Avaliação do metabolismo ósseo em modelos de plasticidade ontogenética

O aumento da prevalência da obesidade e osteoporose, bem como a identificação de mecanismos comuns que ligam a osteogênese e a adipogênese, sugerem que a obesidade e osteoporose podem ser distúrbios relacionados, e além disso, ambos podem ter suas origens no início da vida. Em 3 modelos diferentes de plasticidade ontogenética foi observado obesidade na vida adulta. Sendo assim, o objetivo deste trabalho foi investigar o impacto desses 3 modelos, o desmame precoce mecânico (DPM) e o farmacológico (DPF), e a supernutrição neonatal (SN) no tecido ósseo da prole durante o desenvolvimento. Para tanto, 2 experimentos foram realizados. No experimento 1, ratas lactantes foram divididas em 3 grupos: controle - os filhotes tiveram livre acesso ao leite durante toda a lactação; DPM - as mães foram envolvidas com uma atadura nos últimos 3 dias de lactação; DPF - as mães foram tratadas com bromocriptina (0,5 mg/duas vezes/dia) 3 dias antes do desmame padrão. No experimento 2, o tamanho da ninhada foi reduzido para 3 filhotes machos no 3o dia de lactação até o desmame (SN); o grupo controle permaneceu com 10 filhotes durante toda a lactação. Realizou-se absorciometria de raios-x de dupla energia, tomografia computadorizada, microtomografia computadorizada, teste biomecânico e análises séricas. Os dados foram considerados significativos quando P<0,05. No experimento 1, ao desmame, os filhotes DPM e DPF apresentaram menor massa corporal, massa gorda, densidade mineral óssea total (DMO), conteúdo mineral ósseo total (CMO), área óssea e osteocalcina sérica, e maior telopeptídeo carboxi-terminal do colágeno tipo I (CTX-I). O cálcio ionizado sérico foi menor apenas na prole DPM, a 25-hidroxivitamina D (25(OH)D) foi maior e o PTH menor apenas na prole DPF. Aos 180 dias, as proles DPM e DPF apresentaram maior massa corporal, maior massa de gordura visceral, hiperleptinemia, maior 25(OH)D e menor CTX-I. Ambos os grupos apresentaram aumento da DMO total, do CMO, da DMO da coluna vertebral e da área óssea aos 150 e 180 dias de idade. Nas avaliações ósseas individuais, as proles DPM e DPF também apresentaram aumento da DMO do fêmur e da vértebra lombar, da radiodensidade da cabeça femoral e do corpo vertebral; melhora da microarquitetura trabecular óssea e da resistência óssea. No experimento 2, observamos aumento da massa corporal, da massa gorda e da massa magra, do CMO e da área óssea no grupo SN desde o desmame até a idade adulta. Aos 180 dias, a prole SN também apresentou aumento da DMO total, da DMO do fêmur e da vértebra lombar, da radiodensidade da cabeça femoral e do corpo vertebral; melhora da microarquitetura trabecular óssea e da resistência óssea, maior osteocalcina e menor CTX-I. Demonstramos que, apesar de fatores de imprinting opostos, ambos os modelos causam melhora da massa, do metabolismo, da qualidade e da resistência óssea. Porém, parece que este efeito protetor sobre o tecido ósseo não é um resultado direto da programação deste tecido, mas sim consequência das alterações fisiopatológicas da obesidade programada pelos três modelos.

Tipos humanos particularmente estranhos: a síndrome de Asperger como objeto cultural.

A extraordinária atenção social e cultural que nas últimas décadas tem se dado ao diagnóstico do autismo/síndrome de Asperger convida a uma reflexão mais ampla para contextualizar o seu acontecimento como objeto cultural. É nesta direção que se move o presente trabalho, buscando identificar as coordenadas sociais, institucionais e culturais que levaram a tal exposição da deficiência relacional. Fala da história do espectro do autismo e sua pré-história ou a investigação sobre como as formas de não-conformidade com as expectativas da interação na presença do outro foram contextualizados, antes do modelo médico e em seus primeiros dias. Além disso, também têm procurado articular o discurso da contextualização cultural do espectro do autismo na area dos estudos sobre a deficiência chamada Critical Autism Studies por meio de um levantamento analítico dos autores e dos temas.

Tipos humanos particularmente estranhos: a síndrome de Asperger como objeto cultural.

A extraordinária atenção social e cultural que nas últimas décadas tem se dado ao diagnóstico do autismo/síndrome de Asperger convida a uma reflexão mais ampla para contextualizar o seu acontecimento como objeto cultural. É nesta direção que se move o presente trabalho, buscando identificar as coordenadas sociais, institucionais e culturais que levaram a tal exposição da deficiência relacional. Fala da história do espectro do autismo e sua pré-história ou a investigação sobre como as formas de não-conformidade com as expectativas da interação na presença do outro foram contextualizados, antes do modelo médico e em seus primeiros dias. Além disso, também têm procurado articular o discurso da contextualização cultural do espectro do autismo na area dos estudos sobre a deficiência chamada Critical Autism Studies por meio de um levantamento analítico dos autores e dos temas.

盐胁迫对螺旋藻光合作用影响的研究

盐胁迫是限制高等植物和藻类生长和产量的主要环境因子之一。PSII对环境胁迫的响应被认为是光合作用适应逆境过程中最重要的一个环节。尽管盐胁迫对PSII的影响已进行了大量的研究，但有关盐胁迫对PSII作用方式和位点的研究仍存在着争议。我们主要研究了盐胁迫对螺旋藻PSII结构和功能的影响，以探讨盐胁迫对PSII的作用方式和位点以及该藻细胞PSII对盐胁迫的适应机理。主要研究结果如下： 1． 用0、0.2、0.4、0.6、0.8M NaCl处理螺旋藻细胞12小时。随盐浓度的增加，螺旋藻细胞的Chla、carotenoid、PC、APC及蛋白含量均呈下降趋势，说明盐胁迫抑制了上述色素及蛋白的合成或加速了它们的降解，从而影响了螺旋藻的光合作用。 2． 随盐浓度的增加，螺旋藻细胞光合放氧活性和PS II电子传递活性显著降低，表明盐胁迫引起藻细胞PS II活性的下降。 3． 通过放氧活性、热致发光（TL）、多相荧光瞬态上升动力学曲线的测定以及Western 杂交，来探讨盐胁迫对螺旋藻细胞PS II供体侧电子传递及OEC33蛋白含量的影响。结果显示：随盐浓度的增加，螺旋藻细胞光合放氧活性和PS II电子传递活性下降;TL B-band和Q-band强度降低，在0-0.6M NaCl下，B-band的周期性振荡清楚，最大值出现在第二次和第六次闪光，而在0.8M NaCl时，S态振荡基本上消失，S 态氧化还原循环受阻;Fm， J、I和P相荧光水平降低。以上结果都表明盐胁迫使PS II的放氧侧受损伤。且随盐浓度的增加，盐分引起螺旋藻细胞外周蛋白OEC33的降解，在蓝藻中首次提出放氧机构的S态循环受阻，放氧活性降低。 4． 通过OJIP曲线的测定以及JIP-test、闪光诱导的可变荧光衰减动力学、热致发光（TL）的分析，我们研究了盐胁迫对螺旋藻细胞PS II受体侧的影响。结果显示： JIP-test的参数Ψo和φEo随盐浓度的增加而下降,显示QA-到QB 电子传递受阻;可变荧光衰减动力学快相组分半衰期延长，所占总可变荧光百分比下降，表明QA-到QB 电子转移变慢，中相组分半衰期延长、所占百分比下降，说明空的QB位点对PQ的结合减慢，有可能PQ分子对QB位点的结合能力下降;TL B-band和Q-band的峰温度出现了位移，可能QA、QB的氧化还原电势发生了改变。以上结果表明，盐胁迫伤害了PSII受体侧的电子传递。 5． 首次运用闪光诱导下的叶绿素荧光上升及其衰减动力学来研究盐胁迫对PS II受体侧的影响。 6． 盐胁迫下，PS II供体侧和受体侧电子传递受抑制，有活性的PSII反应中心数量下降，说明盐胁迫对螺旋藻细胞PSII的伤害也可能是多位点的作用方式。此外，盐胁迫下，藻细胞放氧活性的下降快于受体侧QA 到QB电子传递所占百分比的下降，有可能PS II放氧侧先受损伤，然后是反应中心和受体侧。上述结果表明盐胁迫下PSII活性的降低是由于PSII供体侧和受体侧电子传递的抑制，有活性的PSII反应中心的减少。 7． 借助螺旋藻类囊体膜的Western杂交分析，来研究盐胁迫对螺旋藻类囊体膜PSII相关蛋白的影响。结果表明，上述PSII活性的抑制是由于类囊体膜蛋白的损失。主要与PSII反应中心CP43、CP47和OEC33蛋白含量的下降有关。 8． PS II机构对盐胁迫的适应涉及以下几个方面：降低吸收横截面，（PC/chla，APC/chla比值的降低）;光系统II光化学反应的改变，通过关闭的PS II反应中心比例的增加，使得PS II机构免于过多激发能的伤害而得以保护;提高了剩余的有活性反应中心的耗能效率（DIo/RC增加）;保持有活性反应中心高的激发能转化效率，比如，TRo/RC保持不变;另外，随盐浓度的增加，由藻胆体向光系统I的能量传递增加，避免过量激发能对 PSII的伤害，使螺旋藻细胞适应盐胁迫环境。

A study on the effect of Zataria multiflora Bioss essential oil and Nisin on the growth of Lactococcus garvieae in the rainbow trout fillet (Oncorhynchus mykiss)

The ever-increasing population of the world and the growing need for animal protein has doubled the modern man’s demand for food. Additionally, the improvement in the general public health, and the worsening of environmental/ecological pollution have prompted today’s world to look for ways to procure healthy food. And one such attempt is the use of natural preservatives to decrease the bacterial load in foodstuffs, in other words, to increase their durability. This study evaluates the effects of different concentrations of Zataria multiflora Bioss (EO 0, 0.005, 0.015, 0.045, 0.135, 0.405%) and Nisin (0, 0.25, 0.5, 0.75 μg/ml) and storage time (9 days) on the growth of Lactococcus garvieae Ir-170A(856bp) alone, and their combination in a food model system (fillets of the rainbow trout (Oncorhynchus mykiss). Additionally, the growth of a sample of this bacteria in laboratory conditions was studied. The results of this study showed that different concentrations of Nisin had a significant impact (p<0.05) on Lactococcus garvieae. With the value of t in 0.75 μg/ml, the effectiveness rose to 65.77%; the biggest effect on Lactococcus garvieae. And the effect at 4 0C exceeded 80C. The study has also demonstrated that all concentrations of Zataria multiflora Bioss were effective against Lactococcus garvieae. However, with the value of t at 0.405%, the effectiveness was 71.91%. This value had the biggest effect on Lactococcus garvieae. At 4 0C, the effect surpassed the one at 80C. The synergistic effects of the EO and Nisin showed that with the value of t at 0.405% EO and 0.75 μg/ml Nisin was 14.62% had the greatest effect on Lactococcus garvieae. In this study, multi-factorial effects for different concentrations of Zataria multiflora Bioss (EO 0, 0.005, 0.015, 0.0025%), three different concentrations of 122 Nisin (0, 0.25,0.75 μg/ml) and two different levels of PH (5.5 , 7) at two incubation temperatures (15,37) on logp% of Lactococcus garvieae during 43 days in BHI broth were evaluated. Most of the effects on Lactococcus garvieae occurred in PH 5.5 and at a temperature of 150C.

Effects of Zataria multiflora Boiss essential oil and nisin on the growth of Staphylococcus aureus in light salted silver carp fillet (Hypophthalmichthys molitrix)

There is an increasing demand in developing newer and safer methods in preserving food products.Among which herbal additives seem to attract evermore attention recently.the major advantage of herbal additives is due to their favorable aroma besides their antimicrobial effects and less expensive than chemical additives. Zataria multiflora Boiss is a native Iranian herb which is used vastly as a food preserver essential oils and also medical usage. Metabolites of harmless bacteria, such as Nisin are also known to be safe preservatives that have antimicrobial activity. However to establish the usefulness of natural antimicrobial preservatives, they must be evaluated alone and in combination with other preservation factors to determine whether there are synergistic effects in rigid media . In this study were evaluated the effects of different concentrations of Zataria multiflora (EO 0, 0.005, 0.015, 0.045, 0.135, 0.405 ,0.810 %) and Nisin(0, 0.15, 0.25, 0.75 μg/ml) and Storage time (up to 21 days) on growth of Staphylococcus aureus ATCC 6538 in a food model system(light salted fish of silver carp, Hypophthalmichthys molitrix). The results on growth of S. aureus were evaluated using SPSS 15.0 statistical software (SPSS 15.0 for windows, SPSS Inc.) and analyzed the logarithm of total count of the bacteria by Tukey Test. Results were considered statistically significant when P≤0.05. The growth of Staphylococcus aureus was affected significantly(P<0.05) by EO and Nisin and also combinations of EO and Nisin. Samples treated with 0.135, 0.405 and 0.810% of thyme essential oil showed a significant decrease on the growth of the bacteria compared with an treated samples(P<0.05). No significant difference was seen on the growth of S.aureus in samples treated with lower concentrations of Z.multiflora(below 0.045%) and untreated group(P>0.05). The most inhibitory effects were seen in samples treated with 0.405% and 0.810% of thyme essential oil until 9 and 12 days after storage,respectively. Also there was significant inhibtory effect(P<0.05) in different concentration of nisin on the organism compared with an treated samples. The synergism effects of the Eo and nisin on the growth rate of the bacteria was significant (P<0.05) compared with untreated samples and samples treated with the Eo or nisin, only. Synergismic effects was observed at concentration of 0.405 and 0.810% of Z. multiflora essential oil with 0.25 μg/ml Nisin, respectively until 15 days after storage. As expected it is preferred to apply the least possible amounts of additives in food preserving that not only are effective and safe but are economically justifiable.

八肋游仆虫两类释放因子的相互作用(英文)

从八肋游仆虫中克隆到两类释放因子基因Eo eRF1和Eo eRF3。在Eo eRF3基因的阅读框中有 3个通用的终止密码子UGA ,在此编码半胱氨酸。为了研究两类释放因子的相互作用 ,用PCR的方法对 3个位点进行了定点突变 ,将UGA突变为通用的编码半胱氨酸的密码子UGU。突变结果经测序确认后 ,在大肠杆菌中获得全长Eo eRF3的正确表达。在此基础上 ,构建酵母双杂交重组质粒 ,用该系统检测了游仆虫两类释放因子的相互作用。结果显示 ,两类释放因子在生物体内形成复合体 ,从而在较原始的真核生物中 ,证实

Digital data transmission using electro-optically modulated vertical-cavity surface-emitting laser with saturable absorber

An electro-optically (EO) modulated oxide-confined vertical-cavity surface-emitting laser (VCSEL) containing a saturable absorber in the VCSEL cavity is studied. The device contains an EO modulator section that is resonant with the VCSEL cavity. A type-II EO superlattice medium is employed in the modulator section and shown to result in a strong negative EO effect in weak electric fields. Applying the reverse bias voltages to the EO section allows triggering of short pulses in the device. Digital data transmission (return-to-zero pseudo-random bit sequence, 27-1) at 10Gb/s at bit-error-rates well below 10-9 is demonstrated. © 2014 AIP Publishing LLC.

Optical properties of NAEC-PMMA nonlinear polymeric thin film

Novel guest nonlinear optical (NLO) chromophore molecules (4-nitrobenzene)-3-azo-9-ethylcarbazole (NAEC) were doped in poly (methyl methacrylate) (PMMA) host with a concentration of approximately 15% by weight. For a useful macroscopic electro-optic (EO) effect, these NLO molecules NAEC were arranged in a noncentrosymmetric structure in the host polymer by corona-onset poling at elevated temperature (COPET). For applying NAEC-PMMA polymer in optical devices such as EO switch, its optical properties have been investigated. The UV/Visible absorption spectra for the unpoled and poled polymer film were determined. The refractive index of the film was also determined from measurements of the coupling angles with the reflective intensity at 632.8 nm wavelength. Using the simple reflection technique, the EO coefficient 33 value was measured as 60 pm/V at 632.8 nm wavelength. The second-order nonlinear coefficient d(33) was characterized by the second-harmonic-generation (SHG) experimental setup and the calculated d(33) value reached 18.4 pm/V at 1064 nm wavelength. The relation between the second-order nonlinear coefficients d(33) and d(13) for the poled polymer film was also discussed in detail and the ratio d(33)/d(13) value was obtained as 3.3. (C) 2002 Kluwer Academic Publishers.

Determination of the macroscopic optical properties for the NAEC/PEK-c guest-host polymer films

The polyetherketone (PEK-c) guest-host polymer films doped with (4'-nitro)-3-azo-9-ethyl-carbazole (NAEC) were prepared. The films were poled by corona-onset poling at elevated temperature (COPET). The orientational order parameter of the chromophores NAEC in poled polymer film was determined by measuring the absorption spectra of the films before and after being poled. By using the two-level model, the measured dispersion of the refractive index of the polymer film, and the dispersion of the first hyperpolarizability of chromophore NAEC, the dispersion of the macroscopic second-order nonlinear optical (NLO) and linear electrooptic (EO) coefficients was evaluated for the NAEC/PEK-c guest-host polymer film. (C) 2001 Elsevier Science Ltd. All rights reserved.

Electro-optical properties and temporal stability of the guest-host DCNP/PEK-c polymer thin film

The polyetherketone (PEK-c) guest-host system thin films in which the range of the weight percent of 3-(1,1-dicyanothenyl)-1-phenyl-4, 5- dihydro-1H-pryazole (DCNP) is from 20% to 50% were prepared. The predicted high value of electro-optical (EO) coefficient gamma(33) = 48.8 pm/V by using two-level model was obtained when the weight percent of DCNP in the polymer system is 40%, whereas EO coefficients are attenuated at higher chromophore loading then 40%. The temporal stability of the EO activity of the guest-host polymer was evaluated by probing the decay of the orientational order of the chromophores in the polymer system.

Simple reflection technique for measuring the linear electro-optic coefficient of the polymer thin films

The simple reflection technique is usually used to measure the linear electro-optic (EO) coefficient (Pockels coefficient) in the development of EO polymer thin films. But there are some problems in some articles in the determination of the phase shift between the s and p light modes of a laser beam waveguided into the polymer film while a modulating voltage is applied across the electrodes, and different expressions for the linear EO coefficient measured have been given in these articles. In our research, more accurate expression of the linear EO coefficient was deduced by suitable considering the phase shift between the s and p light modes. The linear EO coefficients of several polymer thin films were measured by reflection technique, and the results of the Linear EO coefficient calculated by different expressions were compared. The limit of the simple reflection technique for measuring the linear EO coefficient of the polymer thin films was discussed.

One-dimensional modulation instability of broad optical beams in biased photorefractive-photovoltaic crystals under steady-state conditions

We present a comprehensive study of the one-dimensional modulation instability of broad optical beams in biased photo refractive-photovoltaic crystals under steady-state conditions. We obtain the one-dimensional modulation instability growth rate by globally treating the space-charge field and by considering distinction between values of Eo in nonlocal effects and local effects in the space-charge field, where Eo is the field constant correlated with terms in the space-charge field, which depends on the external bias field, the bulk photovoltaic effect, and the ratio of the optical beam's intensity to that of the dark irradiance. The one-dimensional modulation instability growth rate in local effects can be determined from that in nonlocal effects. When the bulk photovoltaic effect is neglectable, irrespective of distinction between values of Eo in nonlocal effects and local effects in the space-charge field, the one-dimensional modulation instability growth rates in nonlocal effects and local effects are those of broad optical beams studied previously in biased photorefractive-nonphotovoltaic crystals. When the external bias field is absent, the one-dimensional modulation instability growth rates in nonlocal effects and local effects predict those of broad optical beams in open- and closed-circuit photorefractive-photovoltaic crystals. (c) 2004 Elsevier B.V. All rights reserved.

钙催化剂在生物降解脂肪族聚酯合成中的应用

生物降解高分子在环境保护以及组织工程、药物控制释放、骨固定等医药领域有着广泛的应用。特别是以聚丙交酷（PLA）、聚乙交酯（PGA）、聚。一己内酯（PCL）以及它们的共聚物为代表的化学合成生物降解高分子材料，由于具有优异的性能、可以大规模生产、成本较低等优点，得到了人们广泛的关注。作为生物医用材料，对无毒性的要求很严。而现在所用的脂肪族聚酯大都是用金属盐、金属有机化合物等作为催化剂合成出来的，不可避免残留一些催化剂所用的金属元素。研究表明，即使是已经获得美国FDA批准的，现在用得最普遍的辛酸亚锡所残留的锡也可能引起一些细胞毒性。因此对毒性小且活性高的催化剂的研究是非常有意义。钙离子对人体是没有毒性的，因而这几年已引起了人们的兴趣，但文献中报道的钙催化剂，如CaHZ等，催化活性尚不够让人满意。本文对高效的钙催化剂在生物降解脂肪族聚酯中的应用进行详细的研究，得到了一些有意义的结论：1、用EO和PO处理的有机氨钙催化剂（Ca／EO和Ca／PO）聚合了CL和LLA。发现CL聚合速度很快，M／I=650时70℃反应3h后收率已达到90％以上，LLA的聚合速度比CL要慢，M／I=650、70℃反应10h后收率才达到90％以上。以上聚合反应有明显的活性聚合的特点：反应初期Mv和收率和聚合时间呈线性关系；Mv在一定范围内和M／I成线性关系。2、用红外、原子吸收和核磁共振等分析手段阐明了有机氨钙催化剂的结构：结构，而且这两个催化剂的活性中心分别是均是Ca-O键。CL和LLA的开环聚合可能是以配位一插入的机理进行的。3、用C。／PO催化剂聚合LLA时有一定程度的消旋化反应发生，曳NMR研究表明相当于88％的LLA和12％外消旋以共聚。提高反应温度到110℃时比旋光度只有-125℃说明消旋化反应比较严重。4、用C。／PO催化剂先聚合CL再聚合LLA的方法合成了PCL-PLA两嵌段共聚物，并用泊NMR，13C NMR，GPC，DSC，WAXD进行了表征。其绝对和相对分子量可以通过M／I和投料比进行控制。定量碳谱图表明有较严重的消旋化反应发生，相当于84％的LLA和16％外消旋LA共聚。DSC和似XD分析表明，PLA段的分子量小时PLA段不结晶，当PLA段的分子量达到一定程度（3000以上）后PCL一PLA嵌段共聚物有相分离现象发生。5、以各种分子量的PEG为引发剂用氨钙催化剂和开环聚合CL，合成了一系列PCL-PEG-PCL三嵌段共聚物，并用妞NMR，laCNMR，GPC，DSC，做XD进行了表征。聚合物的结构可以通过改变PEG的分子量和CL／PEG投料比来调整。从DSC和wAXD分析可以得出以下几个结论：PCL-PEG-PCL嵌段共聚物有相分离现象发生，形成PCL和PEG微相区域；PEG段的结晶行为受先结晶的PCL段的影响；PCL段的分子量越大PEG段的Tc和Tm越低，其结晶度越低。6、以各种分子量的PEG为引发剂用氨钙催化剂80℃下开环聚合LLA24小时，合成了一系列PLA-PEG-PLA三嵌段共聚物，和别的催化剂比起来温度低得多，反应时间也短得多。可以通过改变PEG的分子量和CL／PEG投料比来调整聚合物的结构。DSC和WAXD分析表明，PLA-PEG-PLA三嵌段共聚物中PEG段的结晶能力受PLA段的影响非常大：当PEG段的分子量很小时（如1000）很难结晶；即使当PEG段的分子量较大时如果PLA段的分子量达到一定程度时PEG段同样也不结晶；而且PLA段的结晶行为受本身分子量的影响比较大，其Tc和伽随着分子量增加有较大的提高。7、合成了MPEG-PLA两嵌段共聚物，发现合成PLA段的分子量大的聚合物比较困难，MPEG-PCL两嵌段共聚物很难合成。DsC和WAXD分析表明，PLA段对MPEG段结晶有一定程度的影响，但是比三嵌段共聚物的影响要小得多。8、用荧光光谱和IHNMR研究了上面合成出的几个样品的胶束行为。发现cmc由大到小的顺序为MPEG（5000）-PLA（5100），PLA（3050）-PEG（4600）-PLA（3050），PCL（2270）-PEG（5000）-PCL（2270），PCL（4600）-PEG（4600）-PCL（4600）。PCL-PEG-PCL三嵌段共聚物在水中形成了具有核一壳结构的胶束。9、以苯甲醇处理的有机氨钙催化剂开环聚合了CL。泊NMR谱图表明得到的聚合物具有苯端基。这一结果为用硝苯基乙醇代替苯甲醇制备催化剂，然后开环聚合CL或LA得到硝基苯端基的脂肪族聚酯打下了实验基础。

高分子固体电解质

固体电解质是全塑固态电池不可缺少的一个组成部分，近年来得到了迅速的发展。高分子固体电解质由于质量轻，可塑性强，并具且良好的力学性能和机械加工性能，在固体电解质领域内越来越受到人们的重视和关注。高分子固体电解质一般是由聚醚类的高分子主体物和无机盐形成的复合物。聚氧化乙烯（PEO）是高分子主体物中比较优秀的代表，其盐复合物在高温（100 ℃）时电导率可达2 * 10~(-3)Scm~(-1)，但由于结晶，其室温电导率很低(10~(-8) ～ 10~(-7)Scm~(-1))，远远满足不了室温电池的要求。本工作的目的是利用接技和共聚对PEO进行改性，提高复合物室温电导率。主要工作和结论有下列几点：（1）采用二步法合成了列三种单体：CH_2-CH CH_2O(CH_2CH_2O)_nCH_3 (n = 0,1,2)，通过改进反应条件，提高了产物收率。（2）考察了不同烷基铝多元催化剂对上述单体聚合的催化性能，发现只有Al(i-Bu)_3-Zn(acac)_2-H_2O和AlEt_3-Hacac-H_2O对单体聚合的催化效果较好。（3）DSC分析的结果表明，上述单体的均聚物不易结晶；聚合物玻璃化温度分别为-64 ℃(n = 0)，-75 ℃ (n = 1)和-86 ℃(n = 2)，都比PEO(Tg = -57 ℃)低，这对提高复合物电导率应该是有利的。（4）利用环氧丙烷（Po）与环氧烷（Eo）共聚，大幅度降低了聚合物的结晶性，当共聚物中Po含量达到40％时，聚合物几乎是完全非晶的。（5）利用DSC、X－射线衍射、偏光显微镜等手段对均聚物和共聚物的 NaScN和LiClO_4复合物的聚集态结构进行了研究，发现复合物中没有结晶络合物相存在，这与PEO体系是不同的。复合物结晶度随聚合物结构和盐含量的不同而变化。（6）共聚改性是提高复合物室温电导率的有效手段。共聚物与NaScN和LiClO_4复合物在25 ℃时的电导率分别达到了5 * 10~(-5)Scm~(-1)和1.1 * 10~(-4)Scm~(-1)，与PEO体系相比提高了2 ～ 3个数量级。（7）梳状均聚物虽然结晶度和玻璃化温度都很低，但其盐复合物的室温电导率不高，只有10~(-6)Scm~(-1)数量级，这与我们预期的结果不一致。（8）聚合物一盐复合物的电导率随聚合结构以及盐的种类和含量的变化而不同。对于无机盐来说，阴离子相同时，复合物电导率随阳离子半径的增大而增大，随着盐浓度的变化，复合物电导率出现一个极大值。另外，成膜溶剂、水份等都对复合物电尼率有很大的影响。（9）考察了复合物电导率随温度的变化情况。高温(～100 ℃)时，复合物电导率都比PEO体系低，说明为提高复合物室温电导率而对PEO进行的改性是以牺牲其高温电导率为代价的。