Crystallization behavior of predominantly syndiotactic poly(β-hydroxybutyrate)

Predominantly syndiotactic poly(-hydroxybutyrate), syn-PHB, of variable syndioregularity (syndyad fractions 0.59, 0.62, 0.64, and 0.71) and molecular weight was prepared by the dibutyltin dimethoxide catalyzed ring opening of racemic-butyrolactone (BL). The crystallization behavior of the syn-PHB polymers was investigated by DSC and X-ray diffraction analyses. DSC of films after melting and annealing showed at least one, and often two distinct melting transitions occuring over a broad (often 40°C) temperature range. These results indicate that syn-PHB chain segments of variable syndioregularity form crystalline regions with very different thermodynamic stabilities. Maximum degrees of crystallinity for melt annealed 0.64- and 0.71-syn-PHB was observed at an annealing temperature (T _c ) of 30°C. AtT _c values at 45°C and higher, crystallization of relatively lower syndioregular chain segments was apparently excluded to variable degrees dependent onT _c and sample syndiotactic dyad content. After crystallization of syn-PHB samples at elevated temperatures, ambient temperature annealing resulted in an observed lower temperature melting transition at 50°C. This result showed little to no dependence on syn-PHB syndio-regularity andT _c . Both solution precipitated 0.62-syn-PHB and 0.71-syn-PHB have WAXS patterns with poorly resolved crystalline reflections superimposed on amorphous haloes indicating low levels of crystallinity (17% and 25%, respectively) and poorly formed crystals. Isothermal crystallization monitored by DSC showed that the syn- and natural origin PHB showed fastest crystallization rates at temperatures between 50°C and 70°C and 60°C and 90°C, respectively. From the dependence of the higher melting transition onT _c it was determined that the equilibrium melting temperatures for 0.62-syn-PHB (M _n =83,700 g/mol) and a 0.64-syn-PHB (M _n =11,900 g/mol) were 157 and 154°C, respectively. An Avrami analysis of syn-PHB yielded results similar to that found for natural origin PHB indicating that crystal growth occurs by a two-dimensional mechanism.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

Detection of fetal cells in maternal blood

We report the detection of fetal cells in the maternal circulation by enzymatic amplification of a single copy gene sequence that was fetal-specific. Fetal HLA-A2-positive cells were sorted from maternal HLA-A2-negative cells by flow cytometry and confirmed by demonstration of a fetal-specific HLA-DR4 sequence. However, this sequence could not be detected in unenriched maternal DNA prepared at 28 and 32 weeks' gestation. The sensitivity of detection was 1 HLA-DR4-positive cell in 10⁵ HLA-DR4-negative cells. We conclude that prenatal diagnosis of paternally inherited autosomal-dominant genetic defects may be possible by selective gene amplification of maternal peripheral blood. However, preliminary enrichment for fetal cells may be necessary.     

仿生脂肪细胞制备以及对水体中林丹去除的研究

利用生物体脂肪组织可以对脂溶性有机物有效富集的原理,通过界面聚合合成了类似脂肪细胞结构的仿生脂肪细胞,并对其结构进行了初步表征.仿生脂肪细胞具有亲水性膜以及亲脂性的内部结构,亲水性的膜允许携带脂溶性有机物的水体穿过膜,亲脂性的内含物将脂溶性有机物富集截留.仿生脂肪细胞对林丹具有较好的去除效果,15%三油酸甘油酯含量的仿生脂肪细胞与粉末活性炭具有相当的林丹去除能力.仿生脂肪细胞对林丹的去除机理包括内含物的生物富集以及膜上空腔的物理吸附两部分,而内含物的生物富集作用则是主要作用方式.     

无机高分子絮凝剂聚合硅酸铝铁的研究

以ALCL3，FeCl3，Na2SiO3和盐酸为原料，采用NaOH作为碱化聚合剂，合成了具有不同碱化度（B），不同Al/Fe/Si摩尔比的铝铁硅共聚物（简称PAFSC），通过PH滴定法测定分析了铝、铁在其水解共聚合过程中PH值的变化，然后通过透射电镜和混凝实验对共聚物的晶形貌像和絮凝作用进行了研究，通过对模拟具有色悬浊水样的絮凝实验，并与现有的其它无机絮凝剂作比较后可以看出：在同样投加量情况下，PAFSC处理的水具有更低的剩余浊度和色度。     

Chloroacetic acids in environmental processes

The fate of chloroacetic acids (CAA) in forest soils was studied using radio-indicator methods. We showed that chloroacetic acids are both microbially degraded and simultaneously formed by chloroperoxidase-mediated chlorination of acetic and humic acids. The degree of biodegradation of chloroacetic acids in soil depends on their concentration. Dichloroacetic acid (DCA) is degraded faster than trichloroacetic acid (TCA). Chlorination of acetic acid led to a fast formation of dichloroacetic acid, whereas chlorination of humic acids gave rise to trichloroacetic acid. Both processes lead to a steady state in soil, participate in the chlorine cycle and possibly also in decomposition of organic matter in forest ecosystems.     

Thermal research on the uncontrolled behavior of styrene bulk polymerization

Thermal runaway can occur during the styrene bulk polymerization process because of easily formed local hotspots resulting from the high viscosity of reactants and the difficulty of heat dissipation. To obtain the thermal hazard characteristics, the polymerization behavior of styrene was investigated using differential scanning calorimetry (DSC) at a scanning rate of β = 2 °C/min. Experimental results showed that the exothermic peaks obtained for heat initiation were different from those obtained when initiator was added. The exothermic peak changed from one to two after the initiator was added. The exothermic onset temperature (T₀) was also reduced. Phi-tech II was utilized to study the bulk polymerization of styrene in an adiabatic environment. The adiabatic temperature rise (ΔT_ad), starting temperature of uncontrolled polymerization (T_star), maximum temperature (T_end), and heat of polymerization (ΔH) under different conditions were acquired. When the dose of the additive was increased, the starting temperature of uncontrolled polymerization (T_star) decreased and the adiabatic temperature rise (ΔT_ad) increased gradually. Severity grading was performed based on the severity evaluation criteria of runaway reaction. The results can help designers decide whether it is necessary to take certain measures to reduce risk.     

Chemiluminescence in evaluating thermal oxidative stability of acrylonitrile-butadiene-styrene (ABS) copolymers. IV. Comparative study of various stabilizers in mass polymerization and emulsion resins

The thermal oxidative stability of ionic and emulsion ABS with various antioxidants and UV stabilizers was studied. It was found that Santonox R provides better protection than Irganox 1076 to both resins. It is also the case in formulations with Tinuvin 770 and Tinuvin 328.     

氰化钠生产中聚合废料的利用

对氰化钠生产中的聚合废料进行了吸附试验和氰化钠含量分析，试验结果表明，聚合废料中含有２８％左右的氰化钠，其中黑褐色杂质可用活性炭吸附脱除。生产规模试验证明，用聚合废料为原料生产的硫氰酸钠，产品质量可达到装置设计指标，满足腈纶装置的使用要求。     

The basic properties of poly(lactic acid) produced by the direct condensation polymerization of lactic acid

Poly(lactic acids) with high molecular weights have been synthesized by direct condensation polymerization of lactic acid. These polymers have good mechanical properties and can be processed into products such as cups, film, and fiber, which can be used as compostable materials. This polymerization method can be applied to the synthesis of copolymers of lactic acid and other hydroxyacids. The properties of poly(lactic acid) and copolymers synthesized by the direct process are different from those of polymers obtained by the conventional lactide process.     

Biosynthesis and Characterization of Laccase Catalyzed Poly(Catechol)

Enzymatic polymerization of catechol was conducted batch-wise using laccase enzyme produced by the culture Trametes versicolor (ATCC 200801). The polymerization reaction was carried out in 1:1 (v/v) aqueous-acetone solution, buffered at pH 5.0 with sodium acetate (50 mM) in a sealed, temperature-controlled reactor at 25°C. The molecular weight of the produced polymer was determined with GPC. FT-IR, DSC, and TGA were employed to investigate the structure and thermal behavior of synthesized poly(catechol). It was found that catechol units were linked together with ether bonds and thermal stability of the catechol increased in the poly(catechol) polymeric structure effectively. The number average molecular weight of poly(catechol) was found as 813 ± 3 Da with a very narrow polydispersity value of 1.17 showing selective polymerization of catechol by the enzyme.