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71.
We show that measurements of a Neumann-to-Dirichlet map, with either inputs or outputs restricted to part of the boundary, can determine an electric potential on that domain. Given a convexity condition on the domain, either the set on which measurements are taken, or the set on which input functions are supported, can be made to be arbitrarily small. The result is analogous to the result by Kenig, Sjöstrand, and Uhlmann for the Dirichlet-to-Neumann map. The main new ingredient in the proof is an improved Carleman estimate for the Schrödinger operator with appropriate boundary conditions. This is proved by Fourier analysis of a conjugated operator along the boundary of the domain.  相似文献   
72.
An electrochemical sensor based on the conducting polymer composite with a palladium complex (Pd(C2H4N2S2)2) was developed for the detection of serotonin and dopamine simultaneously in the breast cancer cell and human plasma samples. The proposed sensor was fabricated using the Pd(C2H4N2S2)2 complex‐anchored poly2,2 : 5,2‐terthiophene‐3‐(p‐benzoic acid) (pTBA) layer on the AuNPs decorated reduced graphene oxide (AuNPs@rGO) substrate, which revealed the enhanced anodic current of the target species. The sensor probe was characterized by electrochemical and surface analysis methods. The experimental parameters affecting the sensor performance were optimized, in terms of AuNPs@rGO concentration, the number of electropolymerization cycle for pTBA, immobilization time of Pd(C2H4N2S2)2, and pH. The dynamic ranges for serotonin and dopamine were obtained from 0.02 to 200 μM, and from 0.1 to 200 μM with the detection limit of 2.5, and 24.0 nM, respectively. The reliability of proposed sensor was evaluated using cancer cell lines for the clinical applications.  相似文献   
73.
The deuteriodifluoromethyl group (CF2D) represents a challenging functional group due to difficult deuterium incorporation and unavailability of precursor reagents. Herein, we report the use of chlorodifluoromethane (ClCF2H) gas in the continuous flow deuteriodifluoromethylation and gem‐difluoroalkenylation of aldehydes. Mechanistic studies revealed that the difluorinated oxaphosphetane (OPA) intermediate can proceed via alkaline hydrolysis in the presence of D2O to provide α‐deuteriodifluoromethylated benzyl alcohols or undergo a retro [2+2] cycloaddition under thermal conditions to provide the gem‐difluoroalkenylated product.  相似文献   
74.
2,4-Hexadiyn-1,6-diol (HDO) was polymerized on glass and silicon plates by chemical vapor deposition without transition metal catalysis to form homogeneous thin films. Structural properties of the films were investigated by FT-IR, UV-visible, Raman, x-ray diffraction, and XPS spectroscopic analyses. The structure of CVD-polymerized HDO (CVD-PHDO) films was different from that of metathesis polymerized HDO (metathesis-PHDO), showing a polyacene-based structure but no polyene structure with acetylenic side groups. © 1996 John Wiley & Sons, Inc.  相似文献   
75.
3,4,5-Trichloropyridazin-6-one, 3,4,5,6-tetrachloropyridzine and 4,5-dichloro-3-(N,N-dimethylamino)-pyridazin-6-one were synthesized from 4,5-dichloro-3-nitropyridazin-6-one and dimethylchloromethylene-ammonium chloride selectively.  相似文献   
76.
The use of hydrazine-catalyzed ring-closing carbonyl–olefin metathesis (RCCOM) to synthesize polycyclic heteroaromatic (PHA) compounds is described. In particular, substrates bearing Lewis basic functionalities such as pyridine rings and amines, which strongly inhibit acid catalyzed RCCOM reactions, are shown to be compatible with this reaction. Using 5 mol% catalyst loadings, a variety of PHA structures can be synthesized from biaryl alkenyl aldehydes, which themselves are readily prepared by cross-coupling.

Hydrazine catalysis enables the ring-closing carbonyl–olefin metathesis (RCCOM) to form polycyclic heteroaromatics, especially those with basic functionality.

Polycyclic heteroaromatic (PHA) structures comprise the core framework of many valuable compounds with a diverse range of applications (Fig. 1A).1 For example, polycyclic azines (e.g. quinolines) are embedded in many alkaloid natural products, including diplamine2 and eupolauramine3 to name just a few. These types of structures are also of interest for their biological activity, such as with the inhibitor of the Src-SH3 protein–protein interaction shown in Fig. 1A.4 Many nitrogenous PHAs are also useful as ligands for transition metal catalysis, as exemplified by the widely used ligand 1,10-phenanthroline.5 Meanwhile, chalcogenoarenes6 such as dinaphthofuran7 and benzodithiophene8 have attracted high interest for both their medicinal properties9 and especially for their potential use as organic light-emitting diodes (OLEDs), organic photovoltaics (OPVs), and organic field-effect transistors (OFETs).10 These and numerous other examples have inspired the development of a wide variety of strategies to construct PHAs.1,11–14 Although these approaches are as varied as the structures they target, the wide range of molecular configurations within PHA chemical space and the challenges inherent in exerting control over heteroatom position and global structure make novel syntheses of these structures a topic of continuing interest.Open in a separate windowFig. 1(A) Examples of PHAs. (B) RCCOM strategy for PHA synthesis. (C) Lewis base inhibition for Lewis acid vs. hydrazine catalyzed RCCOM. (D) Hydrazine-catalyzed RCCOM for PHA synthesis.One potentially advantageous strategy for PHA synthesis is the use of ring-closing carbonyl–olefin metathesis15 (RCCOM) to forge one of the PHA rings, starting from a suitably disposed alkenyl aldehyde precursor 2 that can be easily assembled by cross-coupling (Fig. 1B). In related work, the application of RCCOM to form polycyclic aromatic hydrocarbons (PAHs) was reported by Schindler in 2017.16 In this case, 5 mol% FeCl3 catalyzed the metathesis of substrates to form phenanthrenes and related compounds in high yields at room temperature. This method was highly attractive for its efficiency, its use of an earth-abundant metal catalyst, and the production of benign acetone as the only by-product. Nevertheless, one obvious drawback to the use of Lewis acid activation is that the presence of any functionality that is significantly more Lewis basic than the carbonyl group can be expected to strongly inhibit these reactions (Fig. 1C). Such a limitation thus renders this method incompatible with a wide swath of complex molecules, especially PHAs comprised of azine rings. This logic argues for a mechanistically orthogonal RCCOM approach that allows for the synthesis of PHA products with a broader range of ring systems and functional groups.We have developed an alternative approach to catalytic carbonyl–olefin metathesis that makes use of the condensation of 1,2-dialkylhydrazines 5 with aldehydes to form hydrazonium ions 6 as the key catalyst–substrate association step.17–19 This interaction has a much broader chemoorthogonality profile than Lewis acid–base interactions and should thus be much less prone to substrate inhibition than acid-catalyzed approaches. In this Communication, we demonstrate that hydrazine-catalyzed RCCOM enables the rapid assembly of PHAs bearing basic functionality (Fig. 1D).For our optimization studies, we chose biaryl pyridine aldehyde 7 as the substrate (20 salt 11 was also productive (entry 2), albeit somewhat less so. Notably, iron(iii) chloride generated no conversion at either ambient or elevated temperatures (entries 3 and 4). Trifluoroacetic acid (TFA) was similarly ineffective (entry 5). Meanwhile, a screen of various solvents revealed that, while the transformation could occur in a range of media (entries 6–9), THF was optimal. Finally, by raising the temperature to 90 °C (entry 10) or 100 °C (entry 11), up to 96% NMR yield (85% isolated yield) of adduct 8 could be obtained in the same time period.Optimization studiesa
EntryCatalystSolventTemp. (°C)8 yield (%)
110THF8067
211THF8053
3FeCl3DCErt0
4FeCl3DCE800
5TFATHF800b
610i-PrOH8031
710CH3CN8028
810EtOAc8026
910Toluene8024
1010THF9087
1110THF10096c
Open in a separate windowaConditions: substrate 8 (0.2 mmol) and 5 mol% catalyst in 0.4 mL of solvent (0.5 M) in a 5 mL sealed tube were heated to the temperature indicated for 15 h. Yields were determined by 1H NMR using CH2Br2 as an internal standard.b2 equiv. of TFA was used.c85% isolated yield.Using the optimized conditions, we explored the synthesis of various PHAs (Fig. 2). In addition to benzo[h]isoquinoline (8), products 12 and 13 with fluorine substitution at various positions could be generated in good yields. Similarly, benzoisoquinolines 14 and 15 bearing electron-donating methoxy groups and the dioxole-fused product 16 were also accessed efficiently. Furthermore, a phenolic ether product 17 with a potentially acid-labile N-Boc group was generated in modest yield. We found that an even more electron-donating dimethylamino group was also compatible with this chemistry, allowing for the production of 18 in 68% yield. On the other hand, adduct 19 bearing a strongly electron-withdrawing trifluoromethyl group was isolated in only modest yield. The naphtho-fused isoquinoline 20 could be generated as well; however, 20 mol% catalyst was required to realize a 35% yield. The thiophene-fused product 21 was furnished in much better yield, also with the higher catalyst loading. Although not a heterocyclic system, we found that the reaction to form phenanthrene (22) was well-behaved, providing that compound in 83% yield. In addition, an amino-substituted phenanthrene 23 was also formed in good yield. Other thiophene-containing PAHs such as 24–26 were produced efficiently. On the other hand, adduct 27 was generated only in low yield. Naphthofuran (28), which is known to have antitumor and oestrogenic properties,21 was synthesized in good yield. Finally, pharmaceutically important structures such as benzocarbazole2229 and naphthoimidazole2330 could be accessed in moderate yields with increased catalyst loading.Open in a separate windowFig. 2Substrate scope studies for hydrazine 1-catalyzed RCCOM synthesis of polycyclic heteroaromatics. a Conditions: substrate and catalyst 1·(TFA)2 (5 mol%) in THF (0.5 M) were heated to 100 °C in a 5 mL sealed tube for 15 h. Yields were determined on purified products. b 20 mol% catalyst.We also examined the scope of the olefin substitution pattern (
EntrySubstrateTime (h)Yield (%)
1 1596
2 485
3b 4827
4 4854
5 4864
Open in a separate windowaConditions: 5 mol% 10 in THF (0.5 M) in a 5 mL sealed tube were heated to the temperature indicated for 15–48 h. Conversions and yields were determined by 1H NMR using CH2Br2 as an internal standard.bMixture of E/Z (2 : 1) isomers.The vinyl substrate 31 led to very little desired product (entry 2), while the propenyl substrate 32 (2 : 1 mixture of E and Z isomers) was somewhat improved but still low-yielding (entry 3). Finally, styrenyl substrates 33 and 34 (entries 4 and 5) led to improved yields relative to 31 and 32, with the cis isomer 34 being slightly more efficient (entry 5).In order to better understand the facile nature of this RCCOM reaction, we conducted DFT calculations for each step of the proposed reaction pathway (Fig. 3A). Condensation of the substrate 7 with [2.2.1]-hydrazinium 10 to afford the hydrazonium Z-35 was found to be exergonic by −13 kcal mol−1. Isomerization of Z-35 to E-35 comes at a cost of ∼3 kcal mol−1, but the total activation energy for cycloaddition (cf.36), taking into account this isomerization, was still relatively modest at only +21.0 kcal mol−1 with an overall exergonicity of −11.1 kcal mol−1. The energetic change for proton transfer in the conversion of cycloadduct 37a to the cycloreversion precursor 37b was negligible (+1.2 kcal mol−1). Interestingly, including the proton migration step, the cumulative energy barrier for cycloreversion 38 was found to be only +21.7 kcal mol−1, nearly the same as for the cycloaddition. Undoubtedly, the formation of an aromatic ring greatly facilitates this step relative to other types of substrates. Unsurprisingly, the cycloreversion to produce benzoisoquinoline 8 along with hydrazonium 39 was calculated to be strongly exergonic. Finally, the hydrolysis of 39 to regenerate hydrazinium catalyst 10 (and acetone) required an energy input approximately equal to that gained from the condensation with the substrate to form 35.Open in a separate windowFig. 3(A) Computational study of hydrazine 10-catalyzed RCCOM of biaryl aldehyde 7. Calculations were performed at the PCM(THF)-M06-2X/6-311+G(d,p)//6-31G(d) level of theory.24,25 All energies are given in units of kcal mol−1. (B) 1H NMR spectroscopy of the RCCOM reaction of 7 catalyzed by 10 at 60 °C in THF-d8 with mesitylene as internal standard for 5 hours. (C) Plot of the data showing conversion vs. time. SM = starting material 7; CA = cycloadduct 37; Prd = product 8.Given the low activation energy barriers of both the cycloaddition and cycloreversion steps, we reasoned it should be possible for the reaction to proceed at a relatively low temperature. In fact, we observed 82% conversion of biaryl aldehyde 7 to cycloadduct 37 (72%) and benzoisoquinoline 8 (10%) at 40 °C over 6 hours. Attempts to isolate the cycloadduct 37 resulted in complete conversion to 8 during column chromatography. Meanwhile, at 60 °C over approximately 4 hours, 95% of the starting material 7, via the intermediate cycloadduct 37, was converted to benzoisoquinoline product 8 (Fig. 3B and C). The rate of consumption of the cycloadduct was consistent with first-order behavior, and upon fitting, revealed the rate constant for cycloreversion as kCR = 2.14 × 10−4 s−1, with a half-life of 54 minutes. These observations corroborate the computational results, in particular showing that the cycloreversion step is quite facile with these types of substrates compared to other hydrazine-catalyzed COM reactions we have investigated17 and that cycloaddition and cycloreversion have energetically similar activation energies.In conclusion, the development of catalytic carbonyl–olefin metathesis reactions has opened new possibilities for the rapid construction of complex molecules. The current work demonstrates this strategy as a means to rapidly access polycyclic heteroaromatics, which often require lengthy sequences that can be complicated by the presence of basic functionality. The ability of the hydrazine catalysis platform to accommodate such functional groups provides a novel approach to polycyclic heteroaromatic synthesis and greatly expands the landscape of structures accessible by RCCOM.  相似文献   
77.
Thermal Hysteresis Accompanying Incommensurate-Commensurate Phase Transition in Mixed Crystals (K1-xCsx)2ZnCl4     
H. Y. Ahn  S. Y. Jeong  M. S. Jang  W. S. Chung 《Crystal Research and Technology》1995,30(8):1147-1153
The mixed crystal (K1-xCsx)2ZnCl4 with x = 0, 0.001, 0.01, 0.1, and 0.2 with optical quality has been grown by the Czochralski method. Using the Atomic Absorption Spectroscopy (AAS) and Energy Dispersive Spectroscopy (EDS), we determined the amount of Cs ion included in the mixed crystal. By using of DTA and DSC, we observed the change of Tc and Ti. The thermal hysteresis in the dielectric constants show strong dependence on the thermal process and on the amount of impurity which are explained by the influence of the thermal process and impurity, respectively on the creation, annihilation, and growth of discommensuration (DC).  相似文献   
78.
Synthesis and characterization of new aromatic liquid crystalline polyesters having phenyl substituents     
Tae-Gyu Choi  Sung-Jae Chung  Seung-Moo Huh  Yong-Kuk Yun  Jung-Il Jin 《Macromolecular Symposia》1995,98(1):285-292
Two different series of new aromatic liquid crystalline (LC) polyesters were prepared from 3-phenyl-4, 4'-biphenyldicarboxylic acid (PBDA) and 1-phenyl-2, 6-naphthalenedicarboxylic acid (PNDA). PBDA and PNDA were polymerized with various aromatic diols such as hydroquinone, substituted hydroquinones, isomeric naphthalenediols and 4, 4'-biphenol, and the resulting polyesters were characterized by DSC, WAXD, and on a cross-polarizing microscope for the study of their thermal transition and crystallization properties, and mesophases formed therefrom.  相似文献   
79.
Cerium vanadate/carbon nanotube hybrid composite nanostructures as a high-performance anode material for lithium-ion batteries     
D.Narsimulu  Ashok Kumar Kakarla  Jae Su Yu 《Journal of Energy Chemistry》2021,(7):25-32
The pristine CeVO4 and CeVO4/CNT hybrid composite nanostructured samples were facilely synthesized using a simple silicone oil-bath method.From the X-ray diffra...  相似文献   
80.
Domain-Specific On-Device Object Detection Method     
Seongju Kang  Jaegi Hwang  Kwangsue Chung 《Entropy (Basel, Switzerland)》2022,24(1)
Object detection is a significant activity in computer vision, and various approaches have been proposed to detect varied objects using deep neural networks (DNNs). However, because DNNs are computation-intensive, it is difficult to apply them to resource-constrained devices. Here, we propose an on-device object detection method using domain-specific models. In the proposed method, we define object of interest (OOI) groups that contain objects with a high frequency of appearance in specific domains. Compared with the existing DNN model, the layers of the domain-specific models are shallower and narrower, reducing the number of trainable parameters; thus, speeding up the object detection. To ensure a lightweight network design, we combine various network structures to obtain the best-performing lightweight detection model. The experimental results reveal that the size of the proposed lightweight model is 21.7 MB, which is 91.35% and 36.98% smaller than those of YOLOv3-SPP and Tiny-YOLO, respectively. The f-measure achieved on the MS COCO 2017 dataset were 18.3%, 11.9% and 20.3% higher than those of YOLOv3-SPP, Tiny-YOLO and YOLO-Nano, respectively. The results demonstrated that the lightweight model achieved higher efficiency and better performance on non-GPU devices, such as mobile devices and embedded boards, than conventional models.  相似文献   
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