Preparation of core–shell type nanoparticles of diblock copolymers of poly(L‐lactide)/poly(ethylene glycol) and their characterization in vitro

Core–shell type nanoparticles of poly(L ‐lactide)/poly(ethylene glycol) (LE) diblock copolymer were prepared by a dialysis technique. Their size was confirmed as 40–70 nm using photon correlation spectroscopy. The ¹H‐NMR analysis confirmed the formation of core–shell type nanoparticles and drug loading. The particle size, drug loading, and drug release rate of the LE nanoparticles were slightly changed by the initial solvents that were used. The drug release behavior of LE core–shell type nanoparticles showed an initial burst during the first 12 h and then a sustained release until 100 h. The degradation behavior of LE block copolymer nanoparticles was divided into three phases: the initial rapid degradation phase, the stationary phase, and the rapid degradation phase until complete degradation. It was suggested that lidocaine release kinetics were predominantly governed by the diffusion mechanism in the initial burst phase and after that by both of the diffusion and degradation mechanisms. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2625–2634, 2002     

苯乙烯-马来酸酐(SMA)共聚物对颜料的分散及其在喷墨印花中的应用

介绍了苯乙烯-马来酸酐（SMA）共聚物的合成方法和分散性能。探讨了它对颜料分散的机理、影响分散性能的主要因素，以及在喷墨印花中的应用前景作了展望。     

Effect of polymerization conditions on o‐phenylenediamine and o‐phenetidine oxidative copolymers

A series of new o‐phenylenediamine (OPD)/o‐phenetidine (PHT) copolymers with partly phenazine‐like structures has been successfully synthesized at three polymerization temperatures by chemically oxidative polymerization in four different polymerization media. The molecular structures and properties of the resulting OPD/PHT polymers were investigated by IR, UV–vis and high‐resolution ¹H NMR spectroscopies, and DSC, in order to ascertain the effect of reaction temperature, comonomer ratio and acid medium. The copolymerization mechanism of OPD with PHT monomers has been proposed. It is found that the statistical OPD/PHT copolymer obtained at a temperature of 118 °C has a higher degree of polymerization than that obtained at 12–17 °C. The OPD content in the copolymers calculated from NMR spectroscopic analysis is higher than that in the feed OPD content, whereas the OPD content calculated from element analysis is slightly lower than the feed OPD content. It can be predicted that denitrogenation takes place in the OPD units during the polymerization process at OPD/PHT molar ratios of 90/10 and 100/0. These OPD/PHT copolymers exhibit a much better solubility than the OPD homopolymer, hence suggesting an incorporation of PHT units into the phenazine structure of the homopolymer. The thermal behavior of the copolymers was also studied. Copyright © 2004 Society of Chemical Industry     

A Micellar Route to Ordered Arrays of Magnetic Nanoparticles: From Size‐Selected Pure Cobalt Dots to Cobalt–Cobalt Oxide Core–Shell Systems

Starting with Co‐salt‐loaded inverse micelles, which form if the diblock copolymer polystyrene‐block‐poly(2‐vinylpyridine) is dissolved in a selective solvent like toluene and CoCl₂ is added to the solution, monomicellar arrays of such micelles exhibiting a significant hexagonal order can be prepared on top of various substrates with tailored intermicellar distances and structure heights. In order to remove the polymer matrix and to finally obtain arrays of pure Co nanoparticles, the micelles are first exposed to an oxygen plasma, followed by a treatment in a hydrogen plasma. Applying in‐situ X‐ray photoelectron spectroscopy, it is demonstrated that: 1) The oxygen plasma completely removes the polymer, though conserving the original order of the micellar array. Furthermore, the resulting nanoparticles are entirely oxidized with a chemical shift of the Co 2p_3/2 line pointing to the formation of Co₃O₄. 2) By the subsequent hydrogen plasma treatment the nanoparticles are fully reduced to metallic Co. 3) By exposing the pure Co nanoparticles for 100 s to various oxygen partial pressures pequation/tex2gif-inf-5.gif, a stepwise oxidation is observed with a still metallic Co core surrounded by an oxide shell. The data allow the extraction of the thickness of the oxide shell as a function of the total exposure to oxygen (pequation/tex2gif-inf-7.gif × time), thus giving the opportunity to control the ferromagnetic–antiferromagnetic composition of an exchange‐biased magnetic system.     

Synthesis and characterization of poly(N‐vinyl‐2‐pyrrolidone) grafted sodium alginate hydrogel beads for the controlled release of indomethacin

Graft copolymers of sodium alginate (NaAlg) with N‐vinyl‐2‐pyrrolidone were prepared using azobisisobutyronitrile as initiator. The graft copolymers (NaAlg‐g‐PVP) were characterized with Fourier transform infrared spectroscopy, elemental analysis, and differential scanning calorimetry. Polymeric hydrogel beads of NaAlg and NaAlg‐g‐PVP were prepared by crosslinking method using glutaraldehyde (GA) as a crosslinker in the hydrochloric acid catalyst (HCl) and these beads were used to deliver anti‐inflammatory drug, indomethacin (IM). Chemical stability of the IM after encapsulation into beads was confirmed by FTIR. Preparation conditions of the NaAlg‐g‐PVP beads were optimized by considering the percentage entrapment efficiency, particle size, swelling capacity and their release data. In vitro release studies were performed in simulated gastric fluid (pH 1.2) for the initial 2 h, followed by simulated intestinal fluid (pH 7.4) for 4 h. Effects of GA concentration, exposure time to GA, drug/polymer (d/p) ratio, and concentration of HCl on the release of IM were discussed. It was observed that IM release from the beads decreased with increasing GA concentration and exposure time. IM release also decreases with increasing d/p ratio and HCl concentration. The highest IM release was obtained to be 77% for beads crosslinked with 0.027M GA. Swelling experiments were also performed to compute molecular mass between crosslinks of the beads. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of third monomer on the crystal phase transition behavior of ethylene-tetrafluoroethylene copolymer

Crystal phase transition between the low- and high-temperature phases has been investigated for ethylene (E)-tetrafluoroethylene (TFE) alternating copolymer (ETFE) containing the third monomeric species by the temperature dependent measurements of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) and differential scanning calorimetry. Nonafluoro-1-hexene (NFH) and hexafluoropropylene (HFP) were chosen as the third monomers, where they are different in the side-branch length, -(CF₂)₃CF₃ and -CF₃, respectively. In the case of E/TFE/NFH copolymer (ET-C4F9), the crystal phase transition temperature of the original ETFE two-components copolymer was not very much affected by the existence of NFH in the range of NFH content from 0.7 to 3 mol%. Contrarily, the crystal phase transition temperature of E/TFE/HFP copolymer (ET-CF3) was found to decrease drastically with increasing HFP content. The melting temperature and the higher-order structure were also affected sensitively depending on the HFP content. This difference in phase transition behavior between ET-C4F9 and ET-CF3 copolymers is reasonably interpreted as follows: the short side groups (-CF₃) of HFP monomeric unit are included in the crystal lattice of E/TFE chains and the unit cell is expanded gradually with an increment of the HFP content, resulting in the decrease in phase transition point because of easier thermal motion of the chains. On the other hand, the long side groups [-(CF₂)₃CF₃] of NFH monomeric units are excluded out of the crystal lattice and located on the lamellar surfaces or in the amorphous region and do not affect very much the phase transition temperature even when the NFH content is increased. In association with such a change in crystal structure, the long period of stacked lamellar structure was found to decrease remarkably in the case of NFH, whereas it does not change very much for HFP, consistent with the interpretation of the above-mentioned WAXD data.     

甲状腺素T4免疫传感器的研究

报道以甲基丙烯酸羟乙酯与甲基丙烯酸甲酯的共聚物为载体膜材料，研制成非酶标记的Ｔ４免疫传感器，并对载体膜材料的共聚方法及共聚物共聚比与传感器灵敏度的关系进行了探讨。     

Partial or total silylation of dextran with hexamethyldisilazane

The silylation reaction of dextran with 1,1,1,3,3,3-hexamethyldisilazane (HMDS) in DMSO was studied as the first step of the synthesis of new amphiphilic polyester-grafted dextrans. According to the experimental conditions, i.e. dextran molar weight, medium temperature and reaction time, HMDS/OH ratio, addition of a catalyst and co-solvent, partially or totally silylated dextrans were recovered. The highest silylation yields were obtained with the lowest molecular weight dextrans. The increase in temperature medium and/or reaction time, the presence of catalyst or co-solvent favored the protection yield. Whatever the dextran used, complete silylation of the polysaccharide chain could be achieved by adequate selection of the experimental conditions. The thermal properties of resulting silylated polysaccharides were investigated by temperature modulated DSC. It was observed that T_g values of partially silylated dextran were maintained between 120 and 140 °C, independently of the dextran molecular weight. Interestingly, DMSO proved to behave as an efficient plasticizer of (partially) silylated dextrans. The partially silylated dextrans were efficiently used as multifunctional macroinitiators for the controlled ring-opening polymerization (ROP) of lactone. The ROP was then promoted from the remaining hydroxyl groups in the presence of tin or aluminium activator. After polymerization and ultimate deprotection of the silylated dextran backbone, amphiphilic polyester-grafted dextrans were readily recovered.     

PVC／NBR／HDPE共混体系相容性研究（Ⅰ）增容剂对力学性能的影响

采用丁腈橡胶（ＮＢＲ）及其氢化还原后产物（ＨＮＢＲ）为ＰＶＣ／ＨＤＰＥ共混体系的增容剂，研究了增容剂结构、用量及丙烯腈含量对共混体系相容性的影响。发现丁腈橡胶（ＮＢＲ２９及ＨＮＢＲ２９）对ＰＶＣ／ＨＤＰＥ体系有较好的增容作用，而ＮＢＲ４０及ＨＮＢＲ４０较差。当增容剂用量为２％，ＰＥ含量为８％～１２％时，共混物具有较好的相容性，力学性能得到改善。     

有机纤维材料用软膜乳液阻燃剂的制备

采用甲醛、尿素、三聚氰胺、脒基脲磷酸盐为原料,以硼砂、硼酸、氨水为pH调节剂合成了保护胶;在保护胶存在下,以预乳化的丙烯酸酯混合单体于82-88℃共聚合成乳液,将其涂布于有机纤维材料,干燥后得软膜透明阻燃涂层。用其处理的涤棉布阻燃性能为:损毁长度68mm、续燃时间1s、阴燃时间3s、氧指数62、吸附干量287g/kg,处理的纸板的阻燃性能为:平均炭化长度77mm、平均续焰时间2s、平均续灼燃时间32s、吸附干量283g/kg。