全文获取类型
收费全文 | 3070篇 |
免费 | 80篇 |
国内免费 | 23篇 |
专业分类
化学 | 1961篇 |
晶体学 | 21篇 |
力学 | 59篇 |
数学 | 598篇 |
物理学 | 534篇 |
出版年
2023年 | 15篇 |
2022年 | 69篇 |
2021年 | 74篇 |
2020年 | 71篇 |
2019年 | 82篇 |
2018年 | 69篇 |
2017年 | 59篇 |
2016年 | 125篇 |
2015年 | 107篇 |
2014年 | 132篇 |
2013年 | 231篇 |
2012年 | 195篇 |
2011年 | 207篇 |
2010年 | 144篇 |
2009年 | 148篇 |
2008年 | 185篇 |
2007年 | 176篇 |
2006年 | 141篇 |
2005年 | 116篇 |
2004年 | 95篇 |
2003年 | 75篇 |
2002年 | 79篇 |
2001年 | 34篇 |
2000年 | 38篇 |
1999年 | 29篇 |
1998年 | 17篇 |
1997年 | 22篇 |
1996年 | 35篇 |
1995年 | 27篇 |
1994年 | 22篇 |
1993年 | 19篇 |
1992年 | 29篇 |
1991年 | 13篇 |
1990年 | 20篇 |
1989年 | 13篇 |
1988年 | 18篇 |
1987年 | 13篇 |
1986年 | 11篇 |
1985年 | 15篇 |
1984年 | 25篇 |
1983年 | 14篇 |
1982年 | 15篇 |
1981年 | 12篇 |
1980年 | 15篇 |
1979年 | 10篇 |
1978年 | 21篇 |
1977年 | 20篇 |
1976年 | 11篇 |
1970年 | 6篇 |
1968年 | 8篇 |
排序方式: 共有3173条查询结果,搜索用时 15 毫秒
91.
Gabriela Dudek Anna Strzelewicz Monika Krasowska Aleksandra Rybak Roman Turczyn 《Chemical Papers》2014,68(5):579-583
Twenty herbs, showing medicinal benefits on human life, like Taraxacum officinale, Plantago lanceolata, Hypericum perforatum, Ocimum basilicum, Melissa officinalis, Mentha piperita, and others, were tested. The percentage content of pigments, i.e. chlorophylls, carotenoids, and flavonoids, in the chosen herbs was determined. The spectrophotometric method, which is quick and readily available, was used. Measurements required pigment extraction with a solvent. Ethanol was used for the determination of chlorophylls and carotenoids, and acetone for the determination of flavonoids. Hierarchical agglomerative cluster analysis was performed in order to confirm the experimental results. The study of flavonoids content showed an interesting regularity which can be used for the classification of herbs. Plants belonging to the Lamiaceae family showed the flavonoids content in the range from 0.18 % to 0.68 %, whereas those belonging to the Apiaceaehas family showed the flavonoids content in the 0.75–1.20 % range. 相似文献
92.
Elena V. Ukhatskaya Sergey V. Kurkov Roman V. Rodik Vitaly I. Kalchenko Susan E. Matthews Phatsawee Jansook Thorsteinn Loftsson 《Journal of inclusion phenomena and macrocyclic chemistry》2014,79(3-4):473-483
The self-aggregation ability of three amphiphilic cationic calix[4]arenes possessing four quaternary amino groups (aminoCAs) was investigated using a variety of methods. All of the studied compounds possess high aggregation ability. Their critical aggregation concentration (CAC) values in water are in the 0.0009–0.04 % (w/v) concentration range. Several size populations of aggregates were detected by DLS for all three CAs, and restructuring of aggregates was observed to be dependent on concentration. Particles formed above CAC were attributed to formation of vesicular structures (vesicles). The coexistence of other type of aggregates (presumably micelles) with vesicles was observed in the aqueous solution of CAs 2 and 3 from concentrations of 0.5 and 0.8 % (w/v), respectively. The filtration procedure was found to be a significant factor since the obtained data from filtered and unfiltered samples was different. The particle sizes obtained by TEM measurements were somewhat correlated with the DLS data for unfiltered CAs solutions. An analysis of the aggregate composition was undertaken by a size-exclusion method using semi-permeable cellophane membranes with different MWCO. A negative deviation from linearity of permeability flux profile starting from 0.8 % (w/v) concentration of donor phase indicated that the fraction of large aggregates at this point is significant enough that the molecules could not easily permeate through the membranes. 相似文献
93.
Dr. José I. Urgel Dr. Marco Di Giovannantonio Kristjan Eimre Thorsten G. Lohr Dr. Junzhi Liu Shantanu Mishra Dr. Qiang Sun Amogh Kinikar Dr. Roland Widmer Samuel Stolz Max Bommert Dr. Reinhard Berger Dr. Pascal Ruffieux Dr. Carlo A. Pignedoli Prof. Dr. Klaus Müllen Prof. Dr. Xinliang Feng Prof. Dr. Roman Fasel 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13383-13389
Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on-surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well-controlled ultrahigh-vacuum conditions. Here we report the on-surface synthesis of a polymer linked by cumulene-like bonds on a Au(111) surface via sequential thermally activated dehalogenative C−C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene-like pentagon–pentagon and heptagon–heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X-ray photoelectron spectroscopy, complemented by density functional theory calculations. Our results provide perspectives for the on-surface synthesis of cumulene-containing compounds, as well as protocols relevant to the stepwise fabrication of carbon–carbon bonds on surfaces. 相似文献
94.
Roman Schowner Dr. Iris Elser Mathis Benedikter Mohasin Momin Dr. Wolfgang Frey Tanja Schneck Dr. Laura Stöhr Prof. Dr. Michael R. Buchmeiser 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(2):961-968
The origin of hydroxyl group tolerance in neutral and especially cationic molybdenum imido alkylidene N-heterocyclic carbene (NHC) complexes has been investigated. A wide range of catalysts was prepared and tested. Most cationic complexes can be handled in air without difficulty and display an unprecedented stability towards water and alcohols. NHC complexes were successfully used with substrates containing the hydroxyl functionality in acyclic diene metathesis polymerization, homo-, cross and ring-opening cross metathesis reactions. The catalysts remain active even in 2-PrOH and are applicable in ring-opening metathesis polymerization and alkene homometathesis using alcohols as solvent. The use of weakly basic bidentate, hemilabile anionic ligands such as triflate or pentafluorobenzoate and weakly basic aromatic imido ligands in combination with a sterically demanding 1,3-dimesitylimidazol-2-ylidene NHC ligand was found essential for reactive and yet robust catalysts. 相似文献
95.
Paweł Wyżga Igor Veremchuk Matej Bobnar Primož Koželj Steffen Klenner Rainer Pöttgen Andreas Leithe-Jasper Roman Gumeniuk 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(23):5245-5256
The homogeneity range of ternary iron indium thiospinel at 873 K was investigated. A detailed study was focused on two distinct series (y=z): 1) a previously reported charge-balanced (In0.67+0.33y□0.33−0.33y)tetr[In2−zFez]octS4 (A1-series; □ stands for vacancy; the abbreviations “tetr” and “oct” indicate atoms occupying tetrahedral 8a and octahedral 16d sites, respectively) and 2) a new charge-unbalanced (In0.67+y□0.33−y)tetr[In2−zFez]octS4 (A2-series). Fe atoms were confirmed to exclusively occupy an octahedral position in both series. An unusual reduction of the unit cell parameter with increasing Fe content is explained by differences in the ionic radii between Fe and In, as well as by an additional electrostatic attraction originating from charge imbalance (latter only in A2-series). The studied compound is an n-type semiconductor, and its charge carrier concentration increases or decreases for larger Fe content within the A1- and A2-series, respectively. The thermal conductivity κtot is significantly reduced upon increasing vacancy concentration, whereas the change of power factor is insufficient to drastically improve the thermoelectric figure of merit. 相似文献
96.
Luis M. Mateo Qiang Sun Shi‐Xia Liu Jesse J. Bergkamp Kristjan Eimre Carlo A. Pignedoli Pascal Ruffieux Silvio Decurtins Giovanni Bottari Roman Fasel Tomas Torres 《Angewandte Chemie (International ed. in English)》2020,59(3):1334-1339
On‐surface synthesis offers a versatile approach to prepare novel carbon‐based nanostructures that cannot be obtained by conventional solution chemistry. Graphene nanoribbons (GNRs) have potential for a variety of applications. A key issue for their application in molecular electronics is in the fine‐tuning of their electronic properties through structural modifications, such as heteroatom doping or the incorporation of non‐benzenoid rings. In this context, the covalent fusion of GNRs and porphyrins (Pors) is a highly appealing strategy. Herein we present the selective on‐surface synthesis of a Por–GNR hybrid, which consists of two Pors connected by a short GNR segment. The atomically precise structure of the Por–GNR hybrid has been characterized by bond‐resolved scanning tunneling microscopy (STM) and noncontact atomic force microscopy (nc‐AFM). The electronic properties have been investigated by scanning tunneling spectroscopy (STS), in combination with DFT calculations, which reveals a low electronic gap of 0.4 eV. 相似文献
97.
Shantanu Mishra Doreen Beyer Kristjan Eimre Ricardo Ortiz Joaquín Fernndez‐Rossier Reinhard Berger Oliver Grning Carlo A. Pignedoli Roman Fasel Xinliang Feng Pascal Ruffieux 《Angewandte Chemie (International ed. in English)》2020,59(29):12041-12047
Triangular zigzag nanographenes, such as triangulene and its π‐extended homologues, have received widespread attention as organic nanomagnets for molecular spintronics, and may serve as building blocks for high‐spin networks with long‐range magnetic order, which are of immense fundamental and technological relevance. As a first step towards these lines, we present the on‐surface synthesis and a proof‐of‐principle experimental study of magnetism in covalently bonded triangulene dimers. On‐surface reactions of rationally designed precursor molecules on Au(111) lead to the selective formation of triangulene dimers in which the triangulene units are either directly connected through their minority sublattice atoms, or are separated via a 1,4‐phenylene spacer. The chemical structures of the dimers have been characterized by bond‐resolved scanning tunneling microscopy. Scanning tunneling spectroscopy and inelastic electron tunneling spectroscopy measurements reveal collective singlet–triplet spin excitations in the dimers, demonstrating efficient intertriangulene magnetic coupling. 相似文献
98.
Samuel Stolz Marco Di Giovannantonio Jos I. Urgel Qiang Sun Amogh Kinikar Gabriela Borin Barin Max Bommert Roman Fasel Roland Widmer 《Angewandte Chemie (International ed. in English)》2020,59(33):14106-14110
In the emerging field of on‐surface synthesis, dehalogenative aryl–aryl coupling is unarguably the most prominent tool for the fabrication of covalently bonded carbon‐based nanomaterials. Despite its importance, the reaction kinetics are still poorly understood. Here we present a comprehensive temperature‐programmed x‐ray photoelectron spectroscopy investigation of reaction kinetics and energetics in the prototypical on‐surface dehalogenative polymerization of 4,4′′‐dibromo‐p‐terphenyl into poly(para‐phenylene) on two coinage metal surfaces, Cu(111) and Au(111). We find clear evidence for reversible dehalogenation on Au(111), which is inhibited on Cu(111) owing to the formation of organometallic intermediates. The incorporation of reversible dehalogenation in the reaction rate equations leads to excellent agreement with experimental data and allows extracting the relevant energy barriers. Our findings deepen the mechanistic understanding and call for its reassessment for surface‐confined aryl–aryl coupling on the most frequently used metal substrates. 相似文献
99.
Sangeeta Kumari Aundrea Roman Arshad Khan 《Journal of polymer science. Part A, Polymer chemistry》1996,34(14):2975-2980
The experimental UV-vis spectrum of the glycogen-iodine (GI) complex shows certain features remarkably similar to that of the amylopectin-iodine (API) complex [J. Polymer. Chem. 32, 2257 (1994)], suggesting a strong similarity between the API and the GI structures. As in the API complex, a nearly linear polyiodine unit, I4, at an interiodine distance of around 3 Å is expected to exist within the helix of 11 anhydroglucose units (AGUs). There are several other spectral features that suggest the presence of another similar but more loosely bound iodine species with a longer interiodine distance of 3.1 Å. These findings suggest the involvement of two different types of glycogen chains in binding iodine molecules. © 1996 John Wiley & Sons, Inc. 相似文献
100.
The elution order of the hop α- and β-acids has been studied under different modes of electrokinetic separation. A model is advanced to explain the shorter migration times of the more hydrophobic β-acids compared to the α-acids in micellar electrokinetic chromatography (MEKC). For quality control of the bitter principles in hops, the ruggedness of electrokinetic separation could be improved by replacing MEKC by microemulsion electrokinetic chromatography (MEEKC). 相似文献