Films of an α‐cyclodextrin/poly(ε‐caprolactone) inclusion complex have been successfully prepared and show high transparency and heat resistance in comparison to the pure polymer film. The physical properties, such as transparency, mechanical properties, and thermal stability, of the α‐CD‐PCL‐IC films are found to depend on the α‐cyclodextrin‐to‐polymer stoichiometry.
We propose a pressure‐based unified solver for gas‐liquid two‐phase flows where compressible and incompressible flows coexist. Unlike the original thermo–Cubic Interpolated Propagation Combined Unified Procedure (CIP‐CUP) method proposed by Himeno et al (Transactions of the Japan Society of Mechanical Engineers, Series B, 2003), we split the advection term of the governing equations into a conservation part and into the rest. The splitting of advection term has two advantages. One is the high degree of freedom in choosing discretization schemes such as central‐difference schemes, upwind schemes, and Total Variation Diminishing (TVD) schemes. The other is the ease of implementation on unstructured grids. The advantages enable the analyses of various flows such as turbulent and supersonic ones in actual complicated boundaries. Therefore, the solver is useful for practical analyses. The solver was validated on the following test cases: subsonic single‐phase flows, incompressible single‐phase turbulent flows, and incompressible gas‐liquid two‐phase flows. With unstructured grids, we obtained the equivalent results as the ones with structured grids. After the validations, subsonic jet impinging on a water pool was calculated and compared with experimental results. It was confirmed that the calculated results were consistent with the experimental ones. 相似文献
A cross‐coupling reaction between enol derivatives and silyl ketene acetals catalyzed by GaBr3 took place to give the corresponding α‐alkenyl esters. GaBr3 showed the most effective catalytic ability, whereas other metal salts such as BF3?OEt2, AlCl3, PdCl2, and lanthanide triflates were not effective. Various types of enol ethers and vinyl carboxylates as enol derivatives are amenable to this coupling. The scope of the reaction with silyl ketene acetals was also broad. We successfully observed an alkylgallium intermediate by using NMR spectroscopy, suggesting a mechanism involving anti‐carbogallation among GaBr3, an enol derivative, and a silyl ketene acetal, followed by syn‐β‐alkoxy elimination from the alkylgallium. Based on kinetic studies, the turnover‐limiting step of the reaction using a vinyl ether and a vinyl carboxylate involved syn‐β‐alkoxy elimination and anti‐carbogallation, respectively. Therefore, the leaving group had a significant effect on the progress of the reaction. Theoretical calculations analysis suggest that the moderate Lewis acidity of gallium would contribute to a flexible conformational change of the alkylgallium intermediate and to the cleavage of the carbon?oxygen bond in the β‐alkoxy elimination process, which is the turnover‐limiting step in the reaction between a vinyl ether and a silyl ketene acetal. 相似文献
The synthesis of organometallic complexes of modified 26π‐conjugated hexaphyrins with absorption and emission capabilities in the third near‐infrared region (NIR‐III) is described. Symmetry alteration of the frontier molecular orbitals (MOs) of bis‐PdII and bis‐PtII complexes of hexaphyrin via N‐confusion modification led to substantial metal dπ–pπ interactions. This MO mixing, in turn, resulted in a significantly narrower HOMO–LUMO energy gap. A remarkable long‐wavelength shift of the lowest S0→S1 absorption beyond 1700 nm was achieved with the bis‐PtII complex, t ‐Pt2‐3 . The emergence of photoacoustic (PA) signals maximized at 1700 nm makes t ‐Pt2‐3 potentially useful as a NIR‐III PA contrast agent. The rigid bis‐PdII complexes, t ‐Pd2‐3 and c ‐Pd2‐3 , are rare examples of NIR emitters beyond 1500 nm. The current study provides new insight into the design of stable, expanded porphyrinic dyes possessing NIR‐III‐emissive and photoacoustic‐response capabilities. 相似文献
Phthalic anhydride in THF was added to 3-lithiofuran 2 in THF to give 3,3-di-(3-furyl)-1,3-dihy-droisobenzofuran-1-one 4 . On the other hand, 2 in THF was added to phthalic anhydride in THF to give 2-(3-furanoyl)benzoic acid 3 by the inverse addition method. Further, the parent naphtho[2,3-b]furan-4,9-dione 1 was obtained from the reaction of 3 with two equimolar amounts of LDA. 相似文献
We present the result of our accurate measurements of the a- and b-axis resistivity (ρa and ρb), magnetoconductivity Δσ/σ, Hall coefficient RH, and the a-axis thermopower Sa in untwinned YBa2Cu3Oy single crystals in a wide range of doping (6.45≤y≤7.0). The systematics of our data reveals a number of novel 60-K-phase anomalies in the charge transport: (i) temperature dependences of ρa show anomalous overlap below ∼130 K for 6.65≤y≤6.80, (ii) Hall mobility μH shows an enhancement near y?6.65, which is reflected in an anomalous y dependence of σxy, (iii) with decreasing temperature RH shows a marked drop upon approaching Tc only in samples with 6.70≤y≤6.85, (iv) superconducting fluctuation magnetoconductivity is anomalously enhanced near y?6.7, and (v) Hc2 is anomalously reduced near y?6.70. We discuss that the fluctuating charge stripes might be responsible for these anomalies in the charge transport. 相似文献
Construction of a molecular system in which the magnetic lattice exhibits long‐range order is one of the fundamental goals in materials science. In this study, we demonstrate the artificial construction of a ferrimagnetic lattice by doping electrons into acceptor sites of a neutral donor/acceptor metal–organic framework (D/A‐MOF). This doping was achieved by the insertion of Li‐ions into the D/A‐MOF, which was used as the cathode of a Li‐ion battery cell. The neutral D/A‐MOF is a layered system composed of a carboxylate‐bridged paddlewheel‐type diruthenium(II,II) complex as the donor and a TCNQ derivative as the acceptor. The ground state of the neutral form was a magnetically disordered paramagnetic state. Upon discharge of the cell, spontaneous magnetization was induced; the transition temperature was variable. The stability of the magnetically ordered lattice depended on the equilibrium electric potential of the D/A‐MOF cathode, which reflected the electron‐filling level. 相似文献
The interaction between growth inhibition and chirality, especially of diastereomers, has an important modifying effect on cancer cell proliferation. Previously, we have reported on the design, synthesis, and chemical properties of a series of novel, double-stranded peptides, (y-AA-x-AA)(2)-(CH(2))(12), with -y-AA-x-AA- and -z-AA-y-AA-x-AA- sequences conjugated to the spacer. Here, we extend those results by showing that (D-, L-) and (L-, D-) diastereomers are more potent inhibitors of tyrosine phosphorylation than (L-, L-). Although the replacement of the L-Phe-L-Phe sequence with L-Tyr-L-Phe produces a less active inhibitor, the double-stranded peptide conjugated with L-Tyr-D-Phe is more active than that conjugated with L-Tyr-L-Phe. In addition, we show that SDS-PAGE gel profiles of tyrosine phosphorylation following treatment with bis(y-Tyr-x-Phe)-N,N-dodecane-1,12-diamine appear very similar to profiles of tyrosine phosphorylation following treatment with an analog of the tyrosine kinase inhibitor, erbstatin. Moreover, the level of autophosphorylation of the epidermal growth factor receptor kinase domain (EGFRKD) treated with bis(L-Tyr-D-Phe)-N,N-dodecane-1,12-diamine was lower than that seen following treatment with bis(L-Phe-D-Phe)-N,N-dodecane-1,12-diamine. These data provide new insights for the control of cancer cell proliferation through drug designs which replace the less active -L-Phe-L-Phe- (and -D-Phe-L-Phe-) with the more active -L-Tyr-L-Phe- (and -L-Tyr-D-Phe-) sequence. 相似文献
The synthesis of the key intermediate (4) in the proposed route to D8646-2-6 is described. The aldol reaction of the carbohydrate-containing pyrone 7 with the aldehyde 6 was accomplished by using LiHMDS and Sc(OTf)3 or Sn(OTf)2. The stepwise dehydration reaction of the aldol adduct 14, followed by Stille coupling with vinyl stannane 5 which contained phosphonate gave the desired 4. 相似文献