全文获取类型
收费全文 | 703篇 |
免费 | 55篇 |
国内免费 | 1篇 |
专业分类
化学 | 512篇 |
晶体学 | 3篇 |
力学 | 13篇 |
数学 | 88篇 |
物理学 | 87篇 |
无线电 | 56篇 |
出版年
2023年 | 16篇 |
2022年 | 12篇 |
2021年 | 18篇 |
2020年 | 35篇 |
2019年 | 32篇 |
2018年 | 17篇 |
2017年 | 14篇 |
2016年 | 31篇 |
2015年 | 30篇 |
2014年 | 37篇 |
2013年 | 34篇 |
2012年 | 67篇 |
2011年 | 68篇 |
2010年 | 30篇 |
2009年 | 23篇 |
2008年 | 37篇 |
2007年 | 30篇 |
2006年 | 34篇 |
2005年 | 38篇 |
2004年 | 27篇 |
2003年 | 18篇 |
2002年 | 15篇 |
2001年 | 4篇 |
2000年 | 4篇 |
1999年 | 5篇 |
1998年 | 6篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 2篇 |
1994年 | 4篇 |
1993年 | 2篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1970年 | 2篇 |
1960年 | 5篇 |
1929年 | 2篇 |
1928年 | 2篇 |
1875年 | 1篇 |
排序方式: 共有759条查询结果,搜索用时 0 毫秒
21.
Kyle T. Gustafson Zeynep Sayar Hillary Le Steven L. Gustafson Austin Gower Augusta Modestino Stuart Ibsen Michael J. Heller Sadik Esener Sebnem E. Eksi 《Electrophoresis》2022,43(16-17):1784-1798
Cancer is a highly heterogenous disease that requires precise detection tools and active surveillance methods. Liquid biopsy assays provide an agnostic way to follow the complex trajectory of cancer, providing better patient stratification tools for optimized treatment. Here, we present the development of a low-volume liquid biopsy assay called cyc-DEP (cyclic immunofluorescent imaging on dielectrophoretic chip) to profile biomarkers collected on a dielectrophoretic microfluidic chip platform. To enable on-chip cyclic imaging, we optimized a fluorophore quenching method and sequential rounds of on-chip staining with fluorescently conjugated primary antibodies. cyc-DEP allows for the quantification of a multiplex array of proteins using 25 µl of a patient plasma sample. We utilized nanoparticles from a prostate adenocarcinoma (LNCaP) cell line and a panel of six target proteins to develop our proof-of-concept technique. We then used cyc-DEP to quantify blood plasma levels of target proteins from healthy individuals, low-grade and high-grade prostate cancer patients (n = 3 each) in order to demonstrate that our platform is suitable for liquid biopsy analysis in its present form. To ensure accurate quantification of signal intensities and comparisons between different samples, we incorporated a signal intensity normalization method (fluorescent beads) and a custom signal intensity quantification algorithm that account for the distribution of signal across hundreds of collection regions on each chip. Our technique enabled a threefold improvement in multiplicity for detecting proteins associated with fluid samples, opening doors for early detection, and active surveillance through quantification of a multiplex array of biomarkers from low-volume liquid biopsies. 相似文献
22.
Dr. Meaghan M. Deegan Michael R. Dworzak Aeri J. Gosselin Kyle J. Korman Prof. Dr. Eric D. Bloch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(14):4531-4547
Molecules with permanent porosity in the solid state have been studied for decades. Porosity in these systems is governed by intrinsic pore space, as in cages or macrocycles, and extrinsic void space, created through loose, intermolecular solid-state packing. The development of permanently porous molecular materials, especially cages with organic or metal–organic composition, has seen increased interest over the past decade, and as such, incredibly high surface areas have been reported for these solids. Despite this, examples of these materials being explored for gas storage applications are relatively limited. This minireview outlines existing molecular systems that have been investigated for gas storage and highlights strategies that have been used to understand adsorption mechanisms in porous molecular materials. 相似文献
23.
Kyle M. McCall Bogdan M. Benin Michael Wörle Thomas Vonderach Detlef Günther Maksym V. Kovalenko 《Helvetica chimica acta》2021,104(1):e2000206
Inorganic, lead-free metal halides are widely sought after following the rise of the halide perovskites as outstanding optoelectronic materials, due to their enhanced stability and reduced toxicity. Herein, we report on the solvothermal synthesis of Rb7Sb3Br16, which exhibits a 0D structure comprised of [SbBr6]3− octahedra and edge-sharing bioctahedra [Sb2Br10]4− dimers that order into layers along the c-axis. This all-inorganic material is air-stable and exhibits weak orange photoluminescence (PL) at room temperature. Low-temperature PL and PL excitation (PLE) measurements reveal the presence of two distinct emission bands that originate from these structural units, with the high-energy emission quenching as temperature rises beyond 150 K. We are also able to obtain Rb7Bi3Br16 and Rb7Bi3I16 which both crystallize in orthorhombic symmetry, with Rb7Bi3Br16 presenting weak low-temperature luminescence while Rb7Bi3I16 is non-luminescent. This work expands the library of emissive inorganic metal halides and provides further evidence for the efficacy of low-dimensional Sb−X luminescent centers based on octahedral and edge-sharing [Sb2X10]4− dimers. 相似文献
24.
25.
Banerjee A Grewer C Ramakrishnan L Jäger J Gameiro A Breitinger HG Gee KR Carpenter BK Hess GP 《The Journal of organic chemistry》2003,68(22):8361-8367
The synthesis and characterization of a new photolabile protecting group (caging group) for carboxylic acids, the 2-(dimethylamino)-5-nitrophenyl (DANP) group, is described. This compound has a major absorption band in the visible wavelength region with a maximum near 400 nm (epsilon400 = 9077 M(-1) cm(-1) at pH 7.4 and 21 degrees C). The caging group is attached through an ester linkage to the carboxyl functionality of beta-alanine, which activates the inhibitory glycine receptor in the mammalian central nervous system. Such caged compounds play an important role in transient kinetic investigations of fast cellular processes. Upon photolysis of DANP-caged beta-alanine, the caging group is released within 5 micros. Quantum yields of 0.03 and 0.002 were obtained in the UV region (308 and 360 nm) and the visible region (450 nm), respectively. Laser-pulse photolysis experiments, using 337 or 360 nm light, were performed with the caged compound equilibrated with HEK 293 cells transiently transfected with cDNA encoding the alpha1 homomeric, wild-type glycine receptor. The experiments demonstrated that neither DANP-caged beta-alanine nor its byproducts inhibit or activate the glycine receptors on the cell surface. Under physiological conditions, the DANP-caged beta-alanine is water-soluble and stable and can be used for transient kinetic measurements. 相似文献
26.
The 2,5-diketopiperazine (DKP) moiety is a core feature of many natural products and medicinally relevant scaffolds. As part of our efforts directed towards a total synthesis of penicisulfuranol B, we have developed and report herein: (1) the preparation of an N-hydroxy diketopiperazine intermediate accessible via a molybdenum-mediated oxidation of a parent diketopiperazine, and (2) further synthetic studies leading to a novel spirocyclic dihydrobenzofuran-containing diketopiperazine. 相似文献
27.
Kyle Clagg Sara Hold Archana Kumar Stefan G. Koenig Remy Angelaud 《Tetrahedron letters》2019,60(1):5-7
The direct application of Knochel-Hauser derivative arylmagnesium halides in Kumada-Corriu couplings is described. By utilizing the in situ-generated Grignard reagents, the transmetalation with stoichiometric zinc salts to known Negishi coupling conditions is avoided, thereby streamlining the transformation. Several aromatic hetereocycles participate in the deprotonation and couple with a variety of phenyl iodides and bromides in isolated yields up to 81%. The parent system is demonstrated on 6?g scale with 79% yield, and monitored via ReactIR to show the stability of the Grignard and progression of the deprotonation/CC coupling reaction. 相似文献
28.
29.
Sugam Kharel Kyle J. Cluff Nattamai Bhuvanesh John A. Gladysz Janet Blümel 《化学:亚洲杂志》2019,14(15):2704-2711
The three secondary phosphine oxides [CH2=CH(CH2)4]2HPO ( 1 ), [CH2=CH(CH2)5]2HPO ( 2 ), and [CH2=CH(CH2)6]2HPO ( 3 ), and two diphosphine dioxides, {[CH2=CH(CH2)6]2PO(CH2)7}2 ( 4 ) and {[CH2=CH(CH2)6]2PO(CH2)4}2 ( 5 ), incorporating long methylene chains, are described. The single crystal X‐ray structures of 1 , 2 , and 5 have been determined. The phosphine oxides 3 , 4 , and 5 have been adsorbed on silica in submonolayer quantities to give 3 a – 5 a . The 1H, 13C, and 31P solid‐state NMR spectra of polycrystalline 3 – 5 have been analyzed and compared with those of 3 a – 5 a . The changes of the solid‐state NMR characteristics upon adsorption and the surface mobilities of the phosphine oxides are discussed. 相似文献
30.
Kyle A. Mandla Curtis E. Moore Arnold L. Rheingold Joshua S. Figueroa 《Angewandte Chemie (International ed. in English)》2019,58(6):1779-1783
Elemental white phosphorus (P4) is well recognized as a critical precursor to organophosphorus compounds. However, regulatory constraints stemming from the toxic and pyrophoric nature of white phosphorus have significantly limited its accessibility. Herein is described a new approach to white phosphorus storage and release based on a unique example of photolytic reductive elimination of the tetrahedral P4 molecule from a mononuclear cyclo‐P4 molybdenum complex. The latter functions as an air‐stable, chemically‐deactivated source of white phosphorus. The system features efficient photo‐release of white phosphorus using inexpensive violet LED sources. Additionally, high‐yield recapture of unspent white phosphorus by the molybdenum center can be achieved by post‐photolysis heating at convenient temperatures. 相似文献