热塑性甲壳素衍生物N,O-苄基壳聚糖的合成及表征

Chitin derivatives are difficult to be melten because of their very strong inter-molecular and intra-molecular hydrogen bonds. In this paper, N,O-benzyl chitosan was synthesized by means of phase-transfer method. The total degree of substitution for this derivative was 0 8 as determined with 1H NMR and the degree of substitution on nitrogen was 0 3 as determined with elemental analysis. This is a thermoplastic chitin derivative. Its melting point was 470 K as measured with DSC. A viscous isotropic melt occurred at the temperatures between the melting point and the decomposition temperature(513 K) while N,O-benzyl chitosan was heated on a hot stage. DSC results agreed with the results of microscopy observation. The benzyl group can not form hydrogen bonds. It is also non-polar and has larger volume. These factors weaken the interactions between chitosan chains, and therefore decrease the melting point, which was lower than the decomposition temperature. As a result, N,O-benzyl chitosan was able to melt

甲壳素类液晶高分子的研究Ⅶ.N,O-苄基壳聚糖的胆甾螺旋行为

N ,O-苄基壳聚糖在浓溶液中形成胆甾液晶相 .用圆偏光二向色性谱 (CD)研究了这一聚合物的螺旋行为 ,主要包括螺距和螺旋方向 .浓度越高 ,螺距P越大 ,意味着胆甾相的扭转力随浓度增加而减弱 .CD谱图上观测到两类吸收 ,即在 5 70nm附近较宽但较强的吸收和 330nm附近较尖但较弱的吸收 .前者归属于胆甾相层片的超分子螺旋构象 ,而后者可以归属于分子链的螺旋构象 .改变浓度或溶剂性质时这两个层次的构象都会发生符号的变化 .提高浓度 (固定二氧六环为溶剂 )时两种螺旋结构先后发生反转 .以氯仿为溶剂 (固定浓度为 6 5 % )时两种螺旋结构均为左旋 (正Cotton效应 ) ,但二氧六环和四氢呋喃为溶剂时均变为右旋 (负Cotton效应 ) .溶剂的影响可能与溶剂和高分子间形成氢键的能力有

Effects of temperature and host plant transplantation on rice root aphid, Tetraneura nigriabdominalis (Sasaki) (Homoptera: Pemphigidae)

於試驗室中，研究粗長毛禾根綿蚜（Tetraneura nigriabdominalis (Sasaki)）在牛筋草上於10、15、20、25、30及35℃六個定溫下以及在牛筋草、水稻、玉米及高粱四種寄主植物之間的轉換對其若蚜發育時間、成蚜壽命、繁殖率及族群介量之影響。結果顯示粗長毛禾根綿蚜在牛筋草上於10 ~ 30℃之間，若蚜之發育臨界低溫為7.5℃，總積溫為175.75日度（degree-day）；若蚜期發育時間由10℃的42.20天遞減至30℃的7.46天；成蚜壽命由15℃的21.27天漸減至35℃的1.33天；成蚜繁殖率於25及30℃下，平均每隻母蚜可產下超過32隻的子代為最大；在35℃之內在增殖率（r）最小（r＝-0.3272/天），而最大則在30℃（r＝0.2694/天）；終極增長率（λ）由10℃的0.9653/天增加至30℃的1.3092/天；在25℃中之族群具有最高之淨繁殖率（R0 = 32.0 子代/ ♀）；平均世代時間隨著溫度上升而由10℃的49.72天減少至35℃的9.00天。於30℃下進行四組寄主轉換試驗，連續觀察6個世代，結果顯示由牛筋草轉換至水稻、玉米及高粱之第1世代，若蚜存活率皆不到50％，由水稻轉換至牛筋草之第1世代之若蚜存活率為52％，隨著世代數增加，在轉換寄主上若蚜存活率則上升；轉換寄主植物後之成蚜繁殖率、族群內在增殖率、終極增長率及淨繁殖率皆隨世代數增加而明顯上升。比較四種寄主植物上之第6世代，若蚜之發育時間以在水稻上及在牛筋草上為最短，分別為6.89天及7.46天；成蚜壽命以在高粱上之7.36天為最短；成蚜繁殖率以在水稻上為最大（39.85子代/ ♀），而以在高粱上為最小（18.67子代/ ♀）；內在增殖率以在牛筋草及水稻上為最大，分別為1.3092/天及1.3507/天；終極增長率以在牛筋草及水稻上為最大，分別為0.2694/天及0.3006/天；在水稻上族群之淨繁殖率最高（R0 = 36.6子代/ ♀），而在高粱上者為最低（R0 = 14.6子代/ ♀）；平均世代時間以在牛筋草及水稻上為最短，分別為12.29天及11.98天。分析四種寄主植物根部之含氮量顯示，不論有無蚜蟲吸食，含氮量皆以水稻及玉米為最高，高粱為最低，顯示寄主植物含氮量高者，蚜蟲取食具有較高繁殖率，反之亦然。中文摘要………………………………………………………… 1 英文摘要………………………………………………………… 3 前 言………………………………………………………… 5 往昔研究………………………………………………………… 7 一、粗長毛禾根綿蚜之生物學………………………………… 7 二、溫度對蚜蟲之影響………………………………………… 8 三、轉換寄主對蚜蟲之影響……………………………………11 四、寄主植物含氮量對蚜蟲之影響……………………………12 材料與方法………………………………………………………15 一、供試寄主植物之準備………………………………………15 二、供試蟲源之飼育……………………………………………16 三、溫度對粗長毛禾根綿蚜發育、壽命及繁殖之影響………16 四、轉換寄主植物對粗長毛禾根綿蚜壽命、繁殖及族 群介量之影響………………………………………………17 五、不同寄主植物對粗長毛禾根綿蚜發育、壽命、繁 殖及族群介量之影響………………………………………17 六、不同寄主植物根部含氮量測定……………………………18 七、數據分析……………………………………………………19 結 果…………………………………………………………21 一、溫度對粗長毛禾根綿蚜發育、壽命、繁殖及族群 介量之影響…………………………………………………21 二、轉換寄主植物對粗長毛禾根綿蚜壽命、繁殖及族 群介量之影響………………………………………………24 三、不同寄主植物對粗長毛禾根綿蚜發育、壽命、繁 殖及族群介量之影響………………………………………31 四、不同寄主植物根部之含氮量………………………………34 討 論…………………………………………………………35 一、不同定溫對粗長毛禾根綿蚜發育、壽命、繁殖及 族群介量之影響……………………………………………35 二、轉換寄主植物對粗長毛禾根綿蚜壽命、繁殖及族 群介量之影響………………………………………………39 三、不同寄主植物對粗長毛禾根綿蚜發育、壽命、繁 殖及族群介量之影響………………………………………41 四、寄主植物含氮量對粗長禾根綿蚜之影響…………………43 參考文獻…………………………………………………………44 表…………………………………………………………………53 圖…………………………………………………………………6

Simulation of inferior turbinate reduction using computational fluid dynamics methods

目的：建立模拟两种下鼻甲切除术式的计算机流体力学即CFD模型,分析其对鼻腔流体力学的影响。方法：建立单侧下鼻甲肥大鼻腔的CFD模型A,在此基础上模拟下鼻甲切除术分别建立B、C两种术后模型,运用流体分析软件Fluent6.3.26计算三种模型的鼻腔全流场数据。结果：B模型患侧鼻腔面积较原始模型平均面积增大0.36cm^2,C模型增大0.89cm^2;B模型患侧鼻腔的压降差（约8Pa）与原始模型相比无太大改变,C模型压降差明显降低（约3Pa）。B模型患侧鼻腔流量无明显增加,C模型总鼻道下方及下鼻道流量为80ml/s,约为原始模型的8倍。B模型在吸气相及呼气相气流流速及流动方式与原始模型无明显改变,C模型在鼻瓣区流速明显增加,达到1.04m/s,并且涡流的产生与正常鼻腔趋于一致。结论：模型C在恢复鼻腔的正常解剖形态及正常通气生理方面都明显优于模型B。在下鼻甲手术中,恢复鼻腔的正常解剖结构对于鼻腔疾病的治疗具有决定性的意义。Objective：Two computational fluid dynamic（CFD）models of unilateral inferior turbinate reductions（ITR）were constructed and investigate the influences of aerodynamic consequences.Method：A unilateral hypertrophic inferior turbinate CFD model wasestablished.Two kinds of methods in removing of tissue bulk along the length of the hypertrophic inferior turbinate were used,and we got the model B and the model C.Nasal airflow distribution were computed before and after simulated unilateral inferior turbinate reduction in use of Fluent6.3.26.Result：Simulated two kinds of ITR resulted in enlargement in the cross-section area of inferior nasal meatus,0.36cm^2 of the model B and 0.89cm^2 of the model C in average.Model C produced a less reduction in intranasal pressures（approximately 3Pa）than the model B and the original model which are the same as approximately 8Pa.More air was predicted to flow in the affected nasal passage in the model C（approximately 80ml/s）than the model B and the original model.Airspeed in the anterior valve region was improved significantly and more vortices happened in the model C.Conclusion：The model C is significantly better than the model B in restoring normal anatomy and ventilation physiological of the nasal cavity.So,in ITR recoverying normal anatomy structure of the nasal has decisive significance

Sensitive Determination of Chondroitin Sulfate by Fluorescence Recovery of an Anionic Aluminum Phthalocyanine-Cationic Surfactant Ion-Association Complex Used as a Fluorescent Probe Emitting at Red Region

硫酸软骨素的测定在生物医学领域有重要价值,但常规检测法在灵敏度、选择性或简易性方面尚存在不足。本文基于带正电基团的阳离子表面活性剂对具有红区发射特性的强荧光化合物—荷负电的四磺基铝酞菁具有高效荧光猝灭作用,而在生物多糖硫酸软骨素存在下,上述荧光猝灭体系荧光显著恢复的现象,提出酞菁-表面活性剂离子缔合物荧光恢复高灵敏测定硫酸软骨素的新方法,并用于实际样品分析。研究表明,中性介质中,红区荧光探针四磺基铝酞菁(TETrASulfOnATEd AluMInIuM PHTHAlOCyAnInE,AlS4PC)与阳离子表面活性剂十四烷基二甲基苄基氯化铵(TETrAdECyldIMETHylbEnzylAMMOnIuM CHlOrIdE,TdbAC)发生强烈的缔合作用,导致AlS4PC的荧光几乎完全猝灭,从而获得暗背景的荧光体系。在加入带有阴离子基团(磺酸基)的生物多糖硫酸软骨素(CHOndrOITIn SulfATE,CS)后,由于竞争结合作用,AlS4PC被释放而使体系的荧光大幅度恢复,且恢复程度与CS呈线性正相关。优化了反应条件,考察了共存物质的影响,结果表明本法具有较好的选择性。在最佳条件下,线性范围为0.20~10.0μg·Ml-1,检测限为0.070μg·Ml-1,工作曲线方程y=1.04X+2.09,r=0.999 5。该法操作简便,灵敏度、稳定性与准确性好,实际样品的分析结果令人满意。酞菁荧光化合物在分析科学中的应用尚不多见,本文工作进一步开拓了酞菁红区荧光探针的新应用。Determination of chondroitin sulfate in the biomedical field has an important value.The conventional methods for the assay of chondroitin sulfate are still unsatisfactory in sensitivity,selectivity or simplicity.This work aimed at developing a novel method for sensitive and selective determination of chondroitin sulfate by fluorimetry.We found that some kinds of cationic surfactants have the ability to quench the fluorescence of tetrasulfonated aluminum phthalocyanine(AlS4Pc),a strongly fluorescent compound which emits at red region,with high efficiency.But,the fluorescence of the above-mentioned fluorescence quenching system recovered significantly when chondroitin sulfate(CS)exits.Tetradecyl dimethyl benzyl ammonium chloride(TDBAC)which was screened from all of the candidates of cationic surfactants was chosen as the quencher because it shows the most efficient quenching effect.It was found that the fluorescence of AlS4 Pc was extremely quenched by TDBAC because of the formation of association complex between AlS4 Pc and TDBAC.Fluorescence of the association complex recovered dramatically after the addition of chondroitin sulfate(CS)due to the ability of chondroitin sulfate to shift the association equilibrium of the association,leading to the release of AlS4 Pc,thus resulting in an increase in the fluorescence of the reaction system.Based on this phenomenon,a novel method with simplicity,accuracy and sensitivity was developed for quantitative determination of CS.Factors including the reaction time,influencing factors and the effect of coexisting substances were investigated and discussed.Under optimum conditions the linear range of the calibration curve was 0.20~10.0μg·mL-1.The detection limit for CS was 0.070μg·mL-1.The method has been applied to the analysis of practical samples with satisfied results.This work expands the applications of AlS4 Pc in biomedical area.福建省科技重点项目(2012Y0081); 福建省公益类科研院所基本专项项目(2010R1101;2014R1102); 厦门市科技项目(3502Z20143015)资

Synthesis and characterization of thermoplastic chitin derivative N,O-benzyl chitosan

Chitin derivatives are difficult to be melten because of their very strong inter-molecular and intra-molecular hydrogen bonds. In this paper, N, O-benzyl chitosan was synthesized by means of phase-transfer method. The total degree of substitution for this derivative was 0.8 as determined with H-1 NMR and the degree of substitution on nitrogen was 0.3 as determined with elemental analysis. This is a thermoplastic chitin derivative. It's melting point was 470 K as measured with DSC. A viscous isotropic melt occurred at the temperatures between the melting point and the decomposition temperature(513 K) while N,O-benzyl chitosan was heated on a hot stage. DSC results agreed with the results of microscopy observation. The benzyl group can not form hydrogen bonds. It is also non-polar and has larger volume. These factors weaken the interactions between chitosan chains, and therefore decrease the melting point, which was lower than the decomposition temperature. As a result, N,O-benzyl chitosan was able to melt

JUNO Sensitivity on Proton Decay p→νˉK+p\to \bar\nu K^+ Searches

The Jiangmen Underground Neutrino Observatory (JUNO) is a large liquid scintillator detector designed to explore many topics in fundamental physics. In this paper, the potential on searching for proton decay in $p\to \bar\nu K^+$ mode with JUNO is investigated.The kaon and its decay particles feature a clear three-fold coincidence signature that results in a high efficiency for identification. Moreover, the excellent energy resolution of JUNO permits to suppress the sizable background caused by other delayed signals. Based on these advantages, the detection efficiency for the proton decay via $p\to \bar\nu K^+$ is 36.9% with a background level of 0.2 events after 10 years of data taking. The estimated sensitivity based on 200 kton-years exposure is $9.6 \times 10^{33}$ years, competitive with the current best limits on the proton lifetime in this channel

JUNO sensitivity on proton decay p → ν K + searches*

The Jiangmen Underground Neutrino Observatory (JUNO) is a large liquid scintillator detector designed to explore many topics in fundamental physics. In this study, the potential of searching for proton decay in the $p\to \bar{\nu} K^+$ mode with JUNO is investigated. The kaon and its decay particles feature a clear three-fold coincidence signature that results in a high efficiency for identification. Moreover, the excellent energy resolution of JUNO permits suppression of the sizable background caused by other delayed signals. Based on these advantages, the detection efficiency for the proton decay via $p\to \bar{\nu} K^+$ is 36.9% ± 4.9% with a background level of $0.2\pm 0.05({\rm syst})\pm$$0.2({\rm stat})$ events after 10 years of data collection. The estimated sensitivity based on 200 kton-years of exposure is $9.6 \times 10^{33}$ years, which is competitive with the current best limits on the proton lifetime in this channel and complements the use of different detection technologies