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1.
Samuel Clark Ligon Konstanze Seidler Christian Gorsche Markus Griesser Norbert Moszner Robert Liska 《Journal of polymer science. Part A, Polymer chemistry》2016,54(3):394-406
The rapid and uncontrolled nature of network formation from di(meth)acrylate monomers produces high shrinkage stress and results in polymers with oftentimes brittle mechanical properties. Methods for regulating polymerization and network formation are sought. One option is the use of addition–fragmentation chain transfer (AFCT) agents, which are well known to control molecular weight and molecular weight distribution of monofunctional (meth)acrylates. A series of novel and previously described AFCT reagents were synthesized and screened with laser flash photolysis to determine reactivity. Well‐performing AFCT reagents were then tested in polymerizations with monofunctional and difunctional methacrylates. With monofunctional monomers, the molecular weight and polydispersity of the resultant linear polymers tend to decrease with the addition of AFCT agent. In copolymerization with dimethacrylate monomers, the AFCT agents were found to substantially lower and sharpen the glass transition. Sharpness of the glass transition is here indicative of a more regular and homogenous network. After coupling of the instruments, photorheology was performed simultaneously with real‐time IR to show an increase in monomer conversion at the time of gelation, which appears to have a positive effect on reducing shrinkage stress. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 394–406 相似文献
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3.
In a seminal 1994 paper Lusztig (1994) [26], Lusztig extended the theory of total positivity by introducing the totally non-negative part (G/P)?0 of an arbitrary (generalized, partial) flag variety G/P. He referred to this space as a “remarkable polyhedral subspace”, and conjectured a decomposition into cells, which was subsequently proven by the first author Rietsch (1998) [33]. In Williams (2007) [40] the second author made the concrete conjecture that this cell decomposed space is the next best thing to a polyhedron, by conjecturing it to be a regular CW complex that is homeomorphic to a closed ball. In this article we use discrete Morse theory to prove this conjecture up to homotopy-equivalence. Explicitly, we prove that the boundaries of the cells are homotopic to spheres, and the closures of cells are contractible. The latter part generalizes a result of Lusztig's (1998) [28], that (G/P)?0 - the closure of the top-dimensional cell - is contractible. Concerning our result on the boundaries of cells, even the special case that the boundary of the top-dimensional cell (G/P)>0 is homotopic to a sphere, is new for all G/P other than projective space. 相似文献
4.
Dr. P. Seidler 《Analytical and bioanalytical chemistry》1883,22(1):529-530
5.
Hermann Seidler 《Fresenius' Journal of Analytical Chemistry》1877,16(1):198-199
Ohne Zusammenfassung 相似文献
6.
Chondroitin/dermatan sulfate (CS/DS) chain of decorin (DCN) from human skin fibroblasts (HSk) was released by reductive β-elimination reaction and digested with chondroitin AC I lyase. Enzymatic hydrolysis mixture of CS/DS chains was separated by size-exclusion chromatography (SEC). Collected octasaccharide fraction was subjected to fully automated chip-based nanoelectrospray (nanoESI) quadrupole time-of-flight (QTOF) MS and tandem MS (MS/MS). MS of human skin fibroblasts DCN CS/DS displayed a high complexity due to the large variety of glycoforms, which under chip-nanoESI MS readily ionized to form multiply charged ions. Except for the regularly tetrasulfated octasaccharide, the investigated fraction contained four additional octasaccharides of atypical sulfation status. Two new oversulfated glycoforms and two undersulfated species were identified. Remarkably, the series of decasaccharides discovered in the same SEC pool was found to encompass a trisulfated and a novel hexasulfated [4,5-Δ-GlcAGalNAc(IdoAGalNAc)?] species. MS/MS by collision-induced dissociation (CID) on the [M-4H]? ion corresponding to the previously not reported [4,5-Δ-GlcAGalNAc(IdoAGalNAc)?](5S) corroborated for a novel motif in which three N-acetylgalactosamine (GalNAc) moieties are monosulfated, 4,5-Δ-GlcA and the first IdoA from the non-reducing end bear one sulfate group each, while the second N-acetylgalactosamine from the reducing end is unsulfated. 相似文献
7.
By14C-labeling it is shown that the ring contraction reaction of 1,4-benzothiazin-2,3-4H-dione (1), leading via benzthiazol-2-carbonic acid (2) finally to benzthiazole (3), proceeds via hydrolytic opening of the thiolactone-bond in1, irrespectively of H+ or OH– catalysis. 相似文献
8.
Thomas Koch Franz R. Kogler Ulrich Schubert Sabine Seidler 《Monatshefte für Chemie / Chemical Monthly》2007,19(2):293-299
The mechanical properties of hybrid materials consisting of polystyrene (PS), which was cross-linked with different proportions of the multifunctional cluster Zr6O4(OH)4(methacrylate)12 (Zr6) were investigated. With the help of (micro)indentation and scratch testing, the influence of the Zr6 clusters on mechanical properties, such as hardness, stiffness, creep, craze initiation, and scratch resistance was shown.
There was only a slight increase in hardness and in indentation modulus with higher cluster loadings. While this observation
was in agreement with the compression behaviour of the materials, the tensile properties showed a much stronger dependence
on the Zr6 content. With increasing cluster loading, an increase of craze initiation stress, as determined by ball indentation experiments,
was found. Performing scratch testing with constant load, a reduction of pile-up and a stronger recovery were observed for
the hybrid materials compared to the neat PS. Scratch tests with a constant increase of load showed an increase of the critical load for crack opening during scratching. 相似文献
9.
Vinyl Sulfonate Esters: Efficient Chain Transfer Agents for the 3D Printing of Tough Photopolymers without Retardation 下载免费PDF全文
Dr. Konstanze Seidler Dr. Markus Griesser Markus Kury Dr. Reghunathan Harikrishna Dr. Peter Dorfinger Dr. Thomas Koch Anastasiya Svirkova Prof. Martina Marchetti‐Deschmann Prof. Juergen Stampfl Prof. Norbert Moszner Dr. Christian Gorsche Prof. Robert Liska 《Angewandte Chemie (International ed. in English)》2018,57(29):9165-9169
The formation of networks through light‐initiated radical polymerization allows little freedom for tailored network design. The resulting inhomogeneous network architectures and brittle material behavior of such glassy‐type networks limit the commercial application of photopolymers in 3D printing, biomedicine, and microelectronics. An ester‐activated vinyl sulfonate ester (EVS) is presented for the rapid formation of tailored methacrylate‐based networks. The chain transfer step induced by EVS reduces the kinetic chain length of the photopolymer, thus shifting the gel point to higher conversion, which results in reduced shrinkage stress and higher overall conversion. The resulting, more homogeneous network is responsible for the high toughness of the material. The unique property of EVS to promote nearly retardation‐free polymerization can be attributed to the fact that after the transfer step no polymerizable double bond is formed, as is usually seen in classical chain transfer agents. Laser flash photolysis, theoretical calculations, and photoreactor studies were used to elucidate the fast chain transfer reaction and exceptional regulating ability of EVS. Final photopolymer networks exhibit improved mechanical performance making EVS an outstanding candidate for the 3D printing of tough photopolymers. 相似文献
10.
The experimental technique of a new type of polarization measurement especially for use with low-energy polarized targets is described. It is possible to derive the nuclear polarization as well as the nuclear spin-lattice relaxation time from measurements of the internal field. 相似文献