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141.
The Synthesis of B2(SIDip)2 and its Reactivity Between the Diboracumulenic and Diborynic Extremes 下载免费PDF全文
Julian Bhnke Holger Braunschweig Theresa Dellermann William C. Ewing Kai Hammond J. Oscar C. Jimenez‐Halla Thomas Kramer Jan Mies 《Angewandte Chemie (International ed. in English)》2015,54(46):13801-13805
A new compound with the formula L‐B2‐L wherein the stabilizing ligand (L) is 1,3‐bis[diisopropylphenyl]‐4,5‐dihydroimidazol‐2‐ylidene (SIDip) has been synthesized, isolated, and characterized. The π‐acidity of the SIDip ligand, intermediate between the relatively non‐acidic IDip (1,3‐bis[diisopropylphenyl]imidazol‐2‐ylidene) ligand and the much more highly acidic CAAC (1‐[2,6‐diisopropylphenyl]‐3,3,5,5‐tetramethylpyrrolidin‐2‐ylidene) ligand, gives rise to a compound with spectroscopic, electrochemical, and structural properties between those of L‐B2‐L compounds stabilized by CAAC and IDip. Reactions of all three L‐B2‐L compounds with CO demonstrate the differences caused by their respective ligands, as the π‐acidities of the CAAC and SIDip carbenes enabled the isolation of bis(boraketene) compounds (L(OC)B‐B(CO)L), which could not be isolated from reactions with B2(IDip)2. However, only B2(IDip)2 and B2(SIDip)2 could be converted into bicyclic bis(boralactone) compounds. 相似文献
142.
Prof. Dr. Holger Braunschweig Charlotte Brückner Dr. Mehmet Ali Celik Dr. Klaus Dück Dr. Florian Hupp Dr. Thomas Kramer Johannes Krebs Dr. Ivo Krummenacher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):11056-11064
Taking advantage of an improved synthesis of [Ti(η6‐C6H6)2], we report here the first examples of ansa‐bridged bis(benzene) titanium complexes. Deprotonation of [Ti(η6‐C6H6)2] with nBuLi in the presence of N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (pmdta) leads to the corresponding 1,1′‐dilithio salt [Ti(η6‐C6H5Li)2] ? pmdta that enables the preparation of the first one‐ and two‐atom‐bridged complexes by simple salt metathesis. The ansa complexes were fully characterized (NMR spectroscopy, UV/Vis spectroscopy, elemental analysis, and X‐ray crystallography) and further studied electrochemically and computationally. Moreover, [Ti(η6‐C6H6)2] is found to react with the Lewis base 1,3‐dimethylimidazole‐2‐ylidene (IMe) to give the bent sandwich complex [Ti(η6‐C6H6)2(IMe)]. 相似文献
143.
Ansa‐Complexes of [Mn(η5‐C5H5)(η6‐C6H6)]: Preparation,Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3) 下载免费PDF全文
Prof. Dr. Holger Braunschweig Dr. Alexander Damme Dr. Klaus Dück Dr. Marco Fuß Dr. Christian Hörl Dr. Thomas Kramer Dr. Ivo Krummenacher Dr. Thomas Kupfer Valerie Paprocki Christoph Schneider 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):14797-14803
We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa‐bridging elements. Their preparation was achieved by salt‐elimination reactions of the dilithiated precursor [Mn(η5‐C5H4Li)(η6‐C6H5Li)]?pmdta (pmdta=N,N,N′,N′,N′′‐pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single‐atom‐bridged derivatives, [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] and [Mn(η5‐C5H4)(η6‐C6H5)SiPh2], could also be determined by X‐ray structural analysis. We investigated for the first time the reactivity of these ansa‐cyclopentadienyl–benzene manganese compounds. The reaction of the distannyl‐bridged complex [Mn(η5‐C5H4)(η6‐C6H5)Sn2tBu4] with elemental sulfur was shown to proceed through the expected oxidative addition of the Sn?Sn bond to give a triatomic ansa‐bridge. The investigation of the ring‐opening polymerization (ROP) capability of [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] with [Pt(PEt3)3] showed that an unexpected, unselective insertion into the Cipso?Sn bonds of [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] had occurred. 相似文献
144.
145.
Zofia M. Wosinska Faye L. Stump Rajeev Ranjan Edward D. Lorance GeNita N. Finley Priya P. Patel Muzamil A. Khawaja Katie L. Odom Wolfgang H. Kramer Ian R. Gould 《Photochemistry and photobiology》2014,90(2):313-328
Irreversible photooxidation based on N–O bond fragmentation is demonstrated for N‐methoxyheterocycles in both the singlet and triplet excited state manifolds. The energetic requirements for bond fragmentation are studied in detail. Bond fragmentation in the excited singlet manifold is possible for ππ* singlet states with energies significantly larger than the N–O bond dissociation energy of ca 55 kcal mol?1. For the nπ* triplet states, N–O bond fragmentation does not occur in the excited state for orbital overlap and energetic reasons. Irreversible photooxidation occurs in the singlet states by bond fragmentation followed by electron transfer. Irreversible photooxidation occurs in the triplet states via bimolecular electron transfer to the donor followed by bond fragmentation. Using these two sensitization schemes, donors can be irreversibly oxidized with oxidation potentials ranging from ca 1.6–2.2 V vs SCE. The corresponding N‐ethylheterocycles are characterized as conventional reversible photooxidants in their triplet states. The utility of these sensitizers is demonstrated by irreversibly generating the guanosine radical cation in buffered aqueous solution. 相似文献
146.
Baki B. Sadi Chunsheng Li Gary H. Kramer Cassandra L. Johnson Queenie Ko Edward P. C. Lai 《Journal of Radioanalytical and Nuclear Chemistry》2011,290(2):415-425
A new radioanalytical method was developed for rapid determination of 226Ra in drinking water samples. The method is based on extraction and preconcentration of 226Ra from a water sample to an organic solvent using a dispersive liquid-liquid microextraction (DLLME) technique followed by
radiometric measurement using liquid scintillation counting. In DLLME for 226Ra, a mixture of an organic extractant (toluene doped with dibenzo-21-crown-7 and 2-theonyltrifluoroacetone) and a disperser
solvent (acetonitrile) is rapidly injected into the water sample resulting in the formation of an emulsion. Within the emulsion,
226Ra reacts with dibenzo-21-crown-7 and 2-theonyltrifluoroacetone and partitions into the fine droplets of toluene. The water/toluene
phases were separated by addition of acetonitrile as a de-emulsifier solvent. The toluene phase containing 226Ra was then measured by liquid scintillation counting. Several parameters were studied to optimize the extraction efficiency
of 226Ra, including water immiscible organic solvent, disperser and de-emulsifier solvent type and their volume, chelating ligands
for 226Ra and their concentrations, inorganic salt additive and its concentration, and equilibrium pH. With the optimized DLLME conditions,
the accuracy (expressed as relative bias, B
r
) and method repeatability (expressed as relative precision, S
B
) were determined by spiking 226Ra at the maximum acceptable concentration level (0.5 Bq L−1) according to the Guidelines for Canadian Drinking Water Quality. Accuracy and repeatability were found to be less than −5%
(B
r
) and less than 6% (S
B
), respectively, for both tap water and bottled natural spring water samples. The minimum detectable activity and sample turnaround
time for determination of 226Ra was 33 mBq L−1 and less than 3 h, respectively. The DLLME technique is selective for extraction of 226Ra from its decay progenies. 相似文献
147.
The synthesis and characterization of water-soluble dispersions of Ag nanoparticles by the reduction of AgNO(3) using tryptophan under alkaline synthesis conditions are reported. The Ag nanoparticle formation was very slow at low concentration and rapid at extremes. For surface modification and redox reactions, manipulating the interparticles interaction controlled the size of Ag nanoparticles aggregates. Our results suggest that the replacement of the BH(4)(-) ions adsorbed on the nanoparticle surface by tryptophan destabilizes the particles and further caused aggregation. A mechanism is proposed for the formation of silver nanoparticles by tryptophan. The experimental results are supported by theoretical calculations. The Ag nanoparticles were characterized by UV-vis absorption, dynamic light scattering and transmission electron microscopy techniques. 相似文献
148.
149.
Altun M Kramer HB Willems LI McDermott JL Leach CA Goldenberg SJ Kumar KG Konietzny R Fischer R Kogan E Mackeen MM McGouran J Khoronenkova SV Parsons JL Dianov GL Nicholson B Kessler BM 《Chemistry & biology》2011,18(11):1401-1412
Converting lead compounds into drug candidates is a crucial step in drug development, requiring early assessment of potency, selectivity, and off-target effects. We have utilized activity-based chemical proteomics to determine the potency and selectivity of deubiquitylating enzyme (DUB) inhibitors in cell culture models. Importantly, we characterized the small molecule PR-619 as a broad-range DUB inhibitor, and P22077 as a USP7 inhibitor with potential for further development as a chemotherapeutic agent in cancer therapy. A striking accumulation of polyubiquitylated proteins was observed after both selective and general inhibition of cellular DUB activity without direct impairment of proteasomal proteolysis. The repertoire of ubiquitylated substrates was analyzed by tandem mass spectrometry, identifying distinct subsets for general or specific inhibition of DUBs. This enabled identification of previously unknown functional links between USP7 and enzymes involved in DNA repair. 相似文献
150.
A metal-free acetate shift of 3-acetoxy ynamides to access α-iodo, bromo, and chloro acrylamides/acrylimides under very mild conditions is demonstrated. The inherent alkyne activation of ynamides is sufficient to ensure the α-halo acrylamides/acrylimides in high yields without the addition of a catalyst. In all cases high Z-stereoselectivity is observed. 相似文献