全文获取类型
收费全文 | 456篇 |
免费 | 18篇 |
国内免费 | 2篇 |
专业分类
化学 | 262篇 |
晶体学 | 6篇 |
力学 | 9篇 |
数学 | 69篇 |
物理学 | 130篇 |
出版年
2023年 | 3篇 |
2022年 | 6篇 |
2021年 | 12篇 |
2020年 | 4篇 |
2019年 | 5篇 |
2018年 | 5篇 |
2017年 | 12篇 |
2016年 | 12篇 |
2015年 | 11篇 |
2014年 | 14篇 |
2013年 | 31篇 |
2012年 | 21篇 |
2011年 | 19篇 |
2010年 | 17篇 |
2009年 | 10篇 |
2008年 | 15篇 |
2007年 | 10篇 |
2006年 | 15篇 |
2005年 | 15篇 |
2004年 | 14篇 |
2003年 | 13篇 |
2002年 | 40篇 |
2001年 | 18篇 |
2000年 | 9篇 |
1999年 | 15篇 |
1998年 | 7篇 |
1997年 | 4篇 |
1996年 | 4篇 |
1995年 | 9篇 |
1994年 | 5篇 |
1993年 | 6篇 |
1992年 | 6篇 |
1991年 | 8篇 |
1990年 | 10篇 |
1989年 | 7篇 |
1988年 | 6篇 |
1987年 | 7篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 6篇 |
1983年 | 8篇 |
1981年 | 4篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1971年 | 4篇 |
1966年 | 1篇 |
1957年 | 1篇 |
1939年 | 1篇 |
排序方式: 共有476条查询结果,搜索用时 15 毫秒
151.
The infrared spectrum of 13C2HD has been investigated using high-resolution Fourier transform infrared spectroscopy. A large number of ro-vibrational transitions in the spectral region 1000–6600?cm?1 have been recorded and assigned. This paper is focused only on the vibrational bands involving pure stretching, stretching–bending or stretching–stretching modes. In total, 78 bands have been identified and assigned, 29 related to υ1(CH stretch), 27 to υ2(CC stretch), and 22 to υ3(CD stretch). The data pertaining to each stretching mode have been fitted simultaneously in order to obtain accurate sets of rotational and vibrational parameters for the excited states. 相似文献
152.
Rekha Raghunathan Swetha Mahesula Kranthi Kancharla Preethi Janardhanan Yeshwant L. A. Jadhav Robert Nadeau German P. Villa Robert L. Cook Colleen M. Witt Jonathan A. L. Gelfond Thomas G. Forsthuber William E. Haskins 《Particle & Particle Systems Characterization》2013,30(4):355-364
B‐precursor acute lymphoblastic leukemia (B‐ALL) lymphoblast (blast) internalization of anti‐cytokine receptor‐like factor 2 (CRLF2) antibody‐armored biodegradable nanoparticles (AbBNPs) are investigated. First, AbBNPsaere synthesized by adsorbing anti‐CRLF2 antibodies to poly(D,L‐lactide‐co‐glycolide) (PLGA) nanoparticles of various sizes and antibody surface density (Ab/BNP) ratios. Second, AbBNPs are incubated with CRLF2‐overexpressing (CRLF2+) or control blasts. Third, internalization of AbBNPs by blasts is evaluated by multicolor flow cytometry as a function of receptor expression, AbBNP size, and Ab/BNP ratio. Results from these experiments are confirmed by electron microscopy, fluorescence microscopy, and Western blotting. The optimal size and Ab/BNP for internalization of AbBNPs by CRLF2+ blasts is 50 nm with 10 Ab/BNP and 100 nm with 25 Ab/BNP. These studies show that internalization of AbBNPs in childhood B‐ALL blasts is AbBNP size‐ and Ab/BNP ratio‐dependent. All AbBNP combinations are non‐cytotoxic. It is also shown that CD47 is very slightly up‐regulated by blasts exposed to AbBNPs. CD47 is “the marker of self” overexpressed by blasts to escape phagocytosis, or “cellular devouring”, by beneficial macrophages. The results indicate that precise engineering of AbBNPs by size and Ab/BNP ratio may improve the internalization and selectivity of future biodegradable nanoparticles for the treatment of leukemia patients, including drug‐resistant minority children and Down's syndrome patients with CRLF2+B‐ALL. 相似文献
153.
An expedient approach to enhance Mizoroki–Heck coupling reaction by infrared irradiation using palladacycle compounds
下载免费PDF全文
![点击此处可从《应用有机金属化学》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Fernando Ortega‐Jiménez Francisco X. Domínguez‐Villa Alfredo Rosas‐Sánchez Guillermo Penieres‐Carrillo José G. López‐Cortés M. Carmen Ortega‐Alfaro 《应用有机金属化学》2015,29(8):556-560
An alternative and environmentally friendly strategy to promote the Mizoroki–Heck cross‐coupling reaction by the use of infrared irradiation using palladacycles as precatalysts is reported. Coupling products are obtained in high yield and short reaction time. A comparison with the classical use of reflux conditions, and commercial sources of palladium complexes, shows the advantages of this new alternative for promoting coupling reactions. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
154.
155.
Three experimental tasks are of primary interest in biomechanics: determination of the mechanical properties of biomaterials, including tissues and artificial materials; validation of the mechanical reliability of implantable devices; assessment of the compatibility of the mechanical properties of such devices with the surrounding biological environment. Due to the complexity of the in vivo conditions, most of these studies are performed on in vitro models. This contribution presents a review of some methods that are currently utilised at the Laboratory of Biological Structure Mechanics at the Politecnico of Milan. 相似文献
156.
The conversion of alkylboranes to the corresponding alkanes is classically per-formed via protonolysis of alkylboranes. This simple reaction requires the use of severe reaction conditions, that is, treatment with a carboxylic acid at high temperature (>150 °C). We report here a mild radical procedure for the transformation of organoboranes to alkanes. 4-tert-Butylcatechol, a well-established radical inhibitor and antioxidant, is acting as a source of hydrogen atoms. An efficient chain reaction is observed due to the exceptional reactivity of phenoxyl radicals toward alkylboranes. The reaction has been applied to a wide range of organoboron derivatives such as B-alkylcatecholboranes, trialkylboranes, pinacolboronates, and alkylboronic acids. Furthermore, the so far elusive rate constants for the hydrogen transfer between secondary alkyl radical and catechol derivatives have been experimentally determined. Interestingly, they are less than 1 order of magnitude slower than that of tin hydride at 80 °C, making catechols particularly attractive for a wide range of transformations involving C-C bond formation. 相似文献
157.
Yata Praveen Kumar C. Shobha Devi N. Deepika Nazar MD Gabra Nishant Jain A. Srishailam Kotha Laxma Reddy S. Satyanarayana 《Transition Metal Chemistry》2013,38(8):811-819
A new ligand, (2-ethoxy-6-(1H imadazo[4,5-f][1,10]phenanthroline-2-yl)phenol) (HEPIP) and its three Co(III) complexes [Co(phen)2(HEPIP)](ClO4)3 (1), [Co(bpy)2(HEPIP)](ClO4)3 (2) and [Co(dmb)2(HEPIP)](ClO4)3 (3) have been synthesized and characterized. All three Co(III) complexes exhibited antitumor activity against four human tumor cell lines. The interaction of these complexes with calf thymus DNA was studied by absorption and emission spectroscopy, viscosity measurements and DNA cleavage assays. The DNA-binding constants of complexes 1, 2 and 3 were determined as 6.13 × 105, 4.46 × 105 and 3.72 × 105 M?1, respectively. The complexes appear to interact with DNA through intercalation. Studies on the mechanism of photocleavage indicated that both superoxide anion radical and singlet oxygen may play an important role. 相似文献
158.
MD. Akhtaruzzaman Masaaki Tomura Kazuko Takahashi Jun-Ichi Nishida 《Supramolecular chemistry》2013,25(4):239-243
Hydrogen-bonding networks of π-extended 4,4′-bipyridines, 2,5-di(4-pyridyl)thiophene (1), 2,5-di(4-pyridyl)furan (2) and 1,4-di(4-pyridyl)benzene (3) with 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (chloranilic acid, CA) have been investigated. The dipyridyl compounds afforded complexes 4 [(dication of 1)·(monoanion of CA)2], 5 [(dication of 2)·(dianion of CA)·(MeOH)] and 6 [(3)·(dication of 3)·(dianion of CA)·(H2O)6] with CA. X-ray structure analyses revealed the formation of unusual molecular tape and sheet structures involving N–H ?O, O–H ?O, C–H ?O and N–H ?N hydrogen bonds, where the aromatic spacer groups play an important role in constructing the unique crystal structures. 相似文献
159.
Nilay K. Pramanik Ramsankar Haldar Utpal K. Niyogi MD. Sarwar Alam 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(4):296-307
The non-isothermal crystallization kinetics was studied by differential scanning calorimetric analysis on nylon 66 and e-beam irradiated nylon 66 at different cooling rates. The Modified Avrami equation, the Ozawa equation and the Combined Avrami-Ozawa equation were applied to study the kinetics of non-isothermal crystallization of nylon 66. The crystallization behavior of pristine nylon 66 polymer was compared with that of e-beam irradiated nylon 66 and observed that the kinetics of non-isothermal crystallization of nylon66 was affected largely upon e-beam irradiation. E-beam irradiation not only decreased the crystallization temperature of nylon 66, but influenced the mechanism of nucleation and crystal growth and reduced the overall crystallization rate of nylon 66 also. The crystallization activation energy calculated by the Kissinger method for irradiated nylon 66 was lower than that of pristine nylon 66. 相似文献
160.
Palladium‐Catalyzed ortho‐Selective CH Deuteration of Arenes: Evidence for Superior Reactivity of Weakly Coordinated Palladacycles
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Sandy Ma Dr. Giorgio Villa Peter S. Thuy‐Boun Anna Homs Prof. Dr. Jin‐Quan Yu 《Angewandte Chemie (International ed. in English)》2014,53(3):734-737
We disclose a protocol for the palladium‐catalyzed ortho‐selective C? H deuteration of arenes. Phenylacetic acids and benzoic acids are suitable substrates for this reaction. This reaction offers a catalytic route to ortho‐deuterated phenylacetic acids and benzoic acids and demonstrates the sharp difference in reactivity of palladacycle intermediates held together by weak and strong coordination. 相似文献