全文获取类型
收费全文 | 697篇 |
免费 | 67篇 |
国内免费 | 2篇 |
专业分类
化学 | 625篇 |
力学 | 14篇 |
数学 | 59篇 |
物理学 | 68篇 |
出版年
2023年 | 13篇 |
2022年 | 14篇 |
2021年 | 29篇 |
2020年 | 34篇 |
2019年 | 17篇 |
2018年 | 9篇 |
2017年 | 10篇 |
2016年 | 56篇 |
2015年 | 30篇 |
2014年 | 38篇 |
2013年 | 28篇 |
2012年 | 53篇 |
2011年 | 74篇 |
2010年 | 21篇 |
2009年 | 12篇 |
2008年 | 51篇 |
2007年 | 44篇 |
2006年 | 43篇 |
2005年 | 28篇 |
2004年 | 33篇 |
2003年 | 18篇 |
2002年 | 24篇 |
2001年 | 7篇 |
2000年 | 3篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1996年 | 5篇 |
1995年 | 8篇 |
1994年 | 3篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1985年 | 5篇 |
1981年 | 2篇 |
1979年 | 2篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1961年 | 1篇 |
1960年 | 1篇 |
1957年 | 3篇 |
1956年 | 3篇 |
1944年 | 2篇 |
1943年 | 1篇 |
1936年 | 1篇 |
1935年 | 1篇 |
1931年 | 1篇 |
1930年 | 1篇 |
1921年 | 1篇 |
1899年 | 2篇 |
排序方式: 共有766条查询结果,搜索用时 31 毫秒
11.
Feng Xian Liu-Cai Charlotte Pham Farida Bey Gilbert Hervé 《Reaction Kinetics and Catalysis Letters》2002,75(2):305-314
Effects of Cs+, H+ and Cu2+ counterions in the vanadium containing heteropoly compounds CsxH1-xVO[PMo12O40] and CsyH0.5-yCu0.25VO[PMo12O40] on the catalytic oxidation of isobutane and characterization by TGA, IR and ESR spectroscopies are reported. A high selectivity of 76% for methacrylic acid and methacrolein together has been obtained with Cs0.75H0.25VO[PMo12O40] catalysts at a reactivity of 5.3x10-1 mmol/h cm3. 相似文献
12.
Maria Weber Hai-Hao Han Bo-Han Li Maria
L. Odyniec Charlotte E. F. Jarman Yi Zang Steven D. Bull Amanda B. Mackenzie Adam C. Sedgwick Jia Li Xiao-Peng He Tony D. James 《Chemical science》2020,11(32):8567
Reaction-based fluorescent-probes have proven successful for the visualisation of biological species in various cellular processes. Unfortunately, in order to tailor the design of a fluorescent probe to a specific application (i.e. organelle targeting, material and theranostic applications) often requires extensive synthetic efforts and the synthetic screening of a range of fluorophores to match the required synthetic needs. In this work, we have identified Pinkment-OH as a unique “plug-and-play” synthetic platform that can be used to develop a range of ONOO− responsive fluorescent probes for a variety of applications. These include theranostic-based applications and potential material-based/bioconjugation applications. The as prepared probes displayed an excellent sensitivity and selectivity for ONOO− over other ROS. In vitro studies using HeLa cells and RAW 264.7 macrophages demonstrated their ability to detect exogenously and endogenously produced ONOO−. Evaluation in an LPS-induced inflammation mouse model illustrated the ability to monitor ONOO− production in acute inflammation. Lastly, theranostic-based probes enabled the simultaneous evaluation of indomethacin-based therapeutic effects combined with the visualisation of an inflammation biomarker in RAW 264.7 cells. Pinkment, a resorufin based ONOO− selective and sensitive ‘plug and play’ fluorescence-based platform for in vitro and in vivo use, enables facile functionalisation for various imaging and theranostic applications. 相似文献
13.
Paramasivan Halasyamani Kevin R. Heier Michael J. Willis Charlotte L. Stern Kenneth R. Poeppelmeier 《无机化学与普通化学杂志》1996,622(3):479-485
Crystals of CuNb(pyz)2OF5 · (pyz)(H2O) ( 1 ) and [Cu(pyz)2.5]+ [NbF6]? · (pyz) ( 2 ) were grown (150°C and autogeneous pressures) from CuO, 1/2(Nb2O5), (HF)x · pyridine, and H2O in excess pyrazine. Light blue single crystals of ( 1 ) are orthorhombic, crystallizing in space group Cccm (No. 66), with a = 14.547(1) Å, b = 16.135(2) Å, c = 13.803(2) Å, and Z = 8. The structure of ( 1 ) contains corner shared [Cu(pyz)4/2F2/2]+, [Cu(pyz)4/2O2/2], and [NbF4O1/2F1/2]?0.5 octahedra. Orange crystals of ( 2 ) are monoclinic, crystallizing in space group C2/c (No. 15), with a = 11.792(8) Å, b = 17.123(3) Å, c = 17.051(5) Å, β = 90.04(4)°, and Z = 8. The structure of ( 2 ) contains puckered rings of corner shared [Cu(pyz)(pyz)3/2]+ tetrahedra and isolated [NbF6]? anions within the rings. 相似文献
14.
Dash AK Jensen TR Stern CL Marks TJ 《Journal of the American Chemical Society》2004,126(39):12528-12540
Single-site polymerization catalysts generated in situ via activation of Cp*MMe(3) (Cp* = C(5)Me(5); M = Ti, Zr), (CGC)MMe(2) (CGC = C(5)Me(4)SiMe(2)NBu(t)(); M = Ti, Zr), and Cp(2)ZrMe(2) with Ph(3)C(+)B(C(6)F(5))(4)(-) catalyze alkylation of aromatic molecules (benzene, toluene) with alpha-chloronorbornene at room temperature, to regioselectively afford the 1:1 addition products exo-1-chloro-2-arylnorbornane (aryl = C(6)H(5) (1a), C(6)H(4)CH(3) (1b)) in good yields. Analogous deuterium-labeled products exo-1-chloro-2-aryl-d(n)-norbornane-7-d(1) (aryl-d(n) = C(6)D(5) (1a-d(6)), C(6)D(4)CD(3) (1b-d(8))) are obtained via catalytic arylation of alpha-chloronorbornene in either benzene-d(6) or toluene-d(8). Isolated ion-pair complexes such as (CGC)ZrMe(toluene)(+)B(C(6)F(5))(4)(-) and Cp(2)ThMe(+)B(C(6)F(5))(4)(-) also catalyze the reaction of alpha-chloronorbornene in toluene-d(8) to give 1b-d(8) in good yields, respectively. Small quantities of the corresponding bis(1-chloronorbornyl)aromatics 2 are also obtained from preparative-scale reactions. These reactions exhibit turnover frequencies exceeding 120 h(-1) (for the Cp*TiMe(3)/Ph(3)C(+)B(C(6)F(5))(4)(-)-catalyzed system), and chlorine-free products are not observed. Compounds 1 and 2 were characterized by (1)H, (2)H, (13)C, and 2D NMR, GC-MS, and elemental analysis. The aryl group exo-stereochemistry in 1a and 1b is established using (1)H-(1)H COSY, (1)H-(13)C HMBC, and (1)H-(1)H NOESY NMR, and is further corroborated by X-ray analysis of the product 1,4-bis(exo-1-chloro-2-norbornyl)benzene (2a). Control experiments and reactivity studies on each component step suggest a mechanism involving participitation of the metal electrophiles in the catalytic cycle. 相似文献
15.
Charlotte Duval Cécile Nouvel Jean‐Luc Six 《Journal of polymer science. Part A, Polymer chemistry》2014,52(8):1130-1138
Poly(d,l ‐lactide‐co‐glycolide) (PLGA) copolyesters are commonly used in biomedical applications. Researches were carried out on nontoxic or low‐toxic catalysts that are enough efficient to provide short polymerization times, adequate microstructure chains and similar properties than the commercial PLGA materials. In this study, PLGA were synthesized by ring‐opening copolymerization (ROP) using three different catalysts. Stannous octoate is the first catalyst we used, as it is very efficient, even its toxicity is still on debate. Two others low‐toxic catalysts [zinc lactate and bismuth subsalicylate (BiSS)] were also evaluated. The comparison of these ROP was realized in terms of kinetics and control of the polymerization. Then, the influence of the catalyst on the PLGA microstructure chains is reported. Finally, abiotic hydrolytic degradation rate is studied. Results described in this article show that BiSS is one very attractive catalyst to produce low toxic PLGA for biomedical applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1130–1138 相似文献
16.
Dr. Benoit Colasson Dr. Thomas Devic Dr. Joël Gaubicher Dr. Charlotte Martineau-Corcos Prof. Philippe Poizot Dr. Vincent Sarou-Kanian 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(37):9589-9596
The synthesis and characterization of a polyrotaxanated covalent organic network (CON) based on the association between the viologen and pillar[5]arene (P[5]OH) units are reported. The mechanical bond allows for the irreversible insertion of n-type redox centers (P[5]OH macrocycles) within a pristine structure based on p-type viologen redox centers. Both redox units are active on a narrow potential range and, in water, the presence of P[5]OH greatly increases the electroactivity of the material. 相似文献
17.
Influence of Equilibration Time in Solution on the Inclusion/Exclusion Topology Ratio of Host–Guest Complexes Probed by Ion Mobility and Collision‐Induced Dissociation 下载免费PDF全文
Glenn Carroy Charlotte Daxhelet Dr. Vincent Lemaur Dr. Julien De Winter Prof. Edwin De Pauw Prof. Jérôme Cornil Prof. Pascal Gerbaux 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(13):4528-4534
Host–guest complexes are formed by the creation of multiple noncovalent bonds between a large molecule (the host) and smaller molecule(s) or ion(s) (the guest(s)). Ion‐mobility separation coupled with mass spectrometry nowadays represents an ideal tool to assess whether the host–guest complexes, when transferred to the gas phase upon electrospray ionization, possess an exclusion or inclusion nature. Nevertheless, the influence of the solution conditions on the nature of the observed gas‐phase ions is often not considered. In the specific case of inclusion complexes, kinetic considerations must be taken into account beside thermodynamics; the guest ingression within the host cavity can be characterized by slow kinetics, which makes the complexation reaction kinetically driven on the timescale of the experiment. This is particularly the case for the cucurbituril family of macrocyclic host molecules. Herein, we selected para‐phenylenediamine and cucurbit[6]uril as a model system to demonstrate, by means of ion mobility and collision‐induced dissociation measurements, that the inclusion/exclusion topology ratio varies as a function of the equilibration time in solution prior to the electrospray process. 相似文献
18.
Charles Romain Charlotte K. Williams 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(6):1633-1636
A novel chemoselective polymerization control yields predictable (co)polymer compositions from a mixture of monomers. Using a dizinc catalyst and a mixture of caprolactone, cyclohexene oxide, and carbon dioxide enables the selective preparation of either polyesters or polycarbonates or copoly(ester‐carbonates). The selectivity depends on the nature of the zinc–oxygen functionality at the growing polymer chain end, and can be controlled by the addition of exogeneous switch reagents. 相似文献
19.
Dr. Karin Mannerstedt Dr. Narendra Kumar Mishra Dr. Ebbe Engholm Dr. Morten Lundh Dr. Charlotte S. Madsen Dr. Philip J. Pedersen Dr. Priska Le-Huu Dr. Søren L. Pedersen Dr. Nina Buch-Månson Dr. Björn Borgström Dr. Thomas Brimert Dr. Lisbeth N. Fink Dr. Keld Fosgerau Prof. Niels Vrang Prof. Knud J. Jensen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(9):3166-3176
A glucose responsive insulin (GRI) that responds to changes in blood glucose concentrations has remained an elusive goal. Here we describe the development of glucose cleavable linkers based on hydrazone and thiazolidine structures. We developed linkers with low levels of spontaneous hydrolysis but increased level of hydrolysis with rising concentrations of glucose, which demonstrated their glucose responsiveness in vitro. Lipidated hydrazones and thiazolidines were conjugated to the LysB29 side-chain of HI by pH-controlled acylations providing GRIs with glucose responsiveness confirmed in vitro for thiazolidines. Clamp studies showed increased glucose infusion at hyperglycemic conditions for one GRI indicative of a true glucose response. The glucose responsive cleavable linker in these GRIs allow changes in glucose levels to drive the release of active insulin from a circulating depot. We have demonstrated an unprecedented, chemically responsive linker concept for biopharmaceuticals. 相似文献
20.
Kätchen K. Lachmayr Charlotte M. Wentz Prof. Lawrence R. Sita 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(4):1537-1542
“One-component” soft material Frank–Kasper (FK) phases are an intriguing structural form of matter that possess periodically ordered structures arising from the self-reconfiguration and close packing of an initial assembly of identical “deformable” spheres into two or more size- or shape-distinct sets of particles. Significant challenges that must still be addressed to advance the field of soft matter FK phases further, however, include their rare and unpredictable occurrence, uncertain mechanisms of solid-state assembly, and low thermodynamic stability. Here we show that a readily-accessible sugar–polyolefin conjugate quantitatively produces an exceptionally stable solid-state FK A15 phase through a rapid and irreversible thermotropic order–order transition, which contrary to other prevailing proposed mechanisms, does not require mass transfer between particles or large structural reorganization in the bulk to establish unit cell non-equivalency. Our results provide the basis for a realistic strategy for obtaining practical and scalable quantities of a diverse range of sugar–polyolefin FK A15 phases with unique intrinsic physical properties and chemical reactivities not previously seen in such systems. 相似文献