Study on Molecular Chain Morphology of Konjac Glucomannan

The long-range structure of konjac glucomannan(KGM)is studied by using laser light scatter(LLS), gel permeation chromatography(GPC)and method of viscosidity. The weight-average molecular weight(Mw), root-mean-square ratio of gyration[(S2)1/2], second viral coefficient(A2)and multi-dispersion coefficient(Mw/Mn)are 1.04×106, 105. 0±0. 9 nm,(-1. 59±0.28)×10-3 mol ml g-2 and 1.015±0.003, respectively. Mark-Houwink equation is established as [η] = 5. 96×10-2Mw0.73 and the molecular chain parameters are as follows: ML=982. 82 nm-1, Lp = 27. 93 nm, d = 0. 74 nm, h = 0. 26 nm, L = l 054.11 nm. Further more molecular chain morphology of KGM is studied by using atom force microscope(AFM)and transmission electronic microscope(TEM), and the result shows that the KGM molecular is an extending semi-flexible linear chain without branch. Therefore, the image of molecular chain morphology confirms the deduction drawn by Mark-Houwink equation and molecular chain parameters.

Studies on the Molecular Chain Conformation Stability of Aminated Konjac Glucomannan

Konjac glucomannan （KGM） was aminated by 2-chloroethyl-amine （CEA） as reagent so as to study the influence of concentration of CEA （based on the amount of KGM）, concentration of NaOH, reaction time and temperature on the extent of amination. And the molecular simulation technology was adopted to analyze the conformation stability of aminate （AKGM）. The results indicate that when the amount of CEA is higher, the extent of amination is higher. The optimum concentration of NaOH, reaction time and temperature are 10% NaOH, 70 ℃ and 45 rain, respectively. IR shows KGM is successfully aminated. The conformation of AKGM is in a random clew-like shape.

Transverse relaxation characteristic and stress relaxation model considering molecular chains of HTPB coating based on pre-strained thermal aging

In order to accurately describe the transverse relaxation characteristic and stress relaxation modulus of HTPB coating during pre-strain thermal aging process,a one month thermal aging test was carried out at70C with pre-strain of 0%,3%,6%and 9%,respectively.The low-field1 H NMR and stress relaxation modulus tests were carried out for HTPB coating at different aging stages.The stress relaxation model considering the molecular chains was proposed according to the changes of crosslinking chain and dangling chain of HTPB coating during pre-strain aging.The results showed that with the increase of aging time,the decay rate of transverse relaxation curve became faster,the transverse relaxation time decreased,the value of combined parameter q Mrl increased,the proportion of crosslinking chain decreased,while the proportion of dangling chain increased.Moreover,the stress relaxation modulus increased,the crosslinking network structure of HTPB coating became denser and the degree of crosslinking increased.At the initial aging stage,the pre-strain will destroy the crosslinking network structure of HTPB coating to a certain extent.With the increase of aging time,the effect of pre-strain will gradually weaken and the influence of aging on materials will gradually increase.The correlations between the stress relaxation model considering the molecular chains and the test results were more than 0.9950,which can accurately describe the stress relaxation modulus of HTPB coating during the pre-strain thermal aging process.

Effects of Irradiation on the Structure-activity Relationship of Konjac Glucomannan Molecular Chain Membrane

To know the effects of irradiation on the konjac glucomannan （KGM） molecular chain membrane, KGM membrane solution was treated with the irradiation dose of 0-20 kGy in this study, and the structure and properties of KGM membrane were analyzed with Infrared spectrum, Raman spectrum, X-ray, SEM scanning and so on. The results revealed that the effects of different irradiation doses on the KGM molecular chain structure were different. Higher irradiation dose （20 kGy） resulted in partial damage against KGM membrane crystal structure, and there was no obvious change for the amorphous structure; with membrane property test, the tensile strength of KGM membrane gradually increased with the increase of irradiation dose and its elongation at break reduced, but these changes were not significant, WVP value reduced; with SEM, the membrane surface treated with irradiation was smoother even than the membrane without treatment. In addition, when increasing the irradiation dose, membrane surface became more even, and arrangement was more orderly and compact. KGM membrane nrooerties, and it is an ideal Irradiation modification could effectively improve the modification method.

Enhancing Molecular Chain Entanglement and π-π Stacking Toward the Improvement of Shape Memory Performance of Polyimide

Thermoplastic polyimides(PIs)with shape memory potential have received growing attention in recent years.In this work,highperformance thermoplastic PIs were fabricated by introducing PIs with chain rigidity(r-PI)into PI with chain flexibility(f-PI).The influences of molecular chain entanglement andπ-πinteractions on their thermomechanical and shape memory properties were investigated.The degree of molecular chain entanglement was quantitively characterized based on dynamic mechanical analysis(DMA).Theπ-πinteractions were investigated in detail by X-ray diffraction(XRD)and UV-Vis spectroscopy.It was found that the entanglement density increased andπ-πinteractions became stronger with the introduction of r-PI into f-PI,leading to the improvement of shape recovery.Moreover,a broad and increased glass transition temperature(T_(g))was achieved,endowing the PIs with multiple shape memory properties.The synergistic effects of increased entanglement density and enhancedπ-πinteractions were beneficial to regulating interchain interactions and thereby achieving high shape memory performance of the PIs.

Thermal properties of polyurethane elastomer with different flexible molecular chain based on para-phenylene diisocyanate

This work focuses on the relationship between flexibility of molecular chains and thermal properties of polyurethane elastomer（PUE）, which laid the foundation of further research about how to improve thermal properties of PUE. A series of PUE samples with different flexibility of molecular chains was prepared by using 1,4-butanediol（1,4-BDO）/bisphenol-a（BPA） blends with different mole ratios including9/1, 8/2, 7/3, 6/4 and 5/5. As comparison, PUE extended with pure 1,4-BDO and BPA was also synthesized.These samples were characterized by differential scanning calorimetry（DSC）, thermogravimetric analysis（TGA）, dynamic mechanical analysis（DMA）, etc. The results showed that with the decrease in flexibility of molecular chains the glass transition temperature（Tg） increased and low-temperature properties became worse. Besides, all samples had a certain degree of microphase separation, and soft segments in some samples were crystallized, i.e. the decreasing flexibility of molecular chains led to the impossibility of chains tightly packing and crystalline domains forming so that the degree of microphase separation decreased and the thermal properties became worse.

Temperature-induced Molecular Chain Motions of Styrenic Triblock Copolymers Studied by Intrinsic Fluorescence Spectra

The temperature-induced molecular chain motions of styrenic triblock copolymers （SBC）, i.e. polysty- rene-block-polybutadiene-block-polystyrene （SBS） and polystyrene-block-poly（ethylene-co-l-butene）-block-poly- styrene （SEBS）, were studied by intrinsic fluorescence method. For SBS, the glass transition temperatures （Tgs） of B block and S block obtained by intrinsic fluorescence method were in good agreement with differential scanning calorimetry measurements （DSC）. In the case of SEBS, an isoemission point was observed at about 310 nm at ele- vated temperatures, suggesting the slight conversion between the monomer and excimer emission. On this basis, the molecular chain motion of SEBS was monitored by both fluorescence intensity and excimer/monomer fluorescence ratio. Besides the Tgs of S block and EB blocks, a melting point （Tin） of weak crystalline in EB block was unambiguously determined by intrinsic fluorescence. Furthermore, it was found that the melting process directly led to the slight loosening of PS segments in interface and consequently the reduction of the amount of excimer. A reasonable mechanism was proposed to describe the molecular chain movements and phase transitions of SEBS upon heating. Moreover, the influence of temperature on the apparent activation energy of non-radiative process （ E^T ） around Tg of S block was much stronger than that around Tg of B or EB blocks.

Molecular Modeling of the Chain Structures of Polybenzoxazines

The structures and properties of benzoxazines were investigated by virtue of molecular modeling at a molecular level. By means of Cerius software(version 4.0) supplied by Molecular Simulations Inc., the molecular mechanics and the molecular dynamics were performed under a PCFF force field. Five kinds of the polymeric chains of benzoxazines were created by using polymer builder and energy minimization. The relaxation process was conducted with both energy minimization and molecular dynamics.

A steered molecular dynamics study on the elastic behaviour of knotted polymer chains

In this paper the influence of a knot on the structure of a polymethylene （PM） strand in the tensile process is investigated by using the steered molecular dynamics （SMD） method. The gradual increasing of end-to-end distance, R, results in a tighter knot and a more stretched contour. That the break in a knotted rope almost invariably occurs at a point just outside the ＇entrance＇ to the knot, which has been shown in a good many experiments, is further theoretically verified in this paper through the calculation of some structural and thermodynamic parameters. Moreover, it is found that the analyses on bond length, torsion angle and strain energy can facilitate to the study of the localization and the size of a knot in the tensile process. The symmetries of torsion angles, bond lengths and bond angles in the knot result in the whole symmetry of the knot in microstructure, thereby adapting itself to the strain applied. Additionally, the statistical property of the force-dependent average knot size illuminates in detail the change in size of a knot with force f, and therefore the minimum size of the knot in the restriction of the potentials considered in this work for a PM chain is deduced. At the same time, the difference in response to uniaxial strain, between a knotted PM strand and an unknotted one is also investigated. The force-extension profile is easily obtained from the simulation. As expected, for a given f, the knotted chain has an R significantly smaller than that of an unknotted polymer. However, the scaled difference becomes less pronounced for larger values of N, and the results for longer chains approach those of the unknotted chains.

茂金属聚乙烯薄膜晶点的组成及形成原因

采用凝胶渗透色谱仪(GPC)、差示扫描量热仪(DSC)、偏光显微镜以及红外光谱等分析手段,从原料的分子链结构分析了茂金属聚乙烯薄膜晶点的组成及其形成原因。结果表明,茂金属聚乙烯薄膜晶点的结晶形态与无晶点的正常薄膜的不同,构成晶点的晶体尺寸均匀性远不如无晶点的正常薄膜,这是因为晶点中含有类似于纤维状的晶体,这种晶体先结晶,导致随后形成的晶体在此处生长不均匀。此外,分子链上的端基双键(RCH CH 2)在吹膜过程中引起的分子间交联和分子链中存在的亚甲基序列较长的规整结构,是形成类纤维状晶体的主要因素,而较长亚甲基序列的规整结构是由于共聚单体分布不均匀引起的。

Molecular Dynamics Studies of Collapse Stages in the chain folding process of Polyethylene

Molecular dynamics simulations of model polyethylene chains with various lengths up to 4000 CH2 units were performed. Our results verified that the modification of force fields to demonstrate the collapse stages in the folding process is not necessary. The transition between the stages of chain folding became sharp, and the clusters became stable as the chain became longer.

低密度聚乙烯基料链结构对黏弹特性的影响

高压电缆向高电压等级和大长度的发展,对交联聚乙烯绝缘料的加工性能提出了更高的要求。绝缘料的加工性能和电缆绝缘成型质量主要受低密度聚乙烯(LDPE)基料黏弹特性影响,基料的黏弹特性取决于其链结构。然而,由于LDPE基料分子链支化结构复杂,难以建立单一的链结构参数与黏弹特性的关联,因此精准地获得LDPE链结构特征对黏弹特性的影响对电缆绝缘优化升级至关重要。该文采用制备型升温淋洗分级工艺,对管式法LDPE和釜式法LDPE进行分级得到具有不同平均分子量的级份,采用凝胶渗透色谱法和旋转流变仪表征原料和级份的链结构参数及黏弹特性。结果表明,长链支化结构相似时,重均分子量越大,分子链间越容易产生缠结,黏度和模量越高,剪切变稀现象发生频率越低;重均分子量接近时,零切黏度与长链支化度具有非单调关系,过高的长链支化度会削弱分子链间的物理缠结,导致零切黏度降低。基于LDPE黏弹特性构效关系,结合电缆挤出成型工艺,设计更为适宜的基料黏弹特性参数,以此优化调控LDPE的链结构,是未来高端电缆绝缘材料研发的方向。

基于分子链演化的NEPE推进剂基体超弹本构模型

为了揭示硝酸酯增塑聚醚(NEPE)推进剂基体内高分子链结构演化与超弹性力学行为间的构效关系,采用多尺度方法,对复杂变形状态下NEPE推进剂基体内的高分子链演化过程及其表征模型进行了研究。首先,在基体黏合剂、固化剂和增塑剂等组分微观模型的基础上,通过对基体体系的分子动力学模拟,发展了描述复杂变形状态下交联链和自由链构形演化的动力学模型。随后,基于统计力学理论对系统自由能中交联链和自由链演化的贡献进行了定量表征,并建立了考虑高分子链交联、缠结效应的超弹本构模型。最后,结合NEPE推进剂基体胶片准静态拉伸实验数据对本构模型进行了验证。结果表明,相较于经典Arruda-Boyce超弹本构模型,基于物理机制的本构模型中本构参数具有真实的物理意义,可以通过物化实验进行参数标定,能较好地预测复杂变形状态下的基体超弹性行为,从而为推进剂基体力学性能的调控和组分优化提供模型支持。

山药多糖药理作用及提取技术研究进展

山药是传统的药食两用物质,在我国具有悠久的食用历史,被广泛应用于食品、医药、畜牧等行业。山药多糖作为山药的主要化学成分,因具有多种生物活性,如免疫调节、抗肿瘤、降血糖、降血脂、抗氧化、抗炎等而受到广泛关注。基于此,总结了山药多糖的结构及其种类,从免疫调节活性、抗肿瘤活性、降血糖和降血脂活性、抗氧化活性、抗炎和抗菌活性等方面对近些年关于山药多糖药理活性的研究进行综述,并对山药多糖的提取技术进行汇总,最后从提取纯化技术、结构表征技术、临床应用试验等方面进行了展望,为山药多糖组分的未来研究与应用提供参考。

Molecular Chain Flexibility and Dielectric Loss at High-Frequency:Impact of Ester Bond Arrangement in Poly(ester imide)s

The evolution of high-frequency communication has accentuated the significance of controlling dielectric properties in polymer media.Traditionally,it has been theorized that rigid molecular chains lead to lower dielectric loss.However,the validity of this proposition at high frequencies remains uncertain.To scrutinize the correlation between chain flexibility and dielectric properties,we synthesized six poly(ester imide)s(PEIs)with systematically varied molecular chain flexibilities by modifying the ester's substitution on the aromatic ring.The introduction of ester bonds bestowed all PEI films with a low dielectric dissipation factor(D_(f)),ranging from 0.0021 to 0.0038 at 10 GHz in dry conditions.The dry D_(f)displayed a pattern consistent with volume polarizability(P/V).Unexpectedly,PI-mmm-T,featu ring the most flexible molecular chain,exhibited the lowest dielectric loss under both dry(0.0021@10 GHz)and hygroscopic(0.0029@10 GHz)conditions.Furthermore,the observed increase in D_(f)after humidity absorption suggests that the high dielectric loss of PEI in applications may be attributed to its hygroscopic nature.Molecular simulations and characterization of the aggregation structure revealed that the smaller cavities within flexible molecular chains,after close stacking,impede the entry of water molecules.Despite sacrificing high-temperature resistance,the precursor exhibited enhanced solubility properties and could be processed into high-quality films.Our research unveils new insights into the relationship between flexibility and highfrequency dielectric loss,offering innovative perspectives on synthesizing aromatic polymers with exceptional dielectric properties.

不同改性方法对超高分子量聚乙烯纤维蠕变行为的影响

超高分子量聚乙烯(PE-UHMW)纤维因其优异的性能广泛应用于多个领域,但其在长时间负载下易蠕变的问题限制了其更广泛的应用。关于PE-UHMW纤维的研究多关注于纤维本身的蠕变性能优化,对蠕变过程和蠕变行为讨论较少。通过石墨烯共混改性和支化改性两种方法制备得到了不同性能的耐蠕变纤维样品,通过力学性能表征、40%断裂载荷下3 h的蠕变测试和差示扫描量热(DSC)测试,探讨了不同纤维的蠕变行为和对应的蠕变机理。实验对比了常规纤维、掺杂不同含量石墨烯的PE-UHMW纤维以及不同支化度的PE-UHMW纤维和商业耐蠕变纤维Dyneema DM20纤维,研究发现,共混改性和支化改性均能提高PE-UHMW纤维的耐蠕变性能,但表现出不同的蠕变行为和机理。石墨烯的添加能够有效降低PE-UHMW纤维的初始蠕变量,尤其是在石墨烯质量分数为8%时,纤维的蠕变变形减少了37.6%,当石墨烯质量分数大于8%后,初始蠕变量反而增加;支化改性对纤维蠕变性能的影响主要体现在恒定载荷下的抗形变能力。包含支链的纤维初始蠕变量要大于未改性纤维,但其在第二阶段的蠕变速率显著降低,显示出更好的耐蠕变性能。通过对蠕变曲线进行时间外推验证了改性纤维在长期载荷下的稳定性。石墨烯共混改性使纤维的DSC吸热峰值升高至146℃以上,支化改性纤维则展现3个独立吸热峰,表明支链引入新的微观结构。最后讨论分析了不同改性方法对PE-UHMW纤维蠕变行为的影响机制。

WHO(2020)女性生殖系统肿瘤分子分型在子宫内膜癌中的应用与临床意义

目的探讨WHO(2020)女性生殖系统肿瘤分子分型在子宫内膜癌(endometrial cancer,EC)中的临床应用及其意义。方法收集62例EC临床资料,根据WHO(2020)女性生殖系统分子分型标准,采用免疫组化法和PCR法将EC分为4种亚型,即POLE突变型、错配修复缺陷型(mismatch repair deficient,MMRd)、无特异性分子谱型(no specific molecular profile,NMSP)和p53突变型,分析其与临床病理特征的关系。结果POLE突变型3例(4.8%),MMRd型15例(24.2%),NSMP型36例(58.1%),p53突变型8例(12.9%)。POLE基因突变与浸润深度、组织学分级、脉管侵犯、淋巴结转移和FIGO分期,差异均无统计学意义(P>0.05)。15例MMRd型患者中,FIGOⅡ+Ⅲ期患者的比例明显增加,其中1例p53蛋白过表达,2例均完全失表达。36例NSMP型患者与组织学低级别(Grade I+Ⅱ)有关(P<0.05),与其它临床病理特征均无关(P>0.05);8例p53突变型患者与组织学高级别(GradeⅢ级)有关(P<0.05);淋巴结转移、FIGOⅡ+Ⅲ期明显增加,差异均无统计学意义(P>0.05)。结论分子分型在EC的治疗中具有重要应用价值,与POLE基因突变型和NSMP型相比,MMRd型和p53突变型患者预后较差。

低分子量酶解灵芝硒多糖对小鼠肠道菌群的影响

目的研究低分子量灵芝硒多糖对肠道菌群紊乱小鼠的改善调节作用。方法利用生物发酵法培养富集灵芝硒多糖,采用热水浸提法提取灵芝硒多糖,并进一步酶解为低分子量多糖,以水解率为响应值,在单因素基础上,用响应面法优化酶解工艺条件。随后使用超滤膜截取10 kDa以下多糖,以头孢克肟诱导建立肠道紊乱小鼠模型,灌胃低分子量灵芝硒多糖,并测定小鼠体重及肠道内容物短链脂肪酸含量,利用16S rRNA高通量测序分析小鼠肠道菌群变化。结果灵芝硒多糖的富硒量为(327±26)mg/g,多糖含量为(6.14±0.18)%,低分子量多糖的酶解最优工艺为温度50℃、pH 5.5、时间121 min,该条件下的水解率为62.8%。研究表明低分子量多糖对小鼠体重无影响,高通量测序结果显示低分子量灵芝硒多糖能有效改善肠道菌群失调症状,调节肠道菌群的物种组成,显著上调厚壁菌门(Firmicutes)丰度,降低拟杆菌门(Bacteroidetes)丰度,上调产酸菌乳杆菌属(Lactobacillus)、布劳特氏菌属(Blautia)、链球菌(Streptococcus)、样棒菌属(Allobaculum)、颤螺菌属(Oscillospira)等丰度,增加乙酸、丁酸含量,下调普雷沃氏菌(Prevotella)、拟杆菌属(Bacteroides)、梭菌属(Clostridium)、粪球菌属(Coprococcus)、瘤胃球菌属(Ruminococcus)丰度,抑制丙酸分泌。结论低分子量灵芝硒多糖具有改善小鼠肠道菌群失调作用,可能是通过调整菌群组成来影响短链脂肪酸分泌达到保护肠道健康的目的。

叠氮丙啶-实时荧光聚合酶链式反应-高通量测序技术鉴定冷链食品中多种病原菌

目的 应用叠氮丙啶-实时荧光聚合酶链式反应-高通量测序技术鉴定冷链食品中多种病原菌,构建病原菌分子进化树。方法 以冷链食品中的沙门氏菌、金黄色葡萄球菌、蜡样芽胞杆菌、副溶血性弧菌、单核细胞增生李斯特氏菌5种病原菌作为研究对象,应用叠氮丙啶-实时荧光聚合酶链式反应技术作为冷链食品中病原菌检测初筛手段,应用微生物培养法以及生化鉴定仪器法进行方法比对与结果验证,运用高通量测序以及分子进化树构建作为冷链食品中所分离病原菌的种属地位确证方法。结果 叠氮丙啶-实时荧光聚合酶链式反应技术成功扩增了冷链食品中生活状态病原菌的特征性核酸片段,排除了死亡细菌以及阴性对照菌的干扰,病原菌检出限可达到1×10^(3)CFU/mL,一次反应可检测42份试样,可以在18 h内完成检测工作。在冷链食品中病原菌抽样检测调查中,随机采集的751份冷链食品,共检出62株病原菌,病原菌总体检出率为8.3%(62/751)。通过后续的16S rRNA测序以及葡萄球菌属、弧菌属以及李斯特菌属分子进化树的构建,成功溯源了金黄色葡萄球菌的污染来源并完成病原菌种属定位。结论 本方法特异性好、灵敏度高、检测通量高,为冷链食品及相关食品中病原菌的精确检测与溯源分析提供新的思路与方法。