全文获取类型
收费全文 | 66891篇 |
免费 | 3705篇 |
国内免费 | 9168篇 |
专业分类
化学 | 52394篇 |
晶体学 | 1742篇 |
力学 | 1048篇 |
综合类 | 521篇 |
数学 | 12257篇 |
物理学 | 11802篇 |
出版年
2024年 | 50篇 |
2023年 | 477篇 |
2022年 | 1177篇 |
2021年 | 1440篇 |
2020年 | 1483篇 |
2019年 | 1464篇 |
2018年 | 1234篇 |
2017年 | 1816篇 |
2016年 | 1780篇 |
2015年 | 1570篇 |
2014年 | 2279篇 |
2013年 | 5077篇 |
2012年 | 4366篇 |
2011年 | 3552篇 |
2010年 | 3192篇 |
2009年 | 4238篇 |
2008年 | 4324篇 |
2007年 | 4355篇 |
2006年 | 4009篇 |
2005年 | 3507篇 |
2004年 | 3389篇 |
2003年 | 2792篇 |
2002年 | 3523篇 |
2001年 | 2358篇 |
2000年 | 2156篇 |
1999年 | 2052篇 |
1998年 | 1749篇 |
1997年 | 1362篇 |
1996年 | 1115篇 |
1995年 | 1094篇 |
1994年 | 969篇 |
1993年 | 809篇 |
1992年 | 824篇 |
1991年 | 560篇 |
1990年 | 446篇 |
1989年 | 477篇 |
1988年 | 349篇 |
1987年 | 269篇 |
1986年 | 259篇 |
1985年 | 226篇 |
1984年 | 256篇 |
1983年 | 103篇 |
1982年 | 184篇 |
1981年 | 173篇 |
1980年 | 197篇 |
1979年 | 171篇 |
1978年 | 161篇 |
1977年 | 108篇 |
1976年 | 86篇 |
1973年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
11.
Caesium carbonate supported on hydroxyapatite‐encapsulated Ni0.5Zn0.5Fe2O4 nanocrystallites as a novel magnetically basic catalyst for the one‐pot synthesis of pyrazolo[1,2‐b]phthalazine‐5,10‐diones
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)
Behrooz Maleki Samaneh Barat Nam Chalaki Samaneh Sedigh Ashrafi Esmail Rezaee Seresht Farid Moeinpour Amir Khojastehnezhad Reza Tayebee 《应用有机金属化学》2015,29(5):290-295
A novel nanomagnetic basic catalyst of caesium carbonate supported on hydroxyapatite‐coated Ni0.5Zn0.5Fe2O4 magnetic nanoparticles (Ni0.5Zn0.5Fe2O4@HAP‐Cs2CO3) was prepared. This new catalyst was fully characterized using Fourier transform infrared spectroscopy, transmission and scanning electron microscopy, X‐ray diffraction and vibrating sample magnetometry techniques, and then the catalytic activity of this catalyst was investigated in the synthesis of 1H‐pyrazolo[1,2‐b]phthalazine‐5,10‐dione derivatives. Also, Ni0.5Zn0.5Fe2O4@HAP‐Cs2CO3 could be reused at least five times without significant loss of activity and could be recovered easily by applying an external magnet. Thus, the developed nanomagnetic catalyst is potentially useful for the green and economic production of organic compounds. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
12.
Mariia Svyntkivska Tomasz Makowski Ewa Piorkowska Marek Brzezinski Agata Herc Anna Kowalewska 《Molecules (Basel, Switzerland)》2021,26(5)
Electrospun nonwovens of poly(L-lactide) (PLLA) modified with multiwall carbon nanotubes (MWCNT) and linear ladder-like poly(silsesquioxane) with methoxycarbonyl side groups (LPSQ-COOMe) were obtained. MWCNT and LPSQ-COOMe were added to the polymer solution before the electrospinning. In addition, nonwovens of PLLA grafted to modified MWCNT were electrospun. All modified nonwovens exhibited higher tensile strength than the neat PLA nonwoven. The addition of 10 wt.% of LPSQ-COOMe and 0.1 wt.% of MWCNT to PLLA increased the tensile strength of the nonwovens 2.4 times, improving also the elongation at the maximum stress. 相似文献
13.
《Arabian Journal of Chemistry》2021,14(11):103421
Processing of Carapa guianensis seeds to obtain oil on an industrial scale generates a significant amount of by-product, approximately 66% w/w, which is called cake and is a potential source of biomolecules, including simple phenolic structures. For this reason, studies were carried out on the chemical profiles of hydrolyzed extract from this agro-industrial by-product through High Performance Thin-Layer Chromatography (HPTLC) and Gas Chromatography coupled to Mass Spectrometry (GC–MS). These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product. The sample antioxidant capacity was determined by methods of 2,2-diphenyl-1-picrylhydrazyl (DPPH)and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS+) radicals direct sequestration. The hydrolyzed fraction showed a total of 63.47% in the relative abundance of the total of compounds, standing out: p-hydroxybenzoic acid (39.19%) and protocatechuic acid (3,4-dihydroxybenzoic acid) (5.62%), both from hydroxybenzoic acids and 3-(3,4-dihydroxyphenyl)lactic acid, (7.76%) hydroxycinnamic acids derivatives. In these results, the fraction rich in simple phenolic acids was obtained, attributing the prominent behavior of this matrix antioxidant activity, expressed by (IC50: of 16.42 µg/mL and 6.52 µg/mL for DPPH and ABTS+ radicals, respectively). The research demonstrated an alternative to applicability that involves sustainability from agro-industrial. These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product, generating a process capable of converting biomass into a bioproduct, consisting of bioactive compounds, in addition to adding value to the industrial chain. 相似文献
14.
Most notable Kinetoplastids are of the genus Trypanosoma and Leishmania, affecting several millions of humans in Africa and Latin America. Current therapeutic options are limited by several drawbacks, hence the need to develop more efficacious inhibitors. An investigation to decipher the mechanism behind greater inhibitory potency of a chroman-4-one derivative (compound 1) in Trypanosoma brucei pteridine reductase 1 (TbPTR1) and Leishmania major pteridine reductase 1 (LmPTR1) was performed. Estimation of ΔGbind revealed that compound 1 had a greater binding affinity in TbPTR1 with a ΔGbind value of −49.0507 Kcal/mol than −29.2292 Kcal/mol in LmPTR1. The ΔGbind in TbPTR1 were predominantly contributed by “strong” electrostatic energy compared to the “weak” van der Waals in LmPTR1. In addition to this, the NADPH cofactor contributed significantly to the total energy of TbPTR1. A characteristic weak aromatic π interaction common in PTR1 was more prominent in TbPTR1 than LmPTR1. The consistent occurrence of high-affinity conventional hydrogen bond interactions as well as a steady interaction of crucial active site residues like Arg14/Arg17, Ser95/Ser111, Phe97/Phe113 in TbPTR1/LmPTR1 with chroman-4-one moiety equally revealed the important role the moiety played in the activity of compound 1. Overall, the structural and conformational analysis of the active site residues in TbPTR1 revealed them to be more rigid than LmPTR1. This could be the mechanism of interaction TbPTR1 employs in exerting a greater potency than LmPTR1. These findings will further give insight that will be assistive in modifying compound 1 for better potency and the design of novel inhibitors of PTR1. 相似文献
15.
16.
Leila Torkian Mostafa M. Amini Tayebeh Gorji Omid Sadeghi 《Arabian Journal of Chemistry》2019,12(7):1315-1321
In this study, multiwalled carbon nanotube (MWCNT) was modified by the pyridine group using a silane agent and characterized by infrared spectroscopy (IR), thermal analysis (TG/DTA), and elemental analysis (CHN) and scanning electron microscopy (SEM). The application of this sorbent was investigated in determination of lead ions in aqueous samples, using flame atomic absorption spectrometry (FAAS). Through this study, different parameters such as pH and sample flow rate on adsorption process and eluent concentration, volume and flow rate were optimized. The limit of detection (LOD), the relative standard deviation and the recovery of the method were 2 ng mL?1, 1.3% and 99.7%, respectively. Two standard reference materials (NIST 1571 and NIST 1572) were used to verify accuracy of this method. Finally, the sorbent was successfully applied for extraction and determination of low levels of Pb(II) ions in aqueous samples. 相似文献
17.
Naoto Takase Junpei Kuwabara Seong Jib Choi Takeshi Yasuda Liyuan Han Takaki Kanbara 《Journal of polymer science. Part A, Polymer chemistry》2015,53(4):536-542
The Pd‐catalyzed polycondensation of 4‐octylaniline with various dibromoarylenes was carried out under microwave heating. Microwave heating led to a decrease in the reaction time and an increase in the molecular weight of the polymers as compared to conventional heating. Microwave heating also allowed the catalyst loading to be reduced to 1 mol %, yielding polymerization results that were comparable to those under conventional heating and 5 mol % catalyst. Investigations regarding field‐effect transistors and organic photovoltaic cells using the obtained poly(arylamine) with azobenzene units revealed that increasing the molecular weight of the polymer led to improved device performance, including hole mobility and power conversion efficiency. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 536–542 相似文献
18.
Synthesis of diisocyanides with phenolic groups and their polymerization to helically chiral poly(quinoxaline‐2,3‐diyl)s
下载免费PDF全文
![点击此处可从《Journal of polymer science. Part A, Polymer chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Johannes Scholz Michael Reggelin 《Journal of polymer science. Part A, Polymer chemistry》2015,53(11):1320-1329
The development of synthetic routes which lead to five new diisocyanide monomers with one or two phenolic groups is described. Their polymerization behavior is studied with Pd‐ and Ni‐based initiators, as well as under microwave irradiation. The polymerizability is mainly dominated by steric effects as is concluded from experiments using different protecting groups. Chiroptical properties of these new polymers are studied by CD‐spectroscopy. After deprotection, helically chiral poly(quinoxalin‐2,3‐diyl)s are obtained which display a Brønsted function attached to a stereolabile biaryl axis whose configuration should be influenced by the chiral polymer backbone. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1320–1329 相似文献
19.
Mara K. Kuenen James A. Mullin Rachel A. Letteri 《Journal of polymer science. Part A, Polymer chemistry》2021,59(19):2212-2221
With a vast, synthetically accessible compositional space and highly tunable hydrolysis rates, poly(β-amino ester)s (PBAEs) are an attractive degradable polymer platform. Leveraging PBAEs in a wide range of applications hinges on the ability to program degradation, which, thus far, has been frustrated by multiple confounding phenomena contributing to the degradation of these charged polyesters. Basic conditions accelerate hydrolysis, yet reduce solubility, limiting water access to amines and esters. Further, the high buffering capacity of PBAEs can render buffers ineffective at controlling solution pH. To unify understanding of PBAE degradation and solution properties, this study examines PBAE hydrolysis as a function of pH and buffer concentration as well as polymer hydrophobicity. At low buffer concentrations, the PBAE amines and the acid produced during hydrolysis control solution pH. Meanwhile, at high buffer concentrations that afford relatively constant pH, hydrolysis rate increases with pH, despite the reduced PBAE solubility. Increasing the hydrophobic content of PBAEs eventually hinders the capacity of the polymer to accept protons from solution, limiting the pH increase and slowing hydrolysis. These studies showcase the role of buffering on the pH-dependent degradation and solution properties of PBAEs, providing guidance for programming degradation in applications ranging from drug delivery to thermosets. 相似文献
20.