | 25篇 |
2007年 | 30篇 |
2006年 | 14篇 |
2005年 | 22篇 |
2004年 | 22篇 |
2003年 | 20篇 |
2002年 | 17篇 |
2001年 | 8篇 |
2000年 | 6篇 |
1999年 | 7篇 |
1998年 | 6篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 3篇 |
1994年 | 5篇 |
1993年 | 6篇 |
1992年 | 7篇 |
1990年 | 1篇 |
1989年 | 6篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1979年 | 1篇 |
排序方式: 共有465条查询结果,搜索用时 15 毫秒
11.
Heinrich Lang Bettina Lühmann Roy Buschbeck 《Journal of organometallic chemistry》2004,689(22):3598-3603
A straightforward method for the preparation of metallo carbosiloxanes of type Si(OCH2CH2CH2SiMe2[OCH2PPh2M(CO)n])4 (n = 3, M = Ni, 7a; n = 4, M = Fe, 7b; n = 5: M = Mo, 7c; M = W, 7d), Si(OCH2CH2CH2SiMe[OCH2PPh2Ni(CO)3]2)4 (8) and Me2Si(OCH2CH2CH2SiMe[OCH2PPh2Ni(CO)3]2)2 (11) is described. The reaction of Si(OCH2CH2CH2SiMeXCl)4 (1: X = Me, 2: X = Cl) or Me2Si(OCH2CH2CH2SiMeCl2)2 (9) with HOCH2PPh2 (3) produces Si(OCH2CH2CH2SiMe2(OCH2PPh2))4 (4), Si(OCH2CH2CH2SiMe(OCH2PPh2)2)4 (5) or Me2Si(OCH2CH2CH2SiMe(OCH2PPh2)2)2 (10) in presence of DABCO. Treatment of the latter molecules with Ni(CO)4 (6a), Fe2(CO)9 (6b), M(CO)5(Thf) (6c: M = Mo; 6d: M = W), respectively, gives the title compounds 7a-7d, 8 and 11 in which the PPh2 groups are datively bound to a 16-valence-electron metal carbonyl fragment.The formation of analytical pure and uniform branched and dendritic metallo carbosiloxanes is based on elemental analysis, and IR, 1H, 13C{1H}, 29Si{1H} and 31P{1H} NMR spectroscopic studies. In addition, ESI-TOF mass spectrometric studies were carried out. 相似文献
12.
The mechanism of the solid-solid transformation of NH(4)[N(CN)(2)] into NCN[double bond]C(NH(2))(2), which represents the isolobal analogue of W?hler's historic conversion of ammonium cyanate into urea, has been investigated by temperature-dependent single-crystal and powder X-ray diffraction, neutron powder diffraction, and Raman and solid-state NMR spectroscopy as well as thermoanalytical measurements. The transformation of the ionic dicyanamide into its molecular isomer upon controlled thermal treatment was found to proceed topochemically in the solid state with little molecular motion, giving rise to a single-crystal to single-crystal transformation which manifests itself by a defined metric relation between the unit cells of the two isomers. The exothermic phase transition is thermally activated and was observed to commence at temperatures > or =80 degrees C. The pronounced temperature dependence of the onset of the transformation may be assessed as an indication for the metastability of ammonium dicyanamide at elevated temperatures. Thermal analyses reveal a decrease in the reaction enthalpy (56-13 kJ mol(-1)) at higher heating rates and an average mass loss of 10% gaseous ammonia. Evidence was found for crucial mechanistic steps of the transformation, which is likely to proceed via proton transfer from the ammonium ion to one of the terminal nitrogen atoms of the anion. The protonation is followed by nucleophilic attack of the in situ generated ammonia at the electrophilic nitrile carbon. The proposed mechanistic pathway is based on the results of combined Raman and solid-state NMR spectroscopic as well as neutron powder diffraction measurements. 相似文献
13.
Petersson B Nielsen BB Rasmussen H Larsen IK Gajhede M Nielsen PE Kastrup JS 《Journal of the American Chemical Society》2005,127(5):1424-1430
The X-ray structure of a partly self-complementary peptide nucleic acid (PNA) decamer (H-GTAGATCACT-l-Lys-NH(2)) to 2.60 A resolution is reported. The structure is mainly controlled by the canonical Watson-Crick base pairs formed by the self-complementary stretch of four bases in the middle of the decamer (G(4)A(5)T(6)C(7)). One right- and one left-handed Watson-Crick duplex are formed. The two PNA units C(9)T(10) change helical handedness, so that each PNA strand contains both a right- and a left-handed section. The changed handedness in C(9)T(10) allows formation of Hoogsteen hydrogen bonding between C(9)T(10) and G(4)A(5) of a PNA strand in an adjacent Watson-Crick double helix of the same handedness. Thereby, a PNA-PNA-PNA triplex is formed. The PNA unit A(3) forms a noncanonical base pair with A(8) in a symmetry-related strand of opposite handedness; the base pair is of the A-A reverse Hoogsteen type. The structural diversity of this PNA demonstrates how the PNA backbone is able to adapt to structures governed by the stacking and hydrogen-bonding interactions between the nucleobases. The crystal structure further shows how PNA oligomers containing limited sequence complementarity may form complex hydrogen-bonding networks. 相似文献
14.
15.
Abstract The synthesis of carbon substituted 1, 1-dichloro- and l, l-bis(diethylamino)silacyclobutanes and butenes and their polycondensation reactions with bisphenol A, 1,2-ethanediol and 1,6-hexanediol is described. The monomer silacycles and the organosiloxane polymers are characterized by NMR (1H-, 13C-, 29Si-), GPC, DSC and elemental analysis. 相似文献
16.
Eva-Maria Niehaus Karin Kleigrewe Philipp Wiemann Lena Studt Christian M.K. Sieber Lanelle R. Connolly Michael Freitag Ulrich Güldener Bettina Tudzynski Hans-Ulrich Humpf 《Chemistry & biology》2013,20(8):1055-1066
- Download : Download high-res image (198KB)
- Download : Download full-size image
17.
Bettina Lorantfy Tibor Renkecz Cosima Koch George Horvai Bernhard Lendl Christoph Herwig 《Analytical and bioanalytical chemistry》2014,406(9-10):2421-2432
Extreme halophilic archaea are a yet unexploited source of natural carotenoids. At elevated salinities, however, material corrosivity issues occur and the performance of analytical methods is strongly affected. The goal of this study was to develop a method for identification and downstream processing of potentially valuable bioproducts produced by archaea. To circumvent extreme salinities during analysis, a direct sample preparation method was established to selectively extract both the polar and the nonpolar lipid contents of extreme halophiles with hexane, acetone and the mixture of MeOH/MTBE/water, respectively. Halogenated solvents, as used in conventional extraction methods, were omitted because of environmental considerations and potential process scale-up. The HPLC-MS/MS method using atmospheric pressure chemical ionization was developed and tuned with three commercially available C40 carotenoid standards, covering the wide polarity range of natural carotenoids, containing different number of OH-groups. The chromatographic separation was achieved on a C30 RP-HPLC column with a MeOH/MTBE/water gradient. Polar lipids, the geometric isomers of the C50 carotenoid bacterioruberin, and vitamin MK-8 were the most valuable products found in bioreactor samples. In contrast to literature on shake flask cultivations, no anhydrous analogues of bacterioruberin, as by-products of the carotenoid biosynthesis, were detected in bioreactor samples. This study demonstrates the importance of sample preparation and the applicability of HPLC-MS/MS methods on real samples from extreme halophilic strains. Furthermore, from a biotechnological point-of-view, this study would like to reveal the relevance of using controlled and defined bioreactor cultivations instead of shake flask cultures in the early stage of potential bioproduct profiling. 相似文献
18.
Bettina Albers 《PAMM》2015,15(1):523-524
The theoretical investigation of sound waves in porous materials is motivated by the possible construction of non-destructive testing methods. Here, geotechnical applications are of interest where low frequencies from zero to 100 Hz occur but also systems with higher frequency ranges may be tested non-invasively. Examples are concrete and other construction materials, road surfaces and pavements (some MHz), biological materials like bones and soft tissues, e.g. the surface of the heart (up to 3 MHz) right up to surface coatings by nanomaterials (approximately 100 MHz). (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
19.
Bettina Schweda Dr. Matiss Reinfelds Jakob Hofinger Georg Bäumel Dr. Thomas Rath Dr. Petra Kaschnitz Prof. Dr. Roland C. Fischer Prof. Dr. Michaela Flock Prof. Dr. Heinz Amenitsch Prof. Dr. Markus Clark Scharber Prof. Dr. Gregor Trimmel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(23):e202200276
A series of non-fullerene acceptors based on perylene monoimides coupled in the peri position through phenylene linkers were synthesized via Suzuki-coupling reactions. Various substitution patterns were investigated using density functional theory (DFT) calculations in combination with experimental data to elucidate the geometry and their optical and electrochemical properties. Further investigations of the bulk properties with grazing incidence wide angle X-ray scattering (GIWAXS) gave insight into the stacking behavior of the acceptor thin films. Electrochemical and morphological properties correlate with the photovoltaic performance of devices with the polymeric donor PBDB-T and a maximum efficiency of 3.17 % was reached. The study gives detailed information about structure–property relationships of perylene-linker-perylene compounds. 相似文献
20.
Katharina Röser Bettina Berger Prof. Michael Widhalm Prof. Mario Waser 《ChemistryOpen》2021,10(8):756-759
We herein report an asymmetric protocol to access a series of orthogonally functionalized acyclic chiral target molecules containing a quaternary stereogenic center by carrying out the enantioselective α-alkylation of novel orthogonally functionalized dioxolane-containing cyanoacetates under chiral ammonium salt catalysis. By using just 1 mol % of Maruoka's spirocyclic ammonium salt catalysts enantioselectivities up to e.r.=97.5 : 2.5 could be achieved and further functional group manipulations of the products were carried out as well. 相似文献