全文获取类型
收费全文 | 195篇 |
免费 | 8篇 |
国内免费 | 1篇 |
专业分类
化学 | 160篇 |
晶体学 | 1篇 |
力学 | 9篇 |
数学 | 16篇 |
物理学 | 18篇 |
出版年
2024年 | 2篇 |
2023年 | 2篇 |
2022年 | 6篇 |
2021年 | 4篇 |
2020年 | 5篇 |
2019年 | 7篇 |
2018年 | 3篇 |
2017年 | 5篇 |
2016年 | 6篇 |
2015年 | 7篇 |
2014年 | 7篇 |
2013年 | 15篇 |
2012年 | 20篇 |
2011年 | 21篇 |
2010年 | 5篇 |
2009年 | 8篇 |
2008年 | 10篇 |
2007年 | 10篇 |
2006年 | 10篇 |
2005年 | 11篇 |
2004年 | 9篇 |
2003年 | 8篇 |
2002年 | 3篇 |
2001年 | 2篇 |
2000年 | 4篇 |
1999年 | 4篇 |
1998年 | 2篇 |
1994年 | 1篇 |
1992年 | 1篇 |
1984年 | 2篇 |
1981年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有204条查询结果,搜索用时 15 毫秒
61.
Carney RP DeVries GA Dubois C Kim H Kim JY Singh C Ghorai PK Tracy JB Stiles RL Murray RW Glotzer SC Stellacci F 《Journal of the American Chemical Society》2008,130(3):798-799
A combination of immiscible molecules in the ligand shell of a gold nanoparticle (NP) has been shown to phase separate into a rippled structure; this phase separation can be used to direct the assembly of the NPs into chains. Here we demonstrate that only NPs within a certain size range can form chains, and we conclude that the rippled morphology of the ligand shell also exists only within that given size range. We corroborate this result with simulations of the ligand arrangement on NPs of various sizes. 相似文献
62.
De Angelis F Fantacci S Evans N Klein C Zakeeruddin SM Moser JE Kalyanasundaram K Bolink HJ Grätzel M Nazeeruddin MK 《Inorganic chemistry》2007,46(15):5989-6001
We report a combined experimental and theoretical study on cationic Ir(III) complexes for OLED applications and describe a strategy to tune the phosphorescence wavelength and to enhance the emission quantum yields for this class of compounds. This is achieved by modulating the electronic structure and the excited states of the complexes by selective ligand functionalization. In particular, we report the synthesis, electrochemical characterization, and photophysical properties of a new cationic Ir(III) complex, [Ir(2,4-difluorophenylpyridine)2(4,4'-dimethylamino-2,2'-bipyridine)](PF(6)) (N969), and compare the results with those reported for the analogous [Ir(2-phenylpyridine)2(4,4'-dimethylamino-2,2'-bipyridine)](PF(6)) (N926) and for the prototype [Ir(2-phenylpyridine)2(4,4'-tert-butyl-2,2'-bipyridine)](PF(6)) complex, hereafter labeled N925. The three complexes allow us to explore the (C/\N) and (N/\N) ligand functionalization: considering N925 as a reference, we investigate in N926 the effect of electron-releasing substituents on the bipyridine ligand, while in N969, we investigate the combined effect of electron-releasing substituents on the bipyridine ligand and the effect of electron-withdrawing substituents on the phenylpyridine ligands. For N969 we obtain blue-green emission at 463 nm with unprecedented high quantum yield of 85% in acetonitrile solution at room temperature. To gain insight into the factors responsible for the emission color change and the different quantum yields, we perform DFT and TDDFT calculations on the ground and excited states of the three complexes, characterizing the excited-state geometries and including solvation effects on the calculation of the excited states. This computational procedure allows us to provide a detailed assignment of the excited states involved in the absorption and emission processes and to rationalize the factors determining the efficiency of radiative and nonradiative deactivation pathways in the investigated complexes. This work represents an example of electronic structure-driven tuning of the excited-state properties, thus opening the way to a combined theoretical and experimental strategy for the design of new iridium(III) phosphors with specific target characteristics. 相似文献
63.
Quantitative analysis of trace levels of surface contamination by X‐ray photoelectron spectroscopy. Part I: Statistical uncertainty near the detection limit 下载免费PDF全文
We discuss the problem of quantifying common sources of statistical uncertainties for analyses of trace levels of surface contamination by using X‐ray photoelectron spectroscopy. We examine the propagation of error for peak‐area measurements by using common forms of linear and polynomial background subtraction including the correlation of points used to determine both background and peak areas. This correlation has been neglected in previous analyses, but we show that it contributes significantly to the peak‐area uncertainty near the detection limit. We introduce the concept of relative background subtraction variance (RBSV) that quantifies the uncertainty introduced by the method of background determination relative to the uncertainty of the background area itself. The uncertainties of the peak area and atomic concentration and of the detection limit are expressed using the RBSV, which separates the contributions from the acquisition parameters, the background‐determination method, and the properties of the measured spectrum. These results are then combined to find acquisition strategies that minimize the total measurement time needed to achieve a desired detection limit or atomic‐percentage uncertainty for a particular trace element. Minimization of data‐acquisition time is important for samples that are sensitive to X‐ray dose and also for laboratories that need to optimize throughput. 相似文献
64.
Dr. Stéphanie Norsikian Dr. Cedric Tresse Dr. Marc François-Eude Dr. Louis Jeanne-Julien Dr. Guillaume Masson Vincent Servajean Dr. Grégory Genta-Jouve Prof. Jean-Marie Beau Dr. Emmanuel Roulland 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(16):6674-6678
A total synthesis of tiacumicin B, a natural macrolide whose remarkable antibiotic properties are used to treat severe intestinal infections, is reported. The strategy is in part based on the prior synthesis of the tiacumicin B aglycone, and on the decisive use of sulfoxides as anomeric leaving groups in hydrogen-bond-mediated aglycone delivery (HAD). This new HAD variant permitted highly β-selective rhamnosylation and noviosylation. To increase convergence, the rhamnosylated C1–C3 fragment thus obtained was anchored to the C4–C19 aglycone fragment by adapting the Suzuki–Miyaura cross-coupling used for the aglycone synthesis. Ring-size-selective macrolactonization provided a compound engaged directly in the noviolysation step with virtually total β selectivity. The final efficient removal of all the protecting groups provided synthetic tiacumicin B. 相似文献
65.
Ayers S Graf TN Adcock AF Kroll DJ Shen Q Swanson SM Wani MC Darveaux BA Pearce CJ Oberlies NH 《Tetrahedron letters》2011,52(40):5128-5130
A fungal extract (MSX 63619), from the Mycosynthetix library of over 50,000 fungi, displayed promising cytotoxicity against a human tumor cell panel. Bioactivity-directed fractionation led to the isolation of an o-pyranonaphthoquinone decaketide, which we termed obionin B (1). The structure of 1 was deduced via spectroscopic and spectrometric techniques. The IC50 value of 1 was moderate, ranging from 3 to 13 μM, depending on the cell line tested. 相似文献
66.
Malvolti F Rouxel C Mongin O Hapiot P Toupet L Blanchard-Desce M Paul F 《Dalton transactions (Cambridge, England : 2003)》2011,40(25):6616-6618
We report in this communication the study of the intramolecular electron transfer through a 2,7-diethynylfluorenyl spacer in the Fe(II)/Fe(III) mixed-valent (MV) complex [(η(2)-dppe)(η(5)-C(5)Me(5))FeC≡C(2,7-C(21)H(24))C≡CFe(η(5)-C(5)Me(5))(η(2)-dppe)][PF(6)] (1[PF(6)]). The complex is generated in situ by comproportionation from its homovalent dinuclear Fe(II) and Fe(III) parents (1 and 1[PF(6)](2)). It is shown that electronic delocalization is much more effective through a 2,7-fluorenyl than through a 4,4'-biphenyl bridging unit. 相似文献
67.
Popovici J Bertrand C Jacquemoud D Bellvert F Fernandez MP Comte G Piola F 《Molecules (Basel, Switzerland)》2011,16(3):2323-2333
We report the identification of the allelochemical 3-(1-oxo-3-phenylpropyl)-1,1,5-trimethylcyclo-hexane-2,4,6-trione, known as myrigalone A, from the fruits and leaves of Myrica gale. The structure of the compound was confirmed by high-resolution techniques (UV, MS and NMR analysis). The compound is phytotoxic towards classical plant species used for allelochemical assays and also against Fallopia x bohemica, a highly invasive plant. Application of either powdered dry leaves or dry fruits of M. gale also showed in vitro phytotoxic activity. We hypothesize that M. gale could be used as a green allelopathic shield to control Fallopia x bohemica invasion, in addition to its potential use as an environmentally friendly herbicide. 相似文献
68.
Dr. Cosima Dufour Dr. Joachim Wink Dr. Michael Kurz Dr. Herbert Kogler Helene Olivan Serge Sablé Winfried Heyse Dr. Martin Gerlitz Dr. Luigi Toti Antje Nußer Dr. Astrid Rey Dr. Cedric Couturier Dr. Armin Bauer Dr. Mark Brönstrup 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(50):16123-16128
In an antibiotic lead discovery program, the known strain Streptomyces armeniacus DSM19369 has been found to produce three new natural products when cultivated on a malt‐containing medium. The challenging structural elucidation of the isolated compounds was achieved by using three independent methods, that is, chemical degradation followed by NMR spectroscopy, a computer‐assisted structure prediction algorithm, and X‐ray crystallography. The compounds, named armeniaspirol A–C ( 2 – 4 ), exhibit a compact, hitherto unprecedented chlorinated spiro[4.4]non‐8‐ene scaffold. Labeling experiments with [1‐13C] acetate, [1,2‐13C2] acetate, and [U‐13C] proline suggest a biosynthesis through a rare two‐chain mechanism. Armeniaspirols displayed moderate to high in vitro activities against Gram‐positive pathogens such as methicillin‐resistant S. aureus (MRSA) or vancomycin resistant E. faecium (VRE). As analogue 2 was active in vivo in an MRSA sepsis model, and showed no development of resistance in a serial passaging experiment, it represents a new antibiotic lead structure. 相似文献
69.
70.
A General Entry to Antifeedant Sesterterpenoids: Total Synthesis of (+)‐Norleucosceptroid A, (−)‐Norleucosceptroid B,and (−)‐Leucosceptroid K 下载免费PDF全文
M. Sc. Cedric L. Hugelshofer Dr. Thomas Magauer 《Angewandte Chemie (International ed. in English)》2014,53(42):11351-11355
The first asymmetric total synthesis of the antifeedant terpenoids (+)‐norleucosceptroid A, (?)‐norleucosceptroid B, and (?)‐leucosceptroid K has been accomplished. This highly concise synthetic route was guided by our efforts to develop a platform for the collective synthesis of a whole family of antifeedant natural products. The synthesis features a Hauser–Kraus‐type annulation followed by an unprecedented, highly efficient intramolecular dilactol aldol‐type condensation reaction to produce the 5,6,5 skeleton. The developed synthetic route proceeds for norleucosceptroid A and B in 16 steps (longest linear sequence) from known compounds. 相似文献