全文获取类型
收费全文 | 3264篇 |
免费 | 165篇 |
国内免费 | 15篇 |
专业分类
化学 | 2434篇 |
晶体学 | 27篇 |
力学 | 64篇 |
数学 | 332篇 |
物理学 | 587篇 |
出版年
2023年 | 27篇 |
2022年 | 80篇 |
2021年 | 75篇 |
2020年 | 62篇 |
2019年 | 76篇 |
2018年 | 65篇 |
2017年 | 36篇 |
2016年 | 120篇 |
2015年 | 99篇 |
2014年 | 104篇 |
2013年 | 219篇 |
2012年 | 240篇 |
2011年 | 225篇 |
2010年 | 116篇 |
2009年 | 112篇 |
2008年 | 178篇 |
2007年 | 191篇 |
2006年 | 139篇 |
2005年 | 178篇 |
2004年 | 140篇 |
2003年 | 104篇 |
2002年 | 169篇 |
2001年 | 49篇 |
2000年 | 49篇 |
1999年 | 40篇 |
1998年 | 30篇 |
1997年 | 46篇 |
1996年 | 35篇 |
1995年 | 34篇 |
1994年 | 28篇 |
1993年 | 30篇 |
1992年 | 21篇 |
1991年 | 25篇 |
1990年 | 25篇 |
1989年 | 29篇 |
1988年 | 22篇 |
1987年 | 17篇 |
1986年 | 23篇 |
1985年 | 20篇 |
1984年 | 25篇 |
1983年 | 14篇 |
1982年 | 22篇 |
1981年 | 20篇 |
1980年 | 10篇 |
1979年 | 11篇 |
1978年 | 18篇 |
1977年 | 12篇 |
1976年 | 8篇 |
1975年 | 6篇 |
1973年 | 5篇 |
排序方式: 共有3444条查询结果,搜索用时 15 毫秒
171.
Avoided crossing is one of the unique spectroscopic features of a confined atomic system. Shannon information entropy of the ground state and some of the excited states of confined H atom as a predictor of avoided crossing is studied in this work. This is accomplished by varying the strength of the confinement and examining structure properties like ionization energy and Shannon information entropy. Along with the energy level repulsion at the avoided crossing, Shannon information entropy is also exchanged between the involved states. This work also addresses a question: In addition to that regarding localization, what other property of the system can be extracted from Shannon entropy? Insightful connection is discovered between Shannon entropy and the average value of confinement potential, Coulomb potential, and kinetic energy. 相似文献
172.
Christina Zovko Dr. Sebastian Bestgen Dr. Christoph Schoo Anne Görner Prof. Jose M. Goicoechea Prof. Peter W. Roesky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(58):13191-13202
A bis(diphenyl)-phosphine functionalized β-diketimine (PNac-H) was synthesized as a flexible ligand for transition metal complexes. The newly designed ligand features symmetrically placed phosphine moieties around a β-diketimine unit, forming a PNNP-type pocket. Due to the hard and soft donor atoms (N vs. P) the ligand can stabilize various coordination polyhedra. A complete series ranging from coordination numbers 2 to 6 was realized. Linear, trigonal planar, square planar, tetrahedral, square pyramidal, and octahedral coordination arrangements containing the PNac-ligand around the metal center were observed by using suitable metal sources. Hereby, PNac-H or its anion PNac− acts as mono-, bi- and tetradendate ligand. Such a broad flexibility is unusual for a rigid tetradentate system. The structural motifs were realized by treatment of PNac-H with a series of late transition metal precursors, for example, silver, gold, nickel, copper, platinum, and rhodium. The new complexes have been fully characterized by single crystal X-ray diffraction, NMR, IR, UV/Vis spectroscopy, mass spectrometry as well as elemental analysis. Additionally, selected complexes were investigated regarding their photophysical properties. Thus, PNac-H proved to be an ideal ligand platform for the selective coordination and stabilization of various metal ions in diverse polyhedra and oxidation states. 相似文献
173.
Yuli Zhang Hieu M. Pham Jose G. Munguia-Lopez Joseph M. Kinsella Simon D. Tran 《Molecules (Basel, Switzerland)》2020,25(23)
Hydrogels have been used for a variety of biomedical applications; in tissue engineering, they are commonly used as scaffolds to cultivate cells in a three-dimensional (3D) environment allowing the formation of organoids or cellular spheroids. Egg white-alginate (EWA) is a novel hydrogel which combines the advantages of both egg white and alginate; the egg white material provides extracellular matrix (ECM)-like proteins that can mimic the ECM microenvironment, while alginate can be tuned mechanically through its ionic crosslinking property to modify the scaffold’s porosity, strength, and stiffness. In this study, a frozen calcium chloride (CaCl2) disk technique to homogenously crosslink alginate and egg white hydrogel is presented for 2.5D culture of human salivary cells. Different EWA formulations were prepared and biologically evaluated as a spheroid-like structure platform. Although all five EWA hydrogels showed biocompatibility, the EWA with 1.5% alginate presented the highest cell viability, while EWA with 3% alginate promoted the formation of larger size salivary spheroid-like structures. Our EWA hydrogel has the potential to be an alternative 3D culture scaffold that can be used for studies on drug-screening, cell migration, or as an in vitro disease model. In addition, EWA can be used as a potential source for cell transplantation (i.e., using this platform as an ex vivo environment for cell expansion). The low cost of producing EWA is an added advantage. 相似文献
174.
Meera Mehta Jose M. Goicoechea 《Angewandte Chemie (International ed. in English)》2020,59(7):2715-2719
Molecular compounds featuring nitrogen atoms are typically regarded as Lewis bases and are extensively employed as donor ligands in coordination chemistry or as nucleophiles in organic chemistry. By contrast, electrophilic nitrogen‐containing compounds are much rarer. Nitrenium cations are a new family of nitrogen‐based Lewis acids, the reactivity of which remains largely unexplored. In this work, nitrenium ions are explored as catalysts in five organic transformations. These reactions are the first examples of Lewis acid catalysis employing nitrogen as the site of substrate activation. Moreover, these compounds are readily accessed from commercially available reagents and exhibit remarkable stability toward moisture, allowing for benchtop transformations without the need to pretreat solvents. 相似文献
175.
Kaitlyn A. Perez Cameron R. Rogers Emily A. Weiss 《Angewandte Chemie (International ed. in English)》2020,59(33):14091-14095
This Communication describes the use of CuInS2/ZnS quantum dots (QDs) as photocatalysts for the reductive deprotection of aryl sulfonyl‐protected phenols. For a series of aryl sulfonates with electron‐withdrawing substituents, the rate of deprotection for the corresponding phenyl aryl sulfonates increases with decreasing electrochemical potential for the two electron transfers within the catalytic cycle. The rate of deprotection for a substrate that contains a carboxylic acid, a known QD‐binding group, is accelerated by more than a factor of ten from that expected from the electrochemical potential for the transformation, a result that suggests that formation of metastable electron donor–acceptor complexes provides a significant kinetic advantage. This deprotection method does not perturb the common NHBoc or toluenesulfonyl protecting groups and, as demonstrated with an estrone substrate, does not perturb proximate ketones, which are generally vulnerable to many chemical reduction methods used for this class of reactions. 相似文献
176.
Oscar Cervantes Zaira del Rocio Lopez Norberto Casillas Peter Knauth Nayeli Checa Francisco Apolinar Cholico Rodolfo Hernandez-Gutirrez Luis Hector Quintero Jose Avila Paz Mario Eduardo Cano 《Molecules (Basel, Switzerland)》2022,27(2)
A ferrofluid with 1,2-Benzenediol-coated iron oxide nanoparticles was synthesized and physicochemically analyzed. This colloidal system was prepared following the typical co-precipitation method, and superparamagnetic nanoparticles of 13.5 nm average diameter, 34 emu/g of magnetic saturation, and 285 K of blocking temperature were obtained. Additionally, the zeta potential showed a suitable colloidal stability for cancer therapy assays and the magneto-calorimetric trails determined a high power absorption density. In addition, the oxidative capability of the ferrofluid was corroborated by performing the Fenton reaction with methylene blue (MB) dissolved in water, where the ferrofluid was suitable for producing reactive oxygen species (ROS), and surprisingly a strong degradation of MB was also observed when it was combined with H2O2. The intracellular ROS production was qualitatively corroborated using the HT-29 human cell line, by detecting the fluorescent rise induced in 2,7-dichlorofluorescein diacetate. In other experiments, cell metabolic activity was measured, and no toxicity was observed, even with concentrations of up to 4 mg/mL of magnetic nanoparticles (MNPs). When the cells were treated with magnetic hyperthermia, 80% of cells were dead at 43 °C using 3 mg/mL of MNPs and applying a magnetic field of 530 kHz with 20 kA/m amplitude. 相似文献
177.
Peter Jaein Choi Petr Tomek Moana Tercel Jhannes Reynisson Thomas In Hyeup Park Elizabeth Alexandra Cooper William Alexander Denny Jiney Jose Euphemia Leung 《Molecules (Basel, Switzerland)》2022,27(3)
The CDK4/6 inhibitor palbociclib, combined with endocrine therapy, has been shown to be effective in postmenopausal women with estrogen receptor-positive, HER2-negative advanced or metastatic breast cancer. However, palbociclib is not as effective in the highly aggressive, triple-negative breast cancer that lacks sensitivity to chemotherapy or endocrine therapy. We hypothesized that conjugation of the near-infrared dye MHI-148 with palbociclib can produce a potential theranostic in triple-negative, as well as estrogen receptor-positive, breast cancer cells. In our study, the conjugate was found to have enhanced activity in all mammalian cell lines tested in vitro. However, the conjugate was cytotoxic and did not induce G1 cell cycle arrest in breast cancer cells, suggesting its mechanism of action differs from the parent compound palbociclib. The study highlights the importance of investigating the mechanism of conjugates of near-infrared dyes to therapeutic compounds, as conjugation can potentially result in a change of mechanism or target, with an enhanced cytotoxic effect in this case. 相似文献
178.
Films were obtained by coalescence of different types of latex particles; the purpose of this work was to get informations on the geometric arrangement (so called “morphology”) of the different phases and on the role of interfaces. Such informations are difficult to get by direct investigations (weak contrast in Transmission Electron Microscopy, poor information provided by X-ray measurements on amorphous polymers …) the analysis of experimental data obtained in high resolution mechanical spectrometry appears powerful: it is possible, for instance, to estimate the profile gradient of composition at the interface. Comparison is made between the morphology of the different phases in some films and the correspondent structure of particles. 相似文献
179.
Juan M. Muñoz-Ocaña Ainouna Bouziane Farzeen Sakina Richard T. Baker Ana B. Hungría Jose J. Calvino Antonio M. Rodríguez-Chía Miguel López-Haro 《Particle & Particle Systems Characterization》2020,37(6):2000070
A novel procedure to optimize the 3D morphological characterization of nanomaterials by means of high angle annular dark field scanning-transmission electron tomography is reported and is successfully applied to the analysis of a metal- and halogen-free ordered mesoporous carbon material. The new method is based on a selection of the two parameters (μ and β) which are key in the reconstruction of tomographic series by means of total variation minimization (TVM). The parameter-selected TVM reconstructions obtained using this approach clearly reveal the porous structure of the carbon-based material as consisting of a network of parallel, straight channels of ≈6 nm diameter ordered in a honeycomb-type arrangement. Such an unusual structure cannot be retrieved from a TVM 3D reconstruction using default reconstruction values. Moreover, segmentation and further quantification of the optimized 3D tomographic reconstruction provide values for different textural parameters, such as pore size distribution and specific pore volume that match very closely with those determined by macroscopic physisorption techniques. The approach developed can be extended to other reconstruction models in which the final result is influenced by parameter choice. 相似文献
180.
Jazer Jose H. Togonon Eugene A. Esparcia Jr. Prof. Julie Anne D. del Rosario Prof. Joey D. Ocon 《ChemistryOpen》2021,10(4):471-476
Biodegradable primary batteries, also known as transient batteries, are essential to realize autonomous biodegradable electronic devices with high performance and advanced functionality. In this work, magnesium, copper, iron, and zinc – metals that exist as trace elements in the human body – were tested as materials for biomedical transient electronic devices. Different full cell combinations of Mg and X (where X = Cu, Fe, and Zn and the anodized form of the metals) with phosphate buffered saline (PBS) as electrolyte were studied. To form the cathodes, metal foils were anodized galvanostatically at a current density of 2.0 mA cm−2 for 30 mins. Electrochemical measurements were then conducted for each electrode combination to evaluate full cell battery performance. Results showed that the Mg−Cuanodized chemistry has the highest power density at 0.99 mW/cm2. Nominal operating voltages of 1.26 V for the first 0.50 h and 0.63 V for the next 3.7 h were observed for Mg−Cuanodized which was discharged at a current density of 0.70 mA cm−2. Among the materials tested, Mg−Cuanodized exhibited the best discharge performance with an average specific capacity of 2.94 mAh cm−2, which is comparable to previous reports on transient batteries. 相似文献