全文获取类型
收费全文 | 2363篇 |
免费 | 115篇 |
国内免费 | 3篇 |
专业分类
化学 | 2083篇 |
晶体学 | 14篇 |
力学 | 27篇 |
数学 | 156篇 |
物理学 | 201篇 |
出版年
2024年 | 5篇 |
2023年 | 25篇 |
2022年 | 80篇 |
2021年 | 112篇 |
2020年 | 87篇 |
2019年 | 94篇 |
2018年 | 61篇 |
2017年 | 58篇 |
2016年 | 103篇 |
2015年 | 71篇 |
2014年 | 82篇 |
2013年 | 124篇 |
2012年 | 179篇 |
2011年 | 170篇 |
2010年 | 106篇 |
2009年 | 90篇 |
2008年 | 132篇 |
2007年 | 102篇 |
2006年 | 108篇 |
2005年 | 137篇 |
2004年 | 94篇 |
2003年 | 109篇 |
2002年 | 61篇 |
2001年 | 35篇 |
2000年 | 29篇 |
1999年 | 16篇 |
1998年 | 16篇 |
1997年 | 14篇 |
1996年 | 29篇 |
1995年 | 19篇 |
1994年 | 22篇 |
1993年 | 17篇 |
1992年 | 7篇 |
1991年 | 11篇 |
1990年 | 4篇 |
1989年 | 7篇 |
1988年 | 2篇 |
1987年 | 6篇 |
1986年 | 10篇 |
1985年 | 5篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1982年 | 7篇 |
1981年 | 9篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1971年 | 2篇 |
排序方式: 共有2481条查询结果,搜索用时 15 毫秒
151.
Transalkylation of Higher Trifluoromethylated Fullerenes with C70: A Pathway to New Addition Patterns of C70(CF3)8 下载免费PDF全文
Nikita M. Belov Marina G. Apenova Alexey V. Rybalchenko Eugenia V. Borkovskaya Dr. Natalia S. Lukonina Dr. Alexey A. Goryunkov Dr. Ilya N. Ioffe Prof. Dr. Sergey I. Troyanov Prof. Dr. Lev N. Sidorov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(4):1126-1133
We report three new isomers of C70(CF3)8, structurally related to p7mp‐C70(CF3)10, that are inaccessible by direct trifluoromethylation, but can be easily identified among the products of the transalkylation of higher trifluoromethylfullerenes with C70. The reported compounds are characterized by UV/Vis, 1 D and 2 D COSY 19F NMR spectroscopy, and DFT calculations. A rather unusual addition pattern is observed in p6,i‐C70(CF3)8 in which one addend is attached remotely from the others; polarization of the adjacent unsaturated bonds by the addend makes the molecule readily oxidizable. 相似文献
152.
Josiane Arnaud Isabelle Coté Patrick J. Parsons Marina Patriarca Andrew Taylor Cas Weykamp 《Accreditation and quality assurance》2014,19(3):169-174
Proficiency testing schemes monitor laboratory performance and provide a stimulus for improvement in accuracy. Where several schemes operate in the same analytical sector, there are risks that assessments of performance may be in conflict. Performance assessment for the determination of trace elements such as aluminum in serum is particularly important due to the high risk of contamination and therefore erroneous results. The objectives of this work were (1) to compare several mathematical models to establish a predefined standard deviation for proficiency assessment and (2) to evaluate the influence of instrumental methods and proficiency testing scheme on the assessment of performance for serum aluminum measurements. For this purpose, three samples were sent to the participants of four proficiency testing schemes. Assigned values were calculated according to algorithm A according to ISO 13528 and standard deviation for proficiency assessment according to three methods based on individual variability, state of the art or previous proficiency testing results. The method based on individual variability produced a more stringent standard deviation compared to analytical imprecision based on the state of the art. The instrumental methods gave similar results, whereas significant differences were observed between the four proficiency testing schemes indicating that harmonization of the standard deviation for proficiency assessment fails to allow transferability from one proficiency testing scheme to another and that additional factor(s) contribute to variability in performance assessment. 相似文献
153.
Dr. Jonathan A. Robson Dr. Markéta Kubánková Tamzin Bond Rian A. Hendley Dr. Andrew J. P. White Prof. Dr. Marina K. Kuimova Prof. Dr. James D. E. T. Wilton-Ely 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(48):21615-21619
A new family of robust, non-toxic, water-compatible ruthenium(II) vinyl probes allows the rapid, selective and sensitive detection of endogenous carbon monoxide (CO) in live mammalian cells under normoxic and hypoxic conditions. Uniquely, these probes incorporate a viscosity-sensitive BODIPY fluorophore that allows the measurement of microscopic viscosity in live cells via fluorescence lifetime imaging microscopy (FLIM) while also monitoring CO levels. This is the first example of a probe that can simultaneously detect CO alongside small viscosity changes in organelles of live cells. 相似文献
154.
Prof. Dr. Evgeny V. Tretyakov Dr. Svetlana I. Zhivetyeva Dr. Pavel V. Petunin Dmitry E. Gorbunov Prof. Dr. Nina P. Gritsan Prof. Dr. Irina Yu. Bagryanskaya Dr. Artem S. Bogomyakov Dr. Pavel S. Postnikov Dr. Maxim S. Kazantsev Prof. Dr. Marina E. Trusova Dr. Inna K. Shundrina Dr. Elena V. Zaytseva Dr. Dmitriy A. Parkhomenko Prof. Dr. Elena G. Bagryanskaya Prof. Dr. Victor I. Ovcharenko 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(46):20885-20891
Thermally stable organic diradicals with a triplet ground state along with large singlet-triplet energy gap have significant potential for advanced technological applications. A series of phenylene-bridged diradicals with oxoverdazyl and nitronyl nitroxide units were synthesized via a palladium-catalyzed cross-coupling reaction of iodoverdazyls with a nitronyl nitroxide-2-ide gold(I) complex with high yields. The diradicals exhibit high stability and do not decompose in an inert atmosphere up to 180 °C. For the diradicals, both substantial AF (ΔEST≈−64 cm−1) and FM (ΔEST≥25 and 100 cm−1) intramolecular exchange interactions were observed. The sign of the exchange interaction is determined both by the bridging moiety (para- or meta-phenylene) and by the type of oxoverdazyl block (C-linked or N-linked). Upon crystallization, diradicals with the triplet ground state form unique one-dimensional exchange-coupled chains with strong intra- and weak inter-diradical ferromagnetic coupling. 相似文献
155.
Rail R. Gataullin Zulfia R. Zileeva Marina A. Maksimova Liana F. Zainullina Yuliya V. Vakhitova 《Journal of heterocyclic chemistry》2020,57(3):1236-1248
N-tosyl-2- and N-tosyl-4-halogen-substituted derivatives of 2-(1-methylbut-2-en-1-yl)aniline were synthesized and their molecular iodine-mediated cyclization was investigated. The cyclization upon interaction of N-tosyl-6-methyl-2-(1-methylbut-2-en-1-yl)aniline with molecular iodine in methyl tert-butyl ether or acetonitrile was studied, as well as the interaction of this sulfonamide with N-bromosucinimide in dichloromethane. Synthesized (2R*,3R*)- and (2R*,3S*)-N-arylsulfonyl-2-(1-halogenoethyl)-3-methylindoline derivatives showed cytotoxic activity against HEK293 cells, SH-SY5Y, Jurkat, and HepG2 cell lines. The compounds (2R*,3S*)-N-arylsulfonyl-7-bromo-2-(1-halogenoethyl)-3-methylindoline cis- 4a , stereoisomeric (2R*,3R*)-trans- 4h and (2R*,3S*)-N-tosyl-7-chloro-2-(1-halogenoethyl)-3-methylindoline cis- 4h demonstrated selective toxicity against SH-SY5Y cell line (IC50 ≈ 3 ÷ 5 μM), and did not affect HEK293, Jurkat, and HepG2 cells. 相似文献
156.
ngela Liberal ngela Fernandes Nikolaos Polyzos Spyridon A. Petropoulos Maria Inês Dias Jos Pinela Jovana Petrovi Marina Sokovi Isabel C.F.R. Ferreira Lillian Barros 《Molecules (Basel, Switzerland)》2020,25(23)
Petroselinum crispum Mill., Fuss., is a culinary vegetable used as an aromatic herb that garnishes and flavours a great variety of dishes. In the present study, the chemical profiles and bioactivities of leaf samples from 25 cultivars (three types: plain- and curly-leafed and turnip-rooted) from this species were assessed. Seven phenolic compounds were identified in all the varieties, including apigenin and kaempherol derivates. Apigenin-O-pentoside-O-hexoside was the major compound in all the tested parsley types (20, 22 and 13 mg/g of extract, respectively) and responsible for its excellent antioxidant activity, also investigated in this study. Antimicrobial activities were also explored, and the results revealed a good bioactivity against specific tested pathogens, such as bacteria and fungi. In conclusion, the leaves of all the types of P. crispum are a good source of natural bioactive compounds that confer health benefits, and thus, they should be part of a balanced and diversified diet. 相似文献
157.
Victor Ch. Kravtsov Vasile Lozovan Nikita Siminel Eduard B. Coropceanu Olga V. Kulikova Natalia V. Costriucova Marina S. Fonari 《Molecules (Basel, Switzerland)》2020,25(23)
Eight mixed-ligand coordination networks, [Cd(2-aba)(NO3)(4-bphz)3/2]n·n(dmf) (1), [Cd(2-aba)2(4-bphz)]n·0.75n(dmf) (2), [Cd(seb)(4-bphz)]n·n(H2O) (3), [Cd(seb)(4-bpmhz)]n·n(H2O) (4), [Cd(hpa)(3-bphz)]n (5), [Zn(1,3-bdc)(3-bpmhz)]n·n(MeOH) (6), [Cd(1,3-bdc)(3-bpmhz)]n ·0.5n(H2O)·0.5n(EtOH) (7), and [Cd(NO3)2(3-bphz)(bpe)]n·n(3-bphz) (8) were obtained by interplay of cadmium nitrate tetrahydrate or zinc nitrate hexahydrate with 2-aminobenzenecarboxylic acid (H(2-aba)), three dicarboxylic acids, sebacic (decanedioic acid, H2seb), homophthalic (2-(carboxymethyl)benzoic acid, H2hpa), isophthalic (1,3-benzenedicarboxylic acid, H2(1,3-bdc)) acids, bis(4-pyridyl)ethane (bpe) and with four azine ligands, 1,2-bis(pyridin-4-ylmethylene)hydrazine (4-bphz), 1,2-bis(1-(pyridin-4-yl)ethylidene) hydrazine (4-bpmhz), 1,2-bis(pyridin-3-ylmethylene)hydrazine (3-bphz), and 1,2-bis(1-(pyridin-3-yl) ethylidene)hydrazine (3-bpmhz). Compounds 1 and 2 are 1D coordination polymers, while compounds 3–8 are 2D coordination polymers. All compounds were characterized by spectroscopic and X-ray diffraction methods of analysis. The solvent uptakes and stabilities to the guest evacuation were studied and compared for 1D and 2D coordination networks. The de-solvated forms revealed a significant increase of emission in comparison with the as-synthesized crystals. 相似文献
158.
Maria A. Tikhonova Nadezhda G. Tikhonova Michael V. Tenditnik Marina V. Ovsyukova Anna A. Akopyan Nina I. Dubrovina Tamara G. Amstislavskaya Elena K. Khlestkina 《Molecules (Basel, Switzerland)》2020,25(22)
Functional nutrition is a valuable supplementation to dietary therapy. Functional foods are enriched with biologically active substances. Plant polyphenols attract particular attention due to multiple beneficial properties attributed to their high antioxidant and other biological activities. We assessed the effect of grape polyphenols on the life span of C57BL/6 mice and on behavioral and neuroinflammatory alterations in a transgenic mouse model of Parkinson disease (PD) with overexpression of the A53T-mutant human α-synuclein. C57BL/6 mice were given a dietary supplement containing grape polyphenol concentrate (GPC—1.5 mL/kg/day) with drinking water from the age of 6–8 weeks for life. Transgenic PD mice received GPC beginning at the age of 10 weeks for four months. GPC significantly influenced the cumulative proportion of surviving and substantially augmented the average life span in mice. In the transgenic PD model, the grape polyphenol (GP) diet enhanced memory reconsolidation and diminished memory extinction in a passive avoidance test. Behavioral effects of GP treatment were accompanied by a decrease in α-synuclein accumulation in the frontal cortex and a reduction in the expression of neuroinflammatory markers (IBA1 and CD54) in the frontal cortex and hippocampus. Thus, a GP-rich diet is recommended as promising functional nutrition for aging people and patients with neurodegenerative disorders. 相似文献
159.
Aziz Bouymajane Yassine Oulad El Majdoub Francesco Cacciola Marina Russo Fabio Salafia Alessandra Trozzi Fouzia Rhazi Filali Paola Dugo Luigi Mondello 《Molecules (Basel, Switzerland)》2020,25(22)
Olive oil is an important product in the Mediterranean diet, due to its health benefits and sensorial characteristics. Picholine marocaine is the most cultivated variety in Morocco. The present research aims to evaluate the phenolic compounds, vitamin E and fatty acids of commercial Picholine marocaine virgin olive oils (VOOs) from five different North Moroccan provinces (Chefchaouen, Taounate, Errachidia, Beni Mellal and Taza), using HPLC-photodiode array (PDA)/electrospray ionization (ESI)-MS, normal phase (NP)-HPLC/ fluorescence detector (FLD) and GC-flame ionization detector (FID)/MS, respectively. The obtained results showed an average content of 130.0 mg kg−1 of secoiridoids (oleuropein aglycone, 10-hydroxy-oleuropein aglycone and ligstroside aglycone, oleocanthal and oleacein), 108.1 mg kg−1 of phenolic alcohols (tyrosol and hydroxytyrosol), 34.7 mg kg−1 of phenolic acids (caffeic acid, ferulic acid and elenolic acid), and 8.24 mg kg−1 of flavonoids (luteolin, luteolin glucoside, apigenin). With regard to vitamin E, α-tocopherol was the most abundant vitamin E (57.9 mg kg−1), followed by α-tocotrienol (2.5 mg kg−1), γ-tocopherol (4.5 mg kg−1) and β-tocopherol (1.9 mg kg−1), while δ-tocopherol was not detected. Moreover, 14 fatty acids were found and, among them, oleic acid (76.1%), linoleic acid (8.1%) palmitic acid (8.7%) and stearic acid (2.5%) were the major fatty acids detected. Finally, heat map and principal component analysis allowed us to classify the studied provinces in terms of VOO chemical composition: Chefchaouen (tyrosol and hydroxytyrosol), Taounate (oleuropein aglycone), Errachidia (ferulic acid, w-3 and w-6), Beni Mellal (oleocanthal) and Taza (luteolin and oleic acid). 相似文献
160.
Zheng Zhou James McNeely Joshua Greenough Zheng Wei Haixiang Han Mathieu Rouzires Andrey Yu. Rogachev Rodolphe Clrac Marina A. Petrukhina 《Chemical science》2022,13(13):3864
The synthesis of a novel family of homoleptic COT-based heterotrimetallic self-assemblies bearing the formula [LnKCa(COT)3(THF)3] (Ln(iii) = Gd, Tb, Dy, Ho, Er, Tm, and Yb) is reported followed by their X-ray crystallographic and magnetic characterization. All crystals conform to the monoclinic P21/c space group with a slight compression of the unit cell from 3396.4(2) Å3 to 3373.2(4) Å3 along the series. All complexes exhibit a triple-decker structure having the Ln(iii) and K(i) ions sandwiched by three COT2− ligands with an end-bound {Ca2+(THF)3} moiety to form a non-linear (153.5°) arrangement of three different metals. The COT2− ligands act in a η8-mode with respect to all metal centers. A detailed structural comparison of this unique set of heterotrimetallic complexes has revealed consistent trends along the series. From Gd to Yb, the Ln to ring-centroid distance decreases from 1.961(3) Å to 1.827(2) Å. In contrast, the separation of K(i) and Ca(ii) ions from the COT-centroid (2.443(3) and 1.914(3) Å, respectively) is not affected by the change of Ln(iii) ions. The magnetic property investigation of the [LnKCa(COT)3(THF)3] series (Ln(iii) = Gd, Tb, Dy, Ho, Er, and Tm) reveals that the Dy, Er, and Tm complexes display slow relaxation of their magnetization, in other words, single-molecule magnet (SMM) properties. This behaviour is dominated by thermally activated (Orbach-like) and quantum tunneling processes for [DyKCa(COT)3(THF)3] in contrast to [ErKCa(COT)3(THF)3], in which the thermally activated and Raman processes appear to be relevant. Details of the electronic structures and magnetic properties of these complexes are further clarified with the help of DFT and ab initio theoretical calculations.A new class of heterotrimetallic COT-based self-assemblies accommodates metals from groups I–III in three different oxidation states and enables tuning of electronic and magnetic properties. 相似文献