Polypropylene films of various isotacticities and crystallinities were stretched biaxially in one step in air at 140–152°C or polyaxially in poly(ethylene glycol) at 130–160°C, and the morphological changes were studied by electron microscopy (replica). In the initial stage of stretching, with vA = 1.4, the spherulites of one of the films used for the experiment were broken both from the centers and boundaries, and those of another film were broken mainly from the center. This difference in the deformation behavior seems to be characteristic of the film properties and independent of the method of stretching, although the factors involved are still unknown. On further stretching (vA = 22), well annealed spherulites were broken into many small blocklike fragments with unfolded fibrils running among them, particularly at the low stretching temperature (140°C), and fibrillation proceeded at the expense of the residual fragments. In the case of quenched or slightly crystallized material, the fragments were dendritic and divided into finer and finer fibrils on stretching. At elevated temperature, however, even for well annealed spherulites, the deformation behavior resembles that of the quenched material, and at a high degree of stretching the spherulites take on the fibrillar net structure in every case. In films containing a high amount of atactic fraction, radial, tangential, and boundary cracking occurred more easily, and broad fibrils were observed across the cracks. 相似文献
It was reported that the somatostatin analog TT-232, d-Phe-c(Cys-Tyr-d-Trp-Lys-Cys)-Thr-NH2, exhibited a highly potent antitumor activity in vitro and in vivo. Using pyrazinone analogs and aliphatic amino acids instead of the disulfide bond, we prepared novel type somatostatin analogs including the sequence essential for antitumor activities, Tyr-d-Trp-Lys. These analogs exhibited antiproliferative effect on A431 tumor cells. 相似文献
The dry pulp direct kneading method is an industrially viable, low-energy process for manufacturing cellulose nanofiber (CNF)-reinforced polymer composites, where the chemically modified pulps are nanofibrillated and uniformly dispersed in the polymer matrix during melt compounding. In the present study, cellulose fibers of various sizes ranging from surface-fibrillated pulps (20 μm in width) to fine CNFs (20 nm in width) were prepared from softwood bleached kraft pulps using a refiner and a high-pressure homogenizer. These cellulose fibers were modified with alkenyl succinic anhydride and dried. The dried fibers were used as a feed material for melt compounding in the dry pulp direct kneading method to fabricate CNF-reinforced high-density polyethylene (HDPE). When surface-fibrillated pulps were employed as a feed material, the pulps were nanofibrillated and dispersed uniformly in the HDPE matrix during melt compounding. The resulting composites had much better properties—i.e., much higher tensile modulus and strength values, and much lower coefficient of thermal expansion values—than the composites produced using pulps without pre-fibrillation. However, when CNFs were used as a feed material, they were shortened and agglomerated during melt compounding, and the properties of the composites consequently deteriorated. The study concludes that surface-fibrillated pulp, which can be produced cost-effectively using a refiner on an industrial scale, is more suitable as a feed material than CNFs for melt compounding in the dry pulp direct kneading method. This finding enables the elimination of a preliminary step in the preparation of CNFs from pulps, which is a time-consuming and energy-intensive process.
Electron-transfer reduction of molecular oxygen (O2) by the phenolate anion (1-) of a vitamin E model, 2,2,5,7,8-pentamethylchroman-6-ol (1H), occurred to produce superoxide anion, which could be directly detected by a low-temperature EPR measurement. The rate of electron transfer from 1- to O2 was relatively slow, since this process is energetically unfavourable. The one-electron oxidation potential of 1- determined by cyclic voltammetric measurements is sufficiently negative to reduce 2,2-bis(4-tert-octylphenyl)-1-picrylhydrazyl radical (DOPPH*) to the corresponding one-electron reduced anion, DOPPH-, suggesting that 1- can also act as an efficient radical scavenger. 相似文献
A series of optically active P‐chiral oligophosphines (S,R,R,S)‐ 2 , (S,R,S,S,R,S)‐ 3 , (S,R,S,R,R,S,R,S)‐ 4 , and (S,R,S,R,S,R,R,S,R,S,R,S)‐ 5 with four, six, eight, and 12 chiral phosphorus atoms, respectively, were successfully synthesized by a step‐by‐step oxidative‐coupling reaction from (S,S)‐ 1 . The corresponding optically inactive oligophosphines 1′ – 5′ were also prepared. Their properties were characterized by DSC, XRD, and optical‐rotation analyses. While optically active bisphosphine (S,S)‐ 1 and tetraphosphine (S,R,R,S)‐ 2 behaved as small molecules, octaphosphine (S,R,S,R,R,S,R,S)‐ 4 and dodecaphosphine (S,R,S,R,S,R,R,S,R,S,R,S)‐ 5 exhibited the features of a polymer. Furthermore, DSC and XRD analyses showed that hexaphosphine (S,R,S,S,R,S)‐ 3 is an intermediate between a small molecule and a polymer. Comparison of optically active oligophosphines 1 – 5 with the corresponding optically inactive oligophosphines 1′ – 5′ revealed that the optically active phosphines have higher crystallinity than the optically inactive counterparts. It is considered that the properties of oligophosphines depend on the enantiomeric purity as well as the oligomer chain length. 相似文献
The reaction promoted by Vilsmeier adduct derived from tosyl chloride (TsCl) with N,N-dimethylformamide (DMF) was successfully applied to the preparation of copolyesteramides of high molecular weights directly from aromatic dicarboxylic acids, diamines, and bisphenols. The polycondensation was significantly affected by the reaction of activated dicarboxylic acids with bisphenols and diamines. Addition of a mixture of bisphenols and diamines likely caused gelation of the reaction mixtures, resulting in insoluble polymers, especially with high mol % diamines. Stepweise addition of them, however, gave the homogeneous reaction mixtures and copolymers of better solubility. These phenomena were studied in terms of sequence length distribution of polyester units, which was estimated by thermal analyses of the random copolymers prepared under various conditions for the initial reaction with bisphenols. 相似文献
To achieve targeted distribution of anticancer drugs with sustained activity, ferromagnetic ethylcellulose microcapsules containing
an anticancer drug, mitomycin C (FM-MMC-mc), were prepared by a method based on phase separation principles. Two prototypes
of FM-MMC-mc were made: one with the drug as the core and zinc ferrite on its capsular surface (outer type); the other with
both the drug and zinc ferrite as the core (inner type). Both preparations provided a sustained-release property and a sensitive
response to conventional magnetic force, although certain differences in the release rate of drug, magnetic responsiveness,
and particle size were found between the two dosage forms. Animal studies showed that the magnetic microcapsules could be
magnetically controlled in the artery and urinary bladder. VX2 tumors in the rabbit hind limb and urinary bladder were successfully
treated with magnetic control of FM-MMC-mc. Pharmacokinetic study revealed that the targeting of the microcapsules markedly
enhanced the drug absorption into the surrounding tissues for a prolonged period of time. The results indicate the feasibility
and effectiveness of the magnetic microcapsules as a targeted drug delivery system. 相似文献
Easily prepared, chiral sulfideoxathiane ligands are described which give excellent enantioselectivity (up to 99% ee) in the Pd-catalyzed allylic alkylation of 1,3-diphenyl-2-propenyl acetate with a range of alkyl malonate nucleophiles. 相似文献
UVB irradiation is a well-known apoptosis induction factor. However, we have previously found that low doses of UVB irradiation inhibited apoptosis induced by both serum starvation and lack of extracellular matrix, involving a significant inhibition of caspase-3/7 activation. In this study, we report on the relationship between the UVB-induced anti-apoptotic effect and caspase-3/7 inhibition by reactive oxygen species (ROS). The UVB-induced antiapoptotic effect was partially prevented by an antioxidant agent, N-acetylcysteine. A ROS-generating agent, menadione and a pro-oxidant agent, H2O2 also showed an effect that was similar to the UVB-induced antiapoptotic effect, indicating that ROS contributed to the antiapoptotic effect. UVB irradiation significantly suppressed caspase-3/7 activation, which was caused by the inhibition of proteolysis and not by the inhibition of enzymatic activity itself. The prevention of proteolysis was also confirmed by both the following results: one is the inhibition of in vitro caspase-3/7 and -9 activation in cell lysates exposed to UVB in the presence of cytochrome c and dATP, which was caused by the production of ROS, and the other is the inhibition of in vitro caspase-3/7 activation in the presence of active caspase-9. These results showed that the inhibition of the caspase cascade downstream mitochondria by ROS production, leading to a significant inhibition of caspase-3/7 activation, was one of the causes of the antiapoptotic effect by small doses of UVB irradiation. 相似文献