全文获取类型
收费全文 | 407篇 |
免费 | 14篇 |
专业分类
化学 | 275篇 |
晶体学 | 10篇 |
力学 | 22篇 |
数学 | 48篇 |
物理学 | 66篇 |
出版年
2021年 | 3篇 |
2020年 | 5篇 |
2019年 | 9篇 |
2018年 | 6篇 |
2017年 | 4篇 |
2016年 | 9篇 |
2015年 | 9篇 |
2014年 | 13篇 |
2013年 | 34篇 |
2012年 | 26篇 |
2011年 | 19篇 |
2010年 | 11篇 |
2009年 | 15篇 |
2008年 | 16篇 |
2007年 | 17篇 |
2006年 | 14篇 |
2005年 | 15篇 |
2004年 | 18篇 |
2003年 | 15篇 |
2002年 | 26篇 |
2001年 | 5篇 |
2000年 | 5篇 |
1999年 | 5篇 |
1997年 | 6篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 7篇 |
1992年 | 5篇 |
1991年 | 5篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1986年 | 3篇 |
1985年 | 8篇 |
1984年 | 5篇 |
1983年 | 5篇 |
1982年 | 6篇 |
1981年 | 3篇 |
1980年 | 7篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1975年 | 2篇 |
1974年 | 5篇 |
1973年 | 7篇 |
1972年 | 2篇 |
1971年 | 2篇 |
1970年 | 2篇 |
1897年 | 2篇 |
排序方式: 共有421条查询结果,搜索用时 15 毫秒
11.
Zhibo Liu Maral Pourghiasian Mark Alex Radtke Joseph Lau Dr. Jinhe Pan Gemma M. Dias Dr. Donald Yapp Dr. Kuo‐Shyan Lin Prof. Dr. Francois Bénard Prof. Dr. David M. Perrin 《Angewandte Chemie (International ed. in English)》2014,53(44):11876-11880
A new zwitterionic organotrifluoroborate is appended to three radiosynthons that afford undergo facile bioconjugation to several clinically relevant peptides and one enzyme inhibitor. Molecularly complex bioconjugates are 18F‐labeled in a single aqueous step in rapid time (<15 min) without HPLC purification to afford tracers in good yields (>200 mCi, 20–40 %) at high specific activity (≥3 Ci/μmol) and at >98 % purity. PET imaging shows in vivo stability and tumor uptake. 相似文献
12.
Chitosan loaded with silver nanoparticles,CS‐AgNPs,using thymus syriacus,wild mint,and rosemary essential oil extracts as reducing and capping agents 下载免费PDF全文
Fadi AL‐Shnani Thanaa Al‐Haddad Francois Karabet Abdul Wahab Allaf 《Journal of Physical Organic Chemistry》2017,30(11)
The present study describes the green method for the preparation of chitosan loaded with silver nanoparticles (CS‐AgNPs) in the presence of 3 different extracted essential oils. The essential oils play dual roles as reductant and capping agents. The reducing power and DPPH (2,2‐diphenyl‐1‐picrylhydrazyl) assay for the 3 essential oils—Thymus syriacus (T), wild mint (M), and rosemary (R)—have been reported. The preparation of CS‐AgNPs was performed by 2 steps. The 3 previously extracted essential oils have been used as reducing and capping agent in the first step, while in the second step, silver nanoparticles were integrated in chitosan. The integration of AgNPs in the structure of chitosan was confirmed by ultraviolet‐visible, Fourier transform infrared spectroscopy, scanning electron microscopy techniques, and energy dispersive X‐ray. Surface plasmon resonance confirmed the formation of CS‐AgNPs with maximum absorbance at λmax between 405 ‐ 410 and 410 ‐ 430 nm for colloidal and films of CS‐AgNPs, respectively. The intensity of bands at 3408 cm?1 in the fourier transform infrared spectroscopy measurements was decreased substantially and shifted slightly to lower frequency (?υ = 43 cm?1). Scanning electron microscopy shows a spherical morphology of AgNPs with size of 62 nm for both colloidal and film samples, and energy dispersive X‐ray analysis shows peaks confirming AgNPs formation. 相似文献
13.
Jan W. H. Swanepoel Francois C. Van Graan 《Annals of the Institute of Statistical Mathematics》2002,54(3):531-542
New goodness-of-fit tests, based on bootstrap estimated expectations of probability integral transformed order statistics, are derived for the location-scale model. The resulting test statistics are location and scale invariant, and are sensitive to discrepancies at the tails of the hypothesized distribution. The limiting null distributions of the test statistics are derived in terms of functionals of a certain Gaussian process, and the tests are shown to be consistent against a broad family of alternatives. Critical points for all sample sizes are provided for tests of normality. A simulation study shows that the proposed tests are more powerful than established tests such as Shapiro-Wilk, Cramér-von Mises and Anderson-Darling, for a wide range of alternative distributions. 相似文献
14.
15.
Jean-Franjois Nierengarten Andreas Herrmann Rik R. Tykwinski Markus Riittimann Francois Diederich Corinne Boudon Jean-Paul Gisselbrecht Maurice Gross 《Helvetica chimica acta》1997,80(1):293-316
The synthesis of (E)-hex-3-ene-l, 5-diynes and 3-methylidenepenta-1, 4-diynes with pendant methano[60]-fullerene moieties as precursors to C60-substituted poly(triacetylenes) (PTAs, Fig. 1) and expanded radialenes (Fig. 2) is described. The Bingel reaction of diethyl (E)-2, 3-dialkynylbut-2-ene-1, 4-diyl bis(2-bromopropane-dioates) 5 and 6 with two C60 molecules (Scheme 2) afforded the monomeric, silyl-protected PTA precursors 9 and 10 which, however, could not be effectively desilylated (Scheme 4). Also formed during the synthesis of 9 and 10 , as well as during the reaction of C60 with thedesilylated analogue 16 (Scheme 5 ), were the macrocyclic products 11, 12 , and 17 , respectively, resulting from double Bingel addition to one C-sphere. Rigorous analysis revealed that this novel macrocyclization reaction proceeds with complete regio- and diastereoselectivity. The second approach to a suitable PTA monomer attempted N, N′-dicyclohexylcarbodiimide(DCC)-mediated esterification of (E)-2, 3-diethynylbut-2-ene-l, 4-diol ( 18 , Scheme 6) with mono-esterified methanofullerene-dicarboxylic acid 23 ; however, this synthesis yielded only the corresponding decarboxylated methanofullerene-carboxylic ester 27 (Scheme 7). To prevent decarboxylation, a spacer was inserted between the reacting carboxylic-acid moiety and the methane C-atom in carboxymethyl ethyl 1, 2-methano[60]fullerene-61, 61-dicarboxylate ( 28 , Scheme 8), and DCC-mediated esterification with diol 18 afforded PTA monomer 32 in good yield. The formation of a suitable monomeric precursor 38 to C60-substituted expanded radialenes was achieved in 5 steps starting from dihydroxyacetone (Schemes 9 and 10), with the final step consisting of the DCC-mediated esterification of 28 with 2-[1-ethynyl(prop-2-ynylidene)]propane-1, 3-diol ( 33 ). The first mixed C60-C70 fullerene derivative 49 , consisting of two methano[60]fullerenes attached to a methano[70]fullerene, was also prepared and fully characterized (Scheme 13). The Cs-symmetrical hybrid compound was obtained by DCC-mediated esterification of bis[2-(2-hydroxy-ethoxy)ethyl] 1, 2-methano[70]fullerene-71, 71-dicarboxylate ( 46 ) with an excess of the C60-carboxylic acid 28 . The presence of two different fullerenes in the same molecule was reflected by its UV/VIS spectrum, which displayed the characteristic absorption bands of both the C70 and C60 mono-adducts, but at the same time indicated no electronic interaction between the different fullerene moieties. Cyclic voltammetry showed two reversible reduction steps for 49 , and comparison with the corresponding C70 and C60 mono-adducts 46 and 30 indicated that the three fullerenes in the composite fullerene compound behave as independent redox centers. 相似文献
16.
Diketopyrrolopyrrole‐Porphyrin Conjugates with High Two‐Photon Absorption and Singlet Oxygen Generation for Two‐Photon Photodynamic Therapy 下载免费PDF全文
Julie Schmitt Prof. Valérie Heitz Dr. Angélique Sour Dr. Frédéric Bolze Dr. Hussein Ftouni Prof. Jean‐Francois Nicoud Dr. Lucia Flamigni Dr. Barbara Ventura 《Angewandte Chemie (International ed. in English)》2015,54(1):169-173
Two‐photon photodynamic therapy is a promising therapeutic method which requires the development of sensitizers with efficient two‐photon absorption and singlet‐oxygen generation. Reported here are two new diketopyrrolopyrrole‐porphyrin conjugates as robust two‐photon absorbing dyes with high two‐photon absorption cross‐sections within the therapeutic window. Furthermore, for the first time the singlet‐oxygen generation efficiency of diketopyrrolopyrrole‐containing systems is investigated. A preliminary study on cell culture showed efficient two‐photon induced phototoxicity. 相似文献
17.
Christian Wenz Coral Barbas Ángeles López‐Gonzálvez Antonia Garcia Fernando Benavente Victoria Sanz‐Nebot Tim Blanc Gordon Freckleton Philip Britz‐McKibbin Meera Shanmuganathan Francois de l′Escaille Johann Far Rob Haselberg Sean Huang Carolin Huhn Martin Pattky David Michels Si Mou Feng Yang Christian Neusuess Nora Tromsdorf Edward E.K. Baidoo Jay D. Keasling SungAe Suhr Park 《Journal of separation science》2015,38(18):NA-NA
A collaborative study on the robustness and portability of a capillary electrophoresis‐mass spectrometry method for peptide mapping was performed by an international team, consisting of 13 independent laboratories from academia and industry. All participants used the same batch of samples, reagents and coated capillaries to run their assays, whereas they utilized the capillary electrophoresis‐mass spectrometry equipment available in their laboratories. The equipment used varied in model, type and instrument manufacturer. Furthermore, different types of sheath‐flow capillary electrophoresis–mass spectrometry interfaces were used. Migration time, peak height and peak area of ten representative target peptides of trypsin‐digested bovine serum albumin were determined by every laboratory on two consecutive days. The data were critically evaluated to identify outliers and final values for means, repeatability (precision within a laboratory) and reproducibility (precision between laboratories) were established. For relative migration time the repeatability was between 0.05 and 0.18% RSD and the reproducibility between 0.14 and 1.3% RSD. For relative peak area repeatability and reproducibility values obtained were 3–12 and 9–29% RSD, respectively. These results demonstrate that capillary electrophoresis‐mass spectrometry is robust enough to allow a method transfer across multiple laboratories and should promote a more widespread use of peptide mapping and other capillary electrophoresis‐mass spectrometry applications in biopharmaceutical analysis and related fields. 相似文献
18.
19.
Ania Alik Chafiaa Bouguechtouli Manon Julien Wolfgang Bermel Rania Ghouil Sophie Zinn‐Justin Francois‐Xavier Theillet 《Angewandte Chemie (International ed. in English)》2020,59(26):10411-10415
Abundant phosphorylation events control the activity of nuclear proteins involved in gene regulation and DNA repair. These occur mostly on disordered regions of proteins, which often contain multiple phosphosites. Comprehensive and quantitative monitoring of phosphorylation reactions is theoretically achievable at a residue‐specific level using 1H‐15N NMR spectroscopy, but is often limited by low signal‐to‐noise at pH>7 and T>293 K. We have developed an improved 13Cα‐13CO correlation NMR experiment that works equally at any pH or temperature, that is, also under conditions at which kinases are active. This allows us to obtain atomic‐resolution information in physiological conditions down to 25 μm . We demonstrate the potential of this approach by monitoring phosphorylation reactions, in the presence of purified kinases or in cell extracts, on a range of previously problematic targets, namely Mdm2, BRCA2, and Oct4. 相似文献
20.
We present experimental evidence that pressure solution creep does not establish a steady-state interface microstructure as previously thought. Conversely, pressure solution controlled strain and the characteristic length scale of interface microstructures grow as the cubic root of time. Transient creep with the same scaling is known in metallurgy (Andrade creep). The apparent universal scaling of pressure solution transient creep is explained using an analogy with spinodal dewetting. 相似文献