全文获取类型
收费全文 | 22893篇 |
免费 | 1465篇 |
国内免费 | 3439篇 |
专业分类
化学 | 18601篇 |
晶体学 | 1053篇 |
力学 | 216篇 |
综合类 | 192篇 |
数学 | 3665篇 |
物理学 | 4070篇 |
出版年
2023年 | 169篇 |
2022年 | 243篇 |
2021年 | 654篇 |
2020年 | 542篇 |
2019年 | 536篇 |
2018年 | 423篇 |
2017年 | 558篇 |
2016年 | 590篇 |
2015年 | 550篇 |
2014年 | 816篇 |
2013年 | 1777篇 |
2012年 | 1291篇 |
2011年 | 1487篇 |
2010年 | 1483篇 |
2009年 | 1678篇 |
2008年 | 1625篇 |
2007年 | 1643篇 |
2006年 | 1555篇 |
2005年 | 1341篇 |
2004年 | 1307篇 |
2003年 | 1107篇 |
2002年 | 943篇 |
2001年 | 676篇 |
2000年 | 628篇 |
1999年 | 473篇 |
1998年 | 452篇 |
1997年 | 387篇 |
1996年 | 325篇 |
1995年 | 367篇 |
1994年 | 323篇 |
1993年 | 303篇 |
1992年 | 284篇 |
1991年 | 213篇 |
1990年 | 122篇 |
1989年 | 153篇 |
1988年 | 136篇 |
1987年 | 89篇 |
1986年 | 61篇 |
1985年 | 71篇 |
1984年 | 90篇 |
1983年 | 23篇 |
1982年 | 44篇 |
1981年 | 60篇 |
1980年 | 51篇 |
1979年 | 38篇 |
1978年 | 27篇 |
1977年 | 22篇 |
1976年 | 11篇 |
1975年 | 10篇 |
1973年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
41.
42.
Li‐Na Wang Zhen‐Xun Zhou Dr. Xiao‐Na Li Dr. Tong‐Mei Ma Prof. Sheng‐Gui He 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6957-6961
In addition to generation of a methyl radical, formation of a formaldehyde molecule was observed in the thermal reaction of methane with AuNbO3+ heteronuclear oxide cluster cations. The clusters were prepared by laser ablation and mass‐selected to react with CH4 in an ion‐trap reactor under thermal collision conditions. The reaction was studied by mass spectrometry and DFT calculations. The latter indicated that the gold atom promotes formaldehyde formation through transformation of an Au?O bond into an Au?Nb bond during the reaction. 相似文献
43.
Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides 下载免费PDF全文
Anna Ulmer Dr. Maciej Stodulski Stefanie V. Kohlhepp Christoph Patzelt Dr. Alexander Pöthig Dr. Wolfgang Bettray Dr. Tanja Gulder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1444-1448
A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ3‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ3‐benziodoxolones are involved in these organocatalytic reactions. 相似文献
44.
A sensitive and efficient method for trace analysis of some phenolic compounds using simultaneous derivatization and air‐assisted liquid–liquid microextraction from human urine and plasma samples followed by gas chromatography–nitrogen phosphorous detection 下载免费PDF全文
Mir Ali Farajzadeh Mohammad Reza Afshar Mogaddam Ali Akbar Alizadeh Nabil 《Biomedical chromatography : BMC》2015,29(12):1921-1931
In present study, a simultaneous derivatization and air‐assisted liquid–liquid microextraction method combined with gas chromatography–nitrogen phosphorous detection has been developed for the determination of some phenolic compounds in biological samples. The analytes are derivatized and extracted simultaneously by a fast reaction with 1‐flouro‐2,4‐dinitrobenzene under mild conditions. Under optimal conditions low limits of detection in the range of 0.05–0.34 ng mL?1 are achievable. The obtained extraction recoveries are between 84 and 97% and the relative standard deviations are less than 7.2% for intraday (n = 6) and interday (n = 4) precisions. The proposed method was demonstrated to be a simple and efficient method for the analysis of phenols in biological samples. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
45.
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
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
46.
Resolution and isolation of enantiomers of (±)‐isoxsuprine using thin silica gel layers impregnated with l‐glutamic acid,comparison of separation of its diastereomers prepared with chiral derivatizing reagents having l‐amino acids as chiral auxiliaries 下载免费PDF全文
Thin silica gel layers impregnated with optically pure l ‐glutamic acid were used for direct resolution of enantiomers of (±)‐isoxsuprine in their native form. Three chiral derivatizing reagents, based on DFDNB moiety, were synthesized having l ‐alanine, l ‐valine and S‐benzyl‐l ‐cysteine as chiral auxiliaries. These were used to prepare diastereomers under microwave irradiation and conventional heating. The diastereomers were separated by reversed‐phase high‐performance liquid chromatography on a C18 column with detection at 340 nm using gradient elution with mobile phase containing aqueous trifluoroacetic acid and acetonitrile in different compositions and by thin‐layer chromatography (TLC) on reversed phase (RP) C18 plates. Diastereomers prepared with enantiomerically pure (+)‐isoxsuprine were used as standards for the determination of the elution order of diastereomers of (±)‐isoxsuprine. The elution order in the experimental study of RP‐TLC and RP‐HPLC supported the developed optimized structures of diastereomers based on density functional theory. The limit of detection was 0.1–0.09 µg/mL in TLC while it was in the range of 22–23 pg/mL in HPLC and 11–13 ng/mL in RP‐TLC for each enantiomer. The conditions of derivatization and chromatographic separation were optimized. The method was validated for accuracy, precision, limit of detection and limit of quantification. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
47.
Ban Chen Xican Li Xiaojian Ouyang Jie Liu Yangping Liu Dongfeng Chen 《Molecules (Basel, Switzerland)》2021,26(4)
Synthetic arylamines and dietary phytophenolics could inhibit ferroptosis, a recently discovered regulated cell death process. However, no study indicates whether their inhibitory mechanisms are inherently different. Herein, the ferroptosis-inhibitory mechanisms of selected ferrostatin-1 (Fer-1) and two dietary stilbenes (piceatannol and astringin) were compared. Cellular assays suggested that the ferroptosis-inhibitory and electron-transfer potential levels decreased as follows: Fer-1 >> piceatannol > astringin; however, the hydrogen-donating potential had an order different from that observed by the antioxidant experiments and quantum chemistry calculations. Quantum calculations suggested that Fer-1 has a much lower ionization potential than the two stilbenes, and the aromatic N-atoms were surrounded by the largest electron clouds. By comparison, the C4′O-H groups in the two stilbenes exhibited the lowest bond disassociation enthalpies. Finally, the three were found to produce corresponding dimer peaks through ultra-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry analysis. In conclusion, Fer-1 mainly depends on the electron transfer of aromatic N-atoms to construct a redox recycle. However, piceatannol and astringin preferentially donate hydrogen atoms at the 4′-OH position to mediate the conventional antioxidant mechanism that inhibits ferroptosis, and to ultimately form dimers. These results suggest that dietary phytophenols may be safer ferroptosis inhibitors for balancing normal and ferroptotic cells than arylamines with high electron-transfer potential. 相似文献
48.
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
49.
《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
50.
In recent years ionic liquids (ILs) have attracted much interest because of their widespread use in various fields. Several trimerization and oligomerization catalysts have been evaluated in ILs with different organic–inorganic hybrid structures. High catalytic activity and selectivity, easy product separation, and recycling of the catalyst are the advantages of a biphasic catalyst system compared to the homogeneous catalysts. In this study, the influence of IL counter-anions on activity and selectivity of the ethylene trimerization catalysts based on Cr-SNS-R was investigated. All synthesized materials were characterized using Fourier-transform infrared spectroscopy, 1H NMR, 13C NMR, UV–Vis. spectroscopy, thin-layer chromatography, and elemental analysis (CHNS). In ethylene trimerization reaction, the dodecyl substituent in the SNS ligand exhibited better activity and selectivity than the butyl substituent. The results revealed that the presence of BF4− as a counter-anion in the IL led to an increase in activity and selectivity compared to Br− and I− counter-anions. It was found that the BF4− counter-anion plays a conclusive role in the development of 1-hexene activity and selectivity to a maximum amount of 71,132 g1-C6/(gCr × h) and more than 99%, respectively. Finally, the catalyst was reused thrice without losing its 1-hexene selectivity. 相似文献