全文获取类型
收费全文 | 357篇 |
免费 | 24篇 |
专业分类
化学 | 264篇 |
晶体学 | 6篇 |
力学 | 14篇 |
数学 | 29篇 |
物理学 | 68篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2021年 | 8篇 |
2020年 | 9篇 |
2019年 | 19篇 |
2018年 | 4篇 |
2017年 | 8篇 |
2016年 | 7篇 |
2015年 | 17篇 |
2014年 | 16篇 |
2013年 | 34篇 |
2012年 | 19篇 |
2011年 | 21篇 |
2010年 | 25篇 |
2009年 | 25篇 |
2008年 | 20篇 |
2007年 | 27篇 |
2006年 | 16篇 |
2005年 | 12篇 |
2004年 | 13篇 |
2003年 | 18篇 |
2002年 | 12篇 |
2001年 | 2篇 |
2000年 | 5篇 |
1999年 | 4篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1994年 | 6篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 5篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1984年 | 1篇 |
1982年 | 4篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1977年 | 2篇 |
1975年 | 1篇 |
排序方式: 共有381条查询结果,搜索用时 15 毫秒
1.
Delfino Chamorro-Arenas Alejandro A. Nolasco-Hernández Dr. Lilia Fuentes Dr. Leticia Quintero Prof. Dr. Fernando Sartillo-Piscil 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(21):4671-4676
Remote and multiple functionalization of piperidines without the use of transition-metal catalysts and elaborate directing groups is one of the major challenges in organic synthesis. Herein is reported an unprecedented two-step protocol that enables the multiple functionalization of piperidines to either 4-substituted or trans-3,4-disubstituted 2-piperidones. First, by exploiting the duality of TEMPO reactivity, which under oxidative and thermal conditions fluctuates between cationic and persistent-radical form, a novel multiple C(sp3)-H oxidation of piperidines to α,β-unsaturated 2-piperidones was developed. Second, the intrinsic low reactivity of the unsaturated piperidones toward conjugated Grignard additions was overcome by using trimethylsilyl chloride (TMSCl) as Lewis acid. Subsequently, conjugated Grignard addition/electrophilic trapping protocol provided substituted 2-piperidone intermediates, some of which were then transformed into pharmaceutical alkaloids. 相似文献
2.
Leo Iu Jos A. Fuentes Mesfin E. Janka Kevin J. Fontenot Matthew L. Clarke 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(7):2142-2146
The hydroformylation of propene to give predominantly iso‐butanal has been achieved; class‐leading selectivity is possible even at higher temperatures that deliver fast conversion. Racemic rhodium complexes of bidentate phospholane phosphites derived from tropos‐biphenols and unusual solvent systems are the key to the selectivity observed. 相似文献
3.
Ivan Limachi Mariela Gonzalez-Ramirez Sophie Manner Juan C. Ticona Efrain Salamanca Alberto Gimenez Olov Sterner 《Molecules (Basel, Switzerland)》2021,26(4)
The fractionation of an ethanol extract of the bark of Trichilia adolfi yielded four novel limonoids (trichilinones A-D, 1–4), with five fused rings and related to the hortiolide-type limonoids. Starting with an ε-lactone, which is α,β-unsaturated in trichilinones A and D (1 and 4), attached to a tetrahydrofuran ring that is connected to an unusual bicyclo [5.1.0] hexane system, joined with a cyclopentanone with a 3-furanyl substituent [(2-oxo)-furan-(5H)-3-yl in trichilinone D (4)], the four compounds isolated display a new 7/5/3/5/5 limonoid ring system. Their structures were established based on extensive analysis of NMR spectroscopic data. As the crude extract possessed anti-leishmanial properties, the compounds were assayed for cytotoxic and anti-parasitic activities in vitro in murine macrophages cells (Raw 264.7) and leishmania promastigotes (L. amazoniensis and L. braziliensis), respectively. The compounds showed moderate cytotoxicity (approximately 70 μg/mL), but are not responsible for the leishmanicidal effect of the extract. 相似文献
4.
Peter J. Cumpson Naoko Sano Ian W. Fletcher Jose F. Portoles Mariela Bravo‐Sanchez Anders J. Barlow 《Surface and interface analysis : SIA》2015,47(10):986-993
Principal component analysis (PCA) and other multivariate analysis methods have been used increasingly to analyse and understand depth profiles in X‐ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and secondary ion mass spectrometry (SIMS). These methods have proved equally useful in fundamental studies as in applied work where speed of interpretation is very valuable. Until now these methods have been difficult to apply to very large datasets such as spectra associated with 2D images or 3D depth‐profiles. Existing algorithms for computing PCA matrices have been either too slow or demanded more memory than is available on desktop PCs. This often forces analysts to ‘bin’ spectra on much more coarse a grid than they would like, perhaps even to unity mass bins even though much higher resolution is available, or select only part of an image for PCA analysis, even though PCA of the full data would be preferred. We apply the new ‘random vectors’ method of singular value decomposition proposed by Halko and co‐authors to time‐of‐flight (ToF)SIMS data for the first time. This increases the speed of calculation by a factor of several hundred, making PCA of these datasets practical on desktop PCs for the first time. For large images or 3D depth profiles we have implemented a version of this algorithm which minimises memory needs, so that even datasets too large to store in memory can be processed into PCA results on an ordinary PC with a few gigabytes of memory in a few hours. We present results from ToFSIMS imaging of a citrate crystal and a basalt rock sample, the largest of which is 134GB in file size corresponding to 67 111 mass values at each of 512 × 512 pixels. This was processed into 100 PCA components in six hours on a conventional Windows desktop PC. © 2015 The Authors. Surface and Interface Analysis published by John Wiley & Sons Ltd. 相似文献
5.
Mesoporous Silica Nanoparticles Decorated with Carbosilane Dendrons as New Non‐viral Oligonucleotide Delivery Carriers 下载免费PDF全文
Ángel Martínez Dr. Elena Fuentes‐Paniagua Dr. Alejandro Baeza Dr. Javier Sánchez‐Nieves Dr. Mónica Cicuéndez Dr. Rafael Gómez Dr. F. Javier de la Mata Dr. Blanca González Prof. María Vallet‐Regí 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(44):15651-15666
A novel nanosystem based on mesoporous silica nanoparticles covered with carbosilane dendrons grafted on the external surface of the nanoparticles is reported. This system is able to transport single‐stranded oligonucleotide into cells, avoiding an electrostatic repulsion between the cell membrane and the negatively charged nucleic acids thanks to the cationic charge provided by the dendron coating under physiological conditions. Moreover, the presence of the highly ordered pore network inside the silica matrix would make possible to allocate other therapeutic agents within the mesopores with the aim of achieving a double delivery. First, carbosilane dendrons of second and third generation possessing ammonium or tertiary amine groups as peripheral functional groups were prepared. Hence, different strategies were tested in order to obtain their suitable grafting on the outer surface of the nanoparticles. As nucleic acid model, a single‐stranded DNA oligonucleotide tagged with a fluorescent Cy3 moiety was used to evaluate the DNA adsorption capacity. The hybrid material functionalised with the third generation of a neutral dendron showed excellent DNA binding properties. Finally, the cytotoxicity as well as the capability to deliver DNA into cells, was tested in vitro by using a human osteoblast‐like cell line, achieving good levels of internalisation of the vector DNA/carbosilane dendron‐functionalised material without affecting the cellular viability. 相似文献
6.
Adding a Structural Context to the Deprotometalation and Trans‐Metal Trapping Chemistry of Phenyl‐Substituted Benzotriazole 下载免费PDF全文
Dr. M. Ángeles Fuentes Dr. Alan R. Kennedy Prof. Robert E. Mulvey Dr. John A. Parkinson Dr. Toni Rantanen Dr. Stuart D. Robertson Prof. Victor Snieckus 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):14812-14822
Organometallic bases are becoming increasingly complex, because mixing components can lead to bases superior to single‐component bases. To better understand this superiority, it is useful to study metalated intermediate structures prior to quenching. This study is on 1‐phenyl‐1H‐benzotriazole, which was previously deprotonated by an in situ ZnCl2 ? TMEDA/LiTMP (TMEDA=N,N,N′,N′‐tetramethylethylenediamine; TMP=2,2,6,6‐tetramethylpiperidide) mixture and then iodinated. Herein, reaction with LiTMP exposes the deficiency of the single‐component base as the crystalline product obtained was [{4‐R‐1‐(2‐lithiophenyl)‐1H‐benzotriazole ? 3THF}2], [R=2‐C6H4(Ph)NLi], in which ring opening of benzotriazole and N2 extrusion had occurred. Supporting lithiation by adding iBu2Al(TMP) induces trans‐metal trapping, in which C?Li bonds transform into C?Al bonds to stabilise the metalated intermediate. X‐ray diffraction studies revealed homodimeric [(4‐R′‐1‐phenyl‐1H‐benzotriazole)2], [R′=(iBu)2Al(μ‐TMP)Li], and its heterodimeric isomer [(4‐R′‐1‐phenyl‐1H‐benzotriazole){2‐R′‐1‐phenyl‐1H‐benzotriazole}], whose structure and slow conformational dynamics were probed by solution NMR spectroscopy. 相似文献
7.
8.
Dr. Waqar Rizvi Naxhije Berisha Dr. Christopher Farley Dr. N. V. S. Dinesh K. Bhupathiraju Dr. Chrysafis Andreou Emaad Khwaja German V. Fuentes Dr. Moritz F. Kircher Dr. Ruomei Gao Dr. Charles Michael Drain 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(64):14517-14521
Distortion of nominally planar phthalocyanine macrocycles affects the excited state dynamics in that most of the excited-state energy decays through internal conversion. A click-type annulation reaction on a perfluorophthalocyanine platform appending a seven-membered ring to the β-positions on one or more of the isoindoles distorts the macrocycle and modulates solubility. The distorted derivative enables photoacoustic imaging, photothermal effects, and strong surface-enhanced resonance Raman signals. 相似文献
9.
Silvana P. Ravía Mariela Risso Santiago Kröger Silvana Vero Gustavo A. Seoane Daniela Gamenara 《Tetrahedron: Asymmetry》2013,24(19):1207-1211
(2S,3R)-Sitophilate, the male-produced aggregation pheromone of the granary weevil Sitophilus granarius (L.) was prepared stereoselectively using a novel chemoenzymatic approach in 50% overall yield. The synthetic design was based on an enantioselective fungal reduction of ethyl 2-methyl-3-oxopentanoate with a strain of Aureobasidium pullulans (CCM H1), followed by a Mitsunobu inversion at C3. The last step in the synthetic sequence was a lipase-mediated transesterification using the commercially available Candida antarctica B lipase (CaL B, Novozym 435) using microwave irradiation under solvent-free conditions. 相似文献
10.
Earlier we noted that the hydroboration of the trimethylsilyl enol ether of an acyclic ketone results in an elimination of a trimethylsiloxyborane moiety with the subsequent formation of an olefin.1,2 The olefin formed then undergoes hydroboration giving a monoalcohol upon oxidation. (eq 1) We wish to report here on the utility of this sequence, illustrated in eq 1, in the reductive 1,2 transposition of acyclic ketones.3 相似文献