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41.
Dr. Valentin Radtke Niklas Gebel Denis Priester Andreas Ermantraut Monika Bäuerle Dr. Daniel Himmel Regina Stroh Prof. Thorsten Koslowski Prof. Ivo Leito Prof. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(40):e202200509
Utilizing the “ideal” ionic liquid salt bridge to measure Gibbs energies of transfer of silver ions between the solvents water, acetonitrile, propylene carbonate and dimethylformamide results in a consistent data set with a precision of 0.6 kJ mol−1 over 87 measurements in 10 half-cells. This forms the basis for a coherent experimental thermodynamic framework of ion solvation chemistry. In addition, we define the solvent independent - and the values that account for the electronating potential of any redox system similar to the value of a medium that accounts for its protonating potential. This scale is thermodynamically well-defined enabling a straightforward comparison of the redox potentials (reducities) of all media with respect to the aqueous redox potential scale, hence unifying all conventional solvents′ redox potential scales. Thus, using the Gibbs energy of transfer of the silver ion published herein, one can convert and unify all hitherto published redox potentials measured, for example, against ferrocene, to the scale. 相似文献
42.
Antoine Barthélemy Dr. Harald Scherer Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(53):e202201369
The tetracationic, univalent cluster compounds [{M(dmpe)}4]4+ (M=Ga, In; dmpe=bis(dimethylphosphino)ethane) were synthesized as their pf salts ([pf]−=[Al(ORF)4]−; RF=C(CF3)3). The four-membered ring in [{M(dmpe)}4]4+ is slightly puckered for M=Ga and almost square planar for M=In. Yet, although structurally similar, only the gallium cluster is prevalent in solution, while the indium cluster forms temperature dependent equilibria that include even the monomeric cation [In(dmpe)]+. This system is the first report of one and the same ligand inducing formation of isoelectronic and isostructural gallium/indium cluster cations. The system allows to study systematically analogies and differences with thermodynamic considerations and bonding analyses, but also to outline perspectives for bond activation using cationic, subvalent group 13 clusters. 相似文献
43.
44.
Ulrich Englich Ingo Prass Karin Ruhlandt-Senge Thorsten Schollmeier Frank Uhlig 《Monatshefte für Chemie / Chemical Monthly》2002,133(7):931-943
Summary. Hydrido substituted stannasilanes of the type or (Z = H, Me, Ph; R, R′ = alkyl, Ph) are accessible by reaction of either alkali metal stannides (MSn(Z)R
2; M = Li, Na) with halogen substituted silanes (; X = F, Cl) or chlorostannanes (R
2SnCl2, Ph3SnCl) and fluorosilanes in the presence of magnesium. Stannasilanes with halogen substituents at the silicon as well as the tin atom are formed by
treatment of the hydrido substituted stannasilanes with CHCl3 or CCl4. The hydrido substituted stannasilanes decompose in contact with air to distannanes and siloxanes or to the linear (
t
Bu2Sn(–O–
t
Bu2Si–OH)2) and cyclic ((–
t
Bu2Sn–O–
i
Pr2Si–O–)2) stannasiloxanes.
Received November 29, 2001. Accepted (revised) January 16, 2002 相似文献
45.
Jan Ingo Flege Jan Höcker Jerzy T. Sadowski Sanjaya D. Senanayake Jens Falta 《Surface and interface analysis : SIA》2019,51(1):110-114
The early stages of ceria growth on Rh(111) at high temperature have been investigated by low-energy electron microscopy and photoemission electron microscopy. Ceria was deposited by reactive Ce deposition at substrate temperatures between 700°C and 900°C in an oxygen ambient of 5 × 10−7 Torr. At 700°C, we observe a high nucleation density of 100-nm-sized islands. With elevated temperature, the average island size increases, and the nucleation density decreases. Triangularly shaped islands nucleate preferentially at step edges, with seemingly abrupt interfaces between Ce and Rh. At 900°C, the island edges are still straight, but during growth the islands lose their triangular form. Instead, growth along the substrate step edges becomes favorable, leading to a maze-like morphology. Atomic force microscopy reveals islands of 0.3 to 0.6-nm height, consistent with ceria islands formed by one or two trilayers (O―Ce―O) of ceria. Moreover, the second layer of the islands is also triangularly shaped, with lateral dimensions of 50 nm and similar step heights. IV-LEEM analysis leads to the conclusion that the rhodium surface is covered by a layer of reduced cerium oxide, which is partially overgrown by smaller islands of CeO2. 相似文献
46.
Roland Wilberger Holger Piotrowski Marcus Warchhold Ingo‐Peter Lorenz 《无机化学与普通化学杂志》2003,629(14):2485-2492
Novel Neutral and Cationic Mono‐Aziridine Complexes of the Type [CpMn(CO)2Az], [CpCr(NO)2Az]+, and [(Ph3P)(CO)4ReAz]+ via CO‐, Hydride‐, and Chloride‐Elimination Reactions The monoaziridine complexes 1 — 5 are obtained by three differently induced substitution reactions. The photolytically induced CO substitution reaction of [CpMn(CO)3] with 2, 2‐dimethylaziridine leads to the neutral N‐coordinate aziridine complex [Cp(CO)2Mn{$\overline{N(H)CMe2C}$ H2}] ( 1 ). The protonation of [(Ph3P)(CO)4ReH] with CF3SO3H and consecutive treatment with 2, 2‐dimethylaziridine or 2‐ethylaziridine gives the salt‐like aziridine complexes [(Ph3P)(CO)4Re{$\overline{N(H)CMe2C}$ H2}](CF3SO3) ( 2 ) or [(Ph3P)(CO)4Re{ H2}](CF3SO3) ( 3 ) by hydride elimination reactions. The like‐wise salt‐like complexes [Cp(NO)2Cr{$\overline{N(H)CMe2C}$ H2}](BF4) ( 4 ) and [Cp(NO)2Cr{ H2}](CF3SO3) ( 5 ) are synthesized from [CpCr(NO)2Cl] by chloride elimination with AgX (X = BF4, CF3SO3) in the presence of 2, 2‐dimethylaziridine or 2‐ethylaziridine, respectively. As a result of X‐ray structure analyses, the metal atoms are trigonal pyramidally ( 1, 4, 5 ) or octahedrally ( 2, 3 , cis‐position) configurated; the intact three‐membered rings coordinate through the distorted tetrahedrally configurated N atoms. All compounds 1‐5 are stable with respect to the directed thermal alkene elimination to give the corresponding nitrene complexes; the IR, 1H‐ and 13C{1H}‐NMR, and MS spectra are reported and discussed. 相似文献
47.
Engelbert Reusch Dr. Fabian Holzmeier Marius Gerlach Prof. Dr. Ingo Fischer Dr. Patrick Hemberger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(72):16652-16659
The reaction products of the picolyl radicals at high temperature were characterized by mass-selective threshold photoelectron spectroscopy in the gas phase. Aminomethylpyridines were pyrolyzed to initially produce picolyl radicals (m/z=92). At higher temperatures further thermal reaction products are generated in the pyrolysis reactor. All compounds were identified by mass-selected threshold photoelectron spectroscopy and several hitherto unexplored reactive molecules were characterized. The mechanism for several dissociation pathways was outlined in computations. The spectrum of m/z=91, resulting from hydrogen loss of picolyl, shows four isomers, two ethynyl pyrroles with adiabatic ionization energies (IEad) of 7.99 eV (2-ethynyl-1H-pyrrole) and 8.12 eV (3-ethynyl-1H-pyrrole), and two cyclopentadiene carbonitriles with IE′s of 9.14 eV (cyclopenta-1,3-diene-1-carbonitrile) and 9.25 eV (cyclopenta-1,4-diene-1-carbonitrile). A second consecutive hydrogen loss forms the cyanocyclopentadienyl radical with IE′s of 9.07 eV (T0) and 9.21 eV (S1). This compound dissociates further to acetylene and the cyanopropynyl radical (IE=9.35 eV). Furthermore, the cyclopentadienyl radical, penta-1,3-diyne, cyclopentadiene and propargyl were identified in the spectra. Computations indicate that dissociation of picolyl proceeds initially via a resonance-stabilized seven-membered ring. 相似文献
48.
Ingo Helmers Bowen Shen Kalathil K. Kartha Rodrigo Q. Albuquerque Myongsoo Lee Gustavo Fernndez 《Angewandte Chemie (International ed. in English)》2020,59(14):5675-5682
Pathway complexity has become an important topic in recent years due to its relevance in the optimization of molecular assembly processes, which typically require precise sample preparation protocols. Alternatively, competing aggregation pathways can be controlled by molecular design, which primarily rely on geometrical changes of the building blocks. However, understanding how to control pathway complexity by molecular design remains elusive and new approaches are needed. Herein, we exploit positional isomerism as a new molecular design strategy for pathway control in aqueous self‐assembly. We compare the self‐assembly of two carboxyl‐functionalized amphiphilic BODIPY dyes that solely differ in the relative position of functional groups. Placement of the carboxyl group at the 2‐position enables efficient pairwise H‐bonding interactions into a single thermodynamic species, whereas meso‐substitution induces pathway complexity due to competing hydrophobic and hydrogen bonding interactions. Our results show the importance of positional engineering for pathway control in aqueous self‐assembly. 相似文献
49.
Synthesis and characterization of four iridium(III)-octaethylporphyrins and a π-extended iridium(III)-benzoporphyrin are presented. Strong room-temperature phosphorescence was observed for all of the complexes with quantum yields of up to 30 %. Axial ligands were introduced to tune the photophysical properties and the solubility. Complexes bearing lipophilic ligands such as pyridine or N-(n-butyl)imidazole were incorporated into polystyrene to obtain optical oxygen sensors. Covalent coupling of the dye is possible by introduction of ligands with binding domains (1-imidazoleacetic acid). This enabled preparation of a water-soluble oxygen probe (by staining bovine serum albumin) and a trace oxygen sensor (by coupling to amino-modified silica gel). 相似文献
50.
The phase separation process in a critical mixture of polydimethylsiloxane and polyethylmethylsiloxane (PDMS/PEMS, a system with an upper critical solution temperature) was investigated by time-resolved light scattering during continuous quenches from the one-phase into the two-phase region. Continuous quenches were realized by cooling ramps with different cooling rates kappa. Phase separation kinetics is studied by means of the temporal evolution of the scattering vector qm and the intensity Im at the scattering peak. The curves qm(t) for different cooling rates can be shifted onto a single mastercurve. The curves Im(t) show similar behavior. As shift factors, a characteristic length Lc and a characteristic time tc are introduced. Both characteristic quantities depend on the cooling rate through power laws: Lc approximately kappa(-delta) and tc approximately kappa(-rho). Scaling behavior in isothermal critical demixing is well known. There the temporal evolutions of qm and Im for different quench depths DeltaT can be scaled with the correlation length xi and the interdiffusion coefficient D, both depending on DeltaT through critical power laws. We show in this paper that the cooling rate scaling in nonisothermal demixing is a consequence of the quench depth scaling in the isothermal case. The exponents delta and rho are related to the critical exponents nu and nu* of xi and D, respectively. The structure growth during nonisothermal demixing can be described with a semiempirical model based on the hydrodynamic coarsening mechanism well known in the isothermal case. In very late stages of nonisothermal phase separation a secondary scattering maximum appears. This is due to secondary demixing. We explain the onset of secondary demixing by a competition between interdiffusion and coarsening. 相似文献