全文获取类型
收费全文 | 468篇 |
免费 | 20篇 |
国内免费 | 3篇 |
专业分类
化学 | 380篇 |
晶体学 | 5篇 |
力学 | 8篇 |
数学 | 8篇 |
物理学 | 90篇 |
出版年
2023年 | 5篇 |
2022年 | 12篇 |
2021年 | 26篇 |
2020年 | 15篇 |
2019年 | 24篇 |
2018年 | 17篇 |
2017年 | 15篇 |
2016年 | 16篇 |
2015年 | 17篇 |
2014年 | 14篇 |
2013年 | 42篇 |
2012年 | 21篇 |
2011年 | 29篇 |
2010年 | 25篇 |
2009年 | 17篇 |
2008年 | 11篇 |
2007年 | 16篇 |
2006年 | 13篇 |
2005年 | 14篇 |
2004年 | 10篇 |
2003年 | 7篇 |
2002年 | 13篇 |
2001年 | 8篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1998年 | 4篇 |
1997年 | 2篇 |
1996年 | 4篇 |
1995年 | 17篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 7篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1984年 | 8篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1980年 | 4篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1974年 | 4篇 |
1972年 | 1篇 |
1969年 | 1篇 |
1963年 | 1篇 |
1930年 | 1篇 |
排序方式: 共有491条查询结果,搜索用时 31 毫秒
71.
An efficient,mild and selective Ullmann‐type N‐arylation of indoles catalysed by Pd immobilized on amidoxime‐functionalized mesoporous SBA‐15 as heterogeneous and recyclable nanocatalyst
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)
A wide range of N‐arylated indoles were selectively synthesized through intermolecular C(aryl)? N bond formation from the corresponding aryl iodides and indoles through Ullmann‐type coupling reactions in the presence of a catalytic amount of Pd immobilized on amidoxime‐functionalized mesoporous SBA‐15 (SBA‐15/AO/Pd(0)) under mild reaction conditions. These cross‐coupled products were obtained in excellent yields under mild conditions at extremely low palladium loading (ca 0.3 mol%), and the heterogeneous catalyst can be readily recovered by simple filtration and reused seven times with loss in its activity. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
72.
Saba Hemmati Mohammad Yousefi Mirmehdi Hashemi Salehi Mahdis Amiri Malak Hekmati 《应用有机金属化学》2020,34(8):e5653
This paper develops a green method for in situ decorated of palladium nanoparticles over Fe3O4 nanoparticles, by utilizing Strawberry fruit extract and ultrasound irradiations, with no use of any toxic reducing agent. The structure's characterization is represented via diverse analytical methods such as FT-IR, FE-SEM, TEM, WDX, ICP, EDS and XXPS. Catalytic efficiency of magnetic Fe3O4@Strawberry/Pd nanocatalyst is investigated in production of different biphenyls with good turnover frequencies (TOF) and turnover numbers (TON) through Suzuki coupling reactions. Furthermore, the catalyst could be recovered and reused 7 runs without considerable palladium leaching or alteration in its performance. 相似文献
73.
Journal of Experimental and Theoretical Physics - This paper is devoted to construction of generalized ghost dark energy f(G) model by using correspondence scheme for both interacting and... 相似文献
74.
Recently, metallic nanoparticles have been used for the treatment of several disorders, such as cancer. Indeed, finding the chemotherapeutic drug of nanoparticles is in researching the priority of both developed and developing countries. The present study confirms the ability of aqueous extract of Thymus vulgaris grown under in vitro condition for the biosynthesis of gold nanoparticles (AuNPs). Also, in this study, we indicated the antioxidant, cytotoxicity, and anti-acute myeloid leukemia properties of AuNPs compared to doxorubicin in a leukemic mouse model. The synthesized AuNPs were characterized using different techniques including X-ray diffraction (XRD), energy Dispersive X-ray Spectrometry (EDS), fourier-transform infrared spectroscopy (FT-IR) spectroscopy, ultraviolet–visible spectroscopy (UV–Vis.), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). In vivo design, induction of acute myeloid leukemia was done by 7,12-Dimethylbenz[a]anthracene (DMBA) in 75 mice. Then, the animals were randomly divided into six subgroups, including control, untreated, doxorubicin, AuNPs, T. vulgaris, and HAuCl4. By quantitative real-time PCR, sphingosine-1-phosphate receptor-1 and sphingosine-1-phosphate receptor-5 mRNA expression in lymphocytes were significantly (P ≤ 0.01) raised by treating the leukemic mice with the AuNPs and doxorubicin. Also, AuNPs similar to doxorubicin, significantly (P ≤ 0.01) enhanced the anti-inflammatory cytokines (IL4, IL5, IL10, IL13, and IFNα) and the platelet, lymphocyte, and red blood cell (RBC) parameters and reduced the pro-inflammatory cytokines (IL1, IL6, IL12, IL18, IFNY, and TNFα), and the total white blood cell (WBC), blast, monocyte, neutrophil, eosinophil, and basophil counts as compared to the untreated mice. In vitro design, 2,2-diphenyl-1-picrylhydrazyl (DPPH) test revealed similar antioxidant potentials for doxorubicin and AuNPs. Furthermore, AuNPs similar to doxorubicin had low cell viability dose-dependently against 32D-FLT3-ITD, Human HL-60/vcr, and Murine C1498 cell lines without any cytotoxicity on HUVEC cell line. Above results confirm the excellent antioxidant, cytotoxicity, and anti-acute myeloid leukemia effects of AuNPs compared to doxorubicin. After confirming these results in clinical trial studies, AuNPs can be used as a chemotherapeutic drug for the treatment of acute myeloid leukemia in human. 相似文献
75.
Ahmed Jasim M. Al-Karawi Ali Jasim Hammood Adil A. Awad Al-Ameen Bariz OmarAli Saba Riad Khudhaier Dhafir T. A. Al- Heetimi 《Liquid crystals》2018,45(11):1603-1619
The following organic and organic–inorganic hybrid compounds were prepared as photo-luminescent materials following efficient and practical synthetic methods: 1,3-bis[4-(n-alkoxy)phenyl]-2-propen-1-one (where, n-alkoxy: O(CH2)nH, n = 6,7,8,9 or 10); 3,5-bis[4-(n-alkoxy)phenyl]-1H-pyrazole (where, n-alkoxy: O(CH2)nH, n = 6,7,8,9 or 10) (in case of n = 7, a mixture of 3,5-bis(4-heptyloxyphenyl)-1H-pyrazole and 3,5-bis(4-heptyloxyphenyl)-4H-pyrazole was detected) and bis(3,5-bis [4-(n-alkoxy) phenyl]-1H-pyrazole) silver(I) nitrate (where, n-alkoxy: O(CH2)nH, n = 6,7,8,9 or 10). The prepared compounds have been characterised and their structures were elucidated depending upon (FTIR, UV-Vis, 1HNMR, 13CNMR, 2D 1H-1H-COSY, 2D 1H-13C-HSQC and mass spectra) in addition to molar conductivity measurements for silver(I) complexes. The mesomorphism behaviour of the prepared compounds was studied using polarised light optical microscopy and confirmed with differential scanning calorimetry and X-ray powder diffraction techniques. The studies showed that among all of these compounds only the pyrazole derivatives are liquid crystal materials. The luminescent properties of all the prepared compounds were also investigated which confirmed that all of these compounds are photo-luminescent in the crystalline solid state and in the mesophase. 相似文献
76.
本文报道了一种不使用任何稳定剂或还原剂,原位合成硅胶/聚多巴胺复合物(SiO_2/PDA)负载的Pd纳米颗粒(Pd NPs)的简易方法.该方法先将PDA涂覆的SiO_2颗粒浸在Pd镀液中,然后利用PDA中含N基团的还原能力将Pd物种原位还原为纳米簇合物.并采用高分辨透射电镜、前场扫描电镜、能量散射谱、X射线衍射、X射线光电子能谱、诱导耦合等离子体和红外光谱等手段对所得纳米复合物的结构、形貌和物化性质进行了表征.被PDA基团锚合的Pd NPs具有显著的小颗粒(30–40 nm)特性.作为一个可循环使用的纳米催化剂,SiO_2/PDA/Pd NPs在醇的需氧氧化反应中表现出高活性.另外,催化剂经回收和多次重复使用时未出现明显的失活. 相似文献
77.
Luana Bettanin Sumbal Saba Carlos V. Doerner Marcelo S. Franco Marcelo Godoi Jamal Rafique Antonio L. Braga 《Tetrahedron》2018,74(29):3971-3980
Herein, we described the NH4I-catalyzed CH bond chalcogenation of N-heteroaryls in the presence of a minimum amount of DMSO/H2O/acetic acid as additives (2.5/2.5/1?M equiv., respectively), under metal-free conditions. Under optimized conditions, a wide variety of sulfenyl/selenyl imidazo[1,2-α]pyridines were prepared in very good yields. Moreover, the present approach was also highly efficient for the chalcogenation of different 5-membered N-heteroaryls, e.g., indole, imidazothiazole, indazole and imidazopyrimidine derivatives. 相似文献
78.
Density functional theory (DFT) has been applied to the analysis of the structural and electronic properties of the alkyl-cobalt(III) phthalocyanine complexes, [CoIIIPc]-R (Pc = phthalocyanine, R = Me or Et), and their pyridine adducts. The BP86/6-31G(d) level of theory shows good reliability for the optimized axial bond lengths and bond dissociation energies (BDEs). The mechanism of the reductive cleavage was probed for the [CoIIIPc]-Me complex which is known as a highly effective methyl group donor. In the present analysis, which follows a recent study on the reductive Co-C bond cleavage in methylcobalamin (J. Phys. Chem. B 2007, 111, 7638-7645), it is demonstrated that addition of an electron and formation of the pi-anion radical [CoIII(Pc*)]-Me- significantly lowers the energetic barrier required for homolytic Co-C bond dissociation. Such BDE lowering in [CoIII(Pc*)]-Me- arises from the involvement of two electronic states: upon electron addition, a quasi-degenerate pi*Pc state is initially formed, but when the cobalt-carbon bond is stretched, the unpaired electron moves to a sigma*Co-C state and the final cleavage involves the three-electron (sigma)2(sigma*)1 bond. As in corrin complexes, the pi*Pc-sigma*Co-C states crossing does not take place at the equilibrium geometry of [CoIII(Pc*)]-Me- but only when the Co-C bond is stretched to approximately 2.3 A. The DFT computed Co-C BDE of 23.3 kcal/mol in the one-electron-reduced phthalocyanine species, [CoIII(Pc*)]-Me-, is lowered by approximately 37% compared to the neutral Py-[CoIIIPc]-Me complex where BDE = 36.8 kcal/mol. A similar comparison for the corrin-containing complexes shows that a DFT computed BDE of 20.4 kcal/mol for [CoIII(corrin*)]-Me leads to approximately 45% bond strength reduction, in comparison to 37.0 kcal/mol for Im-[CoIII(corrin)]-Me+. These results suggest some preference by the alkylcorrinoids for the reductive cleavage mechanism. 相似文献
79.
Saba Seyedi Ben Ma Megan Groves Hal King Karl G. Linden 《Photochemistry and photobiology》2023,99(5):1293-1298
“Far UV-C” is an effective disinfection method that can be deployed in occupied areas. Commercially available Krypton Chloride (KrCl*) excimer lamps filtered to emit at 222 nm are effective in disinfecting pathogens and safe for human exposure up to an allowable threshold exposure, which is much longer than for conventional UV lamps emitting at 254 nm. Laboratory and controlled field testing of a filtered KrCl* excimer lamp for disinfection of a virus suspended in a thin film aqueous solution in an occupied office setting was conducted. Complete inactivation of almost 6 log (99.9999%) of Phi6 bacteriophage virus was achieved in ~20 min of exposure time in a field setting, equivalent to a dose of about 10 mJ cm−2. The Phi6 inactivation rate constant for the field test results were not statistically different from laboratory values (P > 0.05, paired t-test). When positioned at 1 m distance from possible human exposure, this device can be used safely for almost 4.5 h of continuous direct exposure without any acute or long-term adverse health effects. This study illustrates the applicability and deployment of Far UV-C for pathogen reduction and can help in decision making for implementation of Far UV-C for disinfection in human-occupied environments. 相似文献
80.
Tritt-Goc J Bielejewski M Luboradzki R Lapiński A 《Langmuir : the ACS journal of surfaces and colloids》2008,24(2):534-540
The studies of the gel-to-sol phase transition by the Raman, FT-IR, and 1H NMR methods of the gel made by low molecular weight organogelator 1,2-O-(1-ethylpropylidene)-alpha-D-glucofuranose with toluene as the solvent are reported. The FT-IR spectra revealed the existence of a hydrogen bond network formed by gelator molecules in the crystalline and gel phase. In both phases, the network formation is dominated by the gelator self-interaction. Upon gelation, only one stretching band of infrared absorption modes nualpha, assigned to the O(6)H hydroxyl protons of gelator, is shifted by Deltaupsilonalpha = 25 cm-1, which indicates the involvement of this proton in the interaction with the solvent molecules. The phase transition measurements performed as a function of gelator concentration allowed the calculation of the energy correlated with the transition from gel to solution phase. The obtained value of 72 kJ/mol is the largest one reported up until now for monosaccharide-based gels. The analysis of the temperature measurements of the toluene 1H NMR spectra provides evidence for a different chemical environment of toluene molecules in the gel. The toluene spin-lattice relaxation in bulk and gel indicate that the viscosity is most likely the main factor that influences the dynamics of toluene. 相似文献