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Synthesis of alginate-cysteine modified gold nanorods for photothermal therapy of oral cancer
No full text本研究的目的是製備出具有良好生物相容性與標靶性的金奈米棒(Gold nanorod)並透過近紅外光源的照射下進行光熱治療來殺死癌細胞。藉由使用EDC活化海藻膠上的羧酸基，並與半胱胺酸(Cysteine)和標靶分子c(RGDfk)上的一級胺生成胜肽鏈，合成具有半胱胺酸與標靶分子的海藻膠高分子來修飾金奈米棒。其中半胱酸上的硫醇基能與金奈米棒形成穩定的硫金鍵結並取代表面的CTAB，海藻膠上的羧酸基與羥基能提供能提供材料高負電性與親水性，防止材料產生聚集，而修飾的c(RGDfk)KKK可用於標靶人類口腔鱗狀上皮細胞SAS。 我們藉由穿透式電子顯微鏡、界面電位分析、紫外光可見光光譜儀與FTIR等結果證實我們成功地製備出海藻膠/半胱胺酸修飾的金奈米棒。利用ICP-MS量測經由修飾標靶分子的材料於SAS細胞中Au的累積量，其結果提升了2倍，將材料使用近紅外光光源照射來進行光熱治療的實驗，GNR@Alg-Cys與GNR@Alg-Cys-RGD的細胞相對存活率為0.5與0.1，證實接上標靶分子的材料因為更容易進入細胞而有更好的治療效果，並且能夠藉由調整照光區域對特定位置進行加熱，在不影響周邊細胞的的情形下進行光熱治療來殺死癌細胞。Gold nanorods/alginate/cysteine (denoted as GNR@Alg-Cys) nanocomposites with good biocompatibility and cell-targeting ability are synthesized for photothermal therapy (PTT). Owing to the carboxylic acid groups on the alginate, we successfully functionalize alginate polymer with the primary amine groups of the cysteine and with targeting molecules (c(RGDfk)) through the formation of peptide bonds. Then, the thiol groups of the cysteine-functionalized alginate polymer can replace the surface protecting molecules (i.e. Cetyltrimethyl Ammonium Bromide; CTAB) on gold nanorods that were previously synthesized, thus connect the Au NRs with alginate polymer through Au-S bonds. In addition, we utilize c(RGDfK) oligopeptide to target the squamous cell carcinoma (i.e. SAS). The successful synthesis of GNR@Alg-Cys nanocomposites is confirmed with TEM, zeta potential, UV-Vis and FTIR analysis. The enhanced endocytosis of RGD-functionalized GNR@Alg-Cys is 1.95 times more than that of GNR@Alg-Cys, according to ICP-MS measurement. For PTT application, the synthesized samples are illuminated by NIR after SAS cell uptake, and the relative cell viabilities of GNR@Alg-Cys and GNR@Alg-Cys-RGD are 0.5 and 0.1, respectively. This result indicates that our GNR@Alg-Cys-RGD sample show great potential in PDT in the future nanomedicine
Synthesis and Characteristics of Polyethylene Glycol Copolymer Using Triphenylamine and Carbazole Derivatives for Perovskite Solar Cells
No full textEnergy-saving Design for the Separation of Two Azeotropic Mixtures
No full text本文探討各類共沸混合物分離之節能設計流程。首先討論共沸物質三級丁醇(tert-butyl alcohol,TBA)和水之各種分離設計流程，包括非均勻相共沸蒸餾(heterogeneous azeotropic distillation)、共沸隔牆塔(azeotropic dividing-wall column)與萃取蒸餾 (extractivedistillation)系統，並透過熱整合的方式節能。若採用非均勻相共沸蒸餾系統，則非均勻共沸蒸餾塔塔頂需產生高流率的汽相出流，造成該塔再沸器之高能秏。若採用共沸隔牆塔系統，隔牆塔的下半部分可視為兩根氣堤塔，故與原來之非均勻相共沸蒸餾系統比較，預濃縮塔的冷凝器被移除，節省了原來冷凝其汽相流所需的能秏及冷凝器之設備成本 (capital cost)。最後發現以甘油 (glycerol)作為萃取劑 (entrainer) 之萃取蒸餾系統，並加上一進料/出流熱交換器(feed-effluent heat exchanger, FEHE) 進行熱整合之設計流程最具經濟效益。 本文亦針對二甲基乙醯胺 (n,n-dimethylacetamide, DMAC) 與醋酸 (acetic acid, HAC)共沸系統的各種分離方法，討論以變壓蒸餾 (pressure swing distillation)、萃取蒸餾系統之程序設計。其中萃取蒸餾系統，除了討論採用傳統有機溶劑三甘醇 (triethylene glyceol, TEG) 作為萃取劑的系統外，也會對分別以純離子液體 (ionic liquid) 1-butyl-3-methylimidazolium Bis [(trifluoromethyl) sulfonyl]-imide ([BMIM][TF2N]) 以及混合溶劑 ([BMIM][TF2N]和TEG) 作為萃取劑的系統進行探討。結果發現以純離子液體[BMIM][TF2N] 作為萃取劑之萃取蒸餾系統最為節能，其次則為以混合溶劑 ([BMIM][TF2N] 和TEG) 作為萃取劑之萃取蒸餾系統。 藉由討論上述之兩個共沸物之節能設計流程，能發現儘管對於特定的混合物系統可以用不只一種方式來完成分離，但若是能夠選擇使用最適合之分離方式則可以大幅節省蒸汽費用與年度總成本。In this thesis, energy-saving design for the separation of azeotropic mixtures will be discussed. For the separation of azeotropicmixture, tert-buyl alcohol (TBA) and water, there are several alternative designs, including heterogeneous azeotropic distillation, azeotropic dividing-wall column (A-DWC) and extractive distillation system, all are investigated in order to save the steam cost and the total annual cost (TAC). For the separation using heterogeneous azeotropic distillation, since large amount of the top vapor of the heterogeneous azeotropic column is requied to generate, more energy is needed for the reboiler.For the separation using A-DWC, the lower part of it can be treated as two stripping columns, compared to the original heterogeneous azeotropic distillation design, the condenser of the preconcentrator is removed and therefore energy carried by the top vapor is conserved, which resulting in lower capital cost and utility cost. Finally, extractive distillation system using glycerol as entrainer with a feed-effluent heat exchanger (FEHE) is considered to be the most economic design. For the separation of the n,n-dimethylacetamide (DMAC) and acetic acid (HAC), the process design of the pressure-swing distillation and extractive distillation is proposed. In addition to use the conventional entrainer triethylene glycol (TEG), using pure ionic liquid 1-butyl-3-methylimidazolium Bis [(trifluoromethyl) sulfonyl]-imide ([BMIM][TF2N]) and mixed entrainer ([BMIM][TF2N] and TEG) is investigated too. The result showed that the most promising method is the extractive distillation system using pure ionic liquid [BMIM][TF2N] as entrainer, and then is the extractive distillation system using the mixed entrainer ([BMIM][TF2N]：TEG=0.6：0.4). In summary, for a particular azeotropic mixture, there are more than one ways to achieve the separation task. However, significant savings on the steam cost and TAC can be achieved if the most suitable separation method can be selected
Predictions of Effective Diffusion Coefficient of Mixed Matrix Membranes with Non-spherical Fillers
No full text複合薄膜兼具有傳統高分子薄膜之低製備成本的優點,其中添加之 填充物具有高選擇性或高透過率的特色,為一有大規模運用之發展潛 力的分離薄膜。就填充物之外型分類,可概括分類為球狀、管狀(一 維)或層狀(二維)。管狀填充物如碳奈米管及金屬氧化物奈米管,其 細長且管壁無法允許分子通透之特性,具有發展為分子篩填充物之潛 力。層狀填充物如層狀沸石或粘土礦物,其厚度薄而大面積之特性, 一般認為可以改變分子透過時之質量傳遞長度,藉此提昇分離時之 選擇性。一般用以計算複合薄膜之有效擴散係數及有效透過率之方程 式為 Maxwell 模型,此為一做廣泛應用於計算有效擴散係數之解析方 程式,此模型將球形填充物分散於基材中之行為類比做電阻串聯或並 聯所推導而出。透過相同之推導邏輯,而後發展出針對管狀填充物之 KJN 模型以及層狀填充物之 Cussler 模型。然而,無論是 Maxwell 模 型、KJN 模型或是 Cussler 模型,解析方程式無法徹底考慮真實管狀或 層狀填充物分散於基材中之行為,因此在模型的預測中往往造成偏差。 本研究使用有限元素分析法進行數值計算,首先建立仿真之三維 模型,並於其中添加管狀或層狀填充物,並調控其佔基材之不同體積 分率,透過 COMSOL MultiphysicsR 軟體進行質傳計算求得濃度分佈, 透過 Fick’s 擴散方程式的推導,進而得到包含更多資訊之數值方程式。 對於管狀填充物而言,本研究進行了長寬比值、擴散係數比值、空間 分布及填充物旋轉方向的探討。研究結果指出,提昇擴散係數比值可 以有效的提升有效擴散係數,且其效應遠大於提昇長寬比值的提升幅 度;而改變空間分布之效應非常顯著,倘若所有填充物延著垂直於擴 散之方向增加比重,其提昇可以遠大於平行於擴散方向之增加比重的 結果。旋轉方向效應亦指出,管壁垂直於擴散方向將不利於有效擴散 係數,且會大幅降低有效擴散係數。本研究亦進行了具有隨機分佈旋 轉方向填充物的效應,其結果指出,填充物的長寬比值效應並部顯著, 但擴散係數比值效應將會大幅改變有效擴散係數。對於層狀填充物 而言,本研究進行了擴散係數比值以及非等向性擴散的效應。研究結 果指出,具有非等向性擴散的填充物對整體有效擴散係數有顯著的影 響。為了驗證本研究中預測模型的正確性,吾人與文獻中若干透過實 驗所量測得之薄膜有效擴散係數,與本研究之模型及 Maxwell、KJN、 Cussler 模型做比較,其結果指出,本研究所預測之模型與其他解析方 程式有較好的準確性。This article presents a series of calculation of the effective diffusivity from the detailed mass transfer modeling of mixed matrix membranes with non-spherical (tubular and layered) fillers. We construct the filler-and-matrix models mimicking the realistic mixed matrix membranes, and perform the mass transfer simulations. A number of mixed matrix membranes'' parameters, including filler to matrix volume ratio, aspect ratio of fillers, filler to membrane''s relative diffusivity, and filler''s orientation are considered in our simulations. Our results show that tubular fillers'' alignment is critical to the effective diffusivity. The aspect ratio of tubular fillers only shows marginal effect on the effective diffusivity. Our results also suggest that the increase of aspect ratio and the intrinsic diffusivity of tubular filler will cause the increase of the overall effective diffusivity. For layered fillers, the effective diffusivity is influenced by the isotropy of the layered fillers caused by the differences in the out-of-plane and in-plane diffusivity. Also, the binary species selectivity in separation of the mixed matrix membranes can be adjust by the difference of the anisotropic diffusivity of the species-filler construction. Finally, we compare our results with selected experimental results in the literature for validation the prediction of the effective diffusivity of mixed matrix membranes
Diagnostic Study of Pulsed Power Solution Plasmas and its Application on the Synthesis of Metal Organic Frameworks
No full text本研究對於脈衝式水溶液電漿系統進行檢測，並嘗試以水溶液電漿製備材料。使用脈衝式電源驅動相較於直流或交流的供應能提供水溶液電漿系統具有更穩定且更佳的再現性表現，此性質使其具有被應用於系統檢測或材料製備的潛力，可藉由調控脈衝式電源之操作參數，控制系統在適當的條件下進行反應。實驗內容分為兩個部分，第一部分為診斷水溶液電漿系統之表現對應於驅動電極與溶液直接接觸面積的影響，第二部分為使用水溶液電漿系統製備類沸石咪唑材料。 第一部分以脈衝式電源激發電漿在 0.1 M 氯化鈉(NaCl)水溶液中生成，分別在驅動電極截面積直徑為0.1、0.3、0.5及1釐米系統中，進行同步化電流電壓、電漿放射光、氣泡動態及單位面積功率耗損的分析。氣泡在電極表面的生成速率與透過積分示波器所紀錄之電流電壓得到的單位面積能量耗損成正比，不受工作時間(Ton)的影響，而單位面積能量耗損則與驅動電極直接接觸溶液的面積成反比，造成在固定工作時間內，氣泡及電流波峰的出現頻率在小電極截面積直徑系統中較高，藉由同步相機與示波器觀察得到電流波峰與氣泡形成機制間存在重要關聯，且此現象與文獻中使用直流電源作驅動的電漿表現一致，而電漿放射光的生成機制不因系統不同而改變，皆伴隨氣泡的破裂或收縮出現，藉由上述之檢測試圖解釋水溶液電漿系統之概要性表現。 第二部分嘗試以脈衝式水溶液電漿，在水相中低反應物濃度條件下製備類沸石咪唑材料，透過以微流體方式注入金屬陽離子，在金屬鹽類溶液及有機配位子溶液接觸區域以電漿進行處理，並在純化過程中之離心與蒸乾步驟中採用甲醇作為溶劑，即本製程於前段反應在水相而於後段純化則在有機相中進行，經過XRD、SEM及FTIR的分析，得到實驗的最終產物為高純度之類沸石咪唑材料，提供一在水相環境中，於短時間內即能在低反應物濃度下合成高純度類沸石咪唑材料的製程。The diagnosis of plasma generated by a pulsed voltage in NaCl electrolytic solution and its potential applications are studied. The pulsed power can offer the solution plasma system a better stability and cycle-to-cycle reproducibility than the performance driven by DC or AC power. The optimum plasma behavior can be represented by regulating the suitable operation parameters, and this advantage gives a potential opportunity of the application for the system diagnosis and material fabrication. The experimental investigations include two parts: Diagnostic study of the effect of the electrode diameter on the behavior of plasmas and Synthesis of metal-organic frameworks by using aqueous solution plasma. In the first part, the effect of the electrode diameter on the discharge behavior of plasmas in saline solution was studied. The measurement of the plasma performance including current and voltage waveforms, discharge emissions, bubble dynamics and power consumptions were detected in the system. The driving electrode was a platinum wire covered by a glass tube to precisely define the area exposed to the solution. Platinum wires of four different diameters, namely 0.1 mm, 0.3 mm, 0.5 mm, and 1 mm, were used. A positive correlation was found between the generating rate of the bubble on the electrode surface and the power density consumption calculated from the IV waveform recorded by the oscilloscope. The result didn’t depended on the working period (Ton). However, a negative correlation existed between the area of the driving electrode exposed to the solution and the power density consumption. The outcome may explain why a higher appearance frequency of the bubbles and the current peaks in the small diameter driving electrode system. The time-resolved bubble dynamics taken by the high speed video show that the vapor formation process in this experiment is the same as the one driven by a DC power supply. The bubble formation mechanism is strong related to the change of the current waveform. The plasma discharges would not form until the vapor layer collapse or shrink in each system. The observations done in the experiment offer an explanation of the general solution plasma behaviors. In the second part, we tried to synthesize metal-organic frameworks by using aqueous solution plasma. The object of this experiment was to develop a fabrication which could synthesize high purity metal-organic frameworks in the conditions of low concentration of the reactants and reduced time. An attempt that the zinc salt microfluidics was introduced to the reaction container and a plasma was ignited in the contact zone between the zinc salt solution and the ligand solution was approached. After the reactants were treated in the aqueous phase, they were dissolved in the methanol for centrifugation and drying. The pure products were confirmed by analyzing the XRD, SEM and FTIR patterns. The experiment results supported that we reach the goal
Carbon Dioxide Absorption to Sodium Hydroxide Glycerol Solution by a Rotating Packed Bed
No full text旋轉填充床為程序強化的重要項目之一，其利用離心力代替重力場強化氣、液、固間的分離程序，使系統操作範圍變廣，且達到提升質傳效率百倍甚至千倍的效果。本研究利用旋轉填充床進行氫氧化鈉甘油水溶液化學吸收二氧化碳實驗，以研究在化學吸收中加入非水溶劑的效果；文中探討氣液流量、轉速、氫氧化鈉濃度以及甘油濃度等變數對吸收百分比、表徵總括氣膜質傳係數以及增強因子之影響。 實驗結果顯示，吸收百分比、表徵總括氣膜質傳係數以及增強因子隨轉速、液體流量以及氫氧化鈉濃度上升而上升，但隨著氣體流量增加而下降；另外，在氫氧化鈉水溶液中加入適量(5到13 wt%)甘油，能夠使吸收百分比、表徵總括氣膜質傳係數以及增強因子上升，化學吸收的效果比氫氧化鈉水溶液更佳，且最高能夠使吸收百分比上升20%左右。 而最後綜合本研究結果、本實驗室及公開文獻資料提出一結合化學吸收及物理氣提/吸收實驗之迴歸式如下： (K_G a)/(D_G a_t^2 ) (1-1.1 V_o/V_t )=0.006〖Re〗_G^0.1 〖Re〗_L^0.4 〖Gr〗_G^0.3 H_y^(-0.4) (1+C_NaOH )^3 (a_t/(a_p^'' ))^0.3Rotating packed bed (RPB) plays an important role in process intensification. The RPB substitutes the centrifugal force for gravitational force to enhance separation process. With the help of the centrifugal force, RPB can provide a wider operating range and better mass transfer efficiency. The absorption of carbon dioxide to sodium hydroxide glycerol/water solution in RPB was investigated. The gas and liquid flow rate, rotating speed, the concentration of sodium hydroxide, and glycerol weight percent were taken into consideration as operating variables to study the influence on absorption fraction, apparent overall volumetric mass transfer coefficient, and enhancement factor. According to experiment results, as the rotating speed, liquid flow rate, and the concentration of sodium hydroxide increased, absorption fraction, apparent overall volumetric mass transfer coefficient, and enhancement factor all increased. But these results were all decreased as gas flow rate increased. Moreover, adding 5 to 13 weight percent glycerol in sodium hydroxide solution could promote chemical absorption efficiency and raised absorption fraction at least 20% higher than sodium hydroxide aqueous solution. In this research, a correlation being applicable for chemical absorption and physical stripping/absorption is presented as: (K_G a)/(D_G a_t^2 ) (1-1.1 V_o/V_t )=0.006〖Re〗_G^0.1 〖Re〗_L^0.4 〖Gr〗_G^0.3 H_y^(-0.4) (1+C_NaOH )^3 (a_t/(a_p^'' ))^0.
Signal Enhancement of Veterinary Drug Residues Analysis by LC-ESI-MS/MS
No full text第一篇： 胺基醣苷類化合物 (aminoglycoside) 屬於高極性化合物。當使用逆相液相層析串聯質譜儀之分析方法需加入全氟羧酸離子對試劑，以提高分析物和靜相之作用力得到更好的分離效果，但離子對試劑之動相溶液具高表面張力和高導電度的特性，會使噴灑不穩定，且其和分析物形成離子對，造成分析物呈現似中性，使胺基醣苷類化合物游離化效率下降，而抑制分析物之訊號。 本研究利用一體式電泳淌度控制裝置 (electrophoretic mobility control device, EMC device) 和液相層析儀 (liquid chromatography, LC) 及電灑質譜儀 (electrospray ionisation mass spectrometry, ESI-MS) 串聯 (LC-EMC-ESI-MS)，本裝置藉由施加正電場於銜接管，使帶正電荷之分析物可進入質譜儀偵測；帶負電荷之七氟丁酸成功回退於分流槽內不進入銜接管；且在液相層析傳輸管和銜接管之間保留一適當間距，避免七氟丁酸受到液相層析儀之流速 (0.2 mL/min) 而衝入銜接管內。以此裝置減緩七氟丁酸進入電灑質譜儀，以提升胺基醣苷類化合物之訊號感度卻不失其解析度，並且將此裝置用於檢測牛奶檢體，確認此裝置於食品中胺基醣苷類化合物之檢測及應用性。 在本實驗得到一體式電泳淌度控制裝置之間距為300 μm及1500 V/cm的電場可成功將七氟丁酸回退且得到良好的胺基醣苷類化合物訊號；檢測牛奶檢體得到回收率為86-105 %，定量極限為2-4 ppb，確認此裝置可用於食品樣品中胺基醣苷類化合物的檢測且具有良好之感度。 第二篇： 超高效能液相層析法 (ultra performance liquid chromatography, UPLC) 使用1.7 μm之填充顆粒管柱，管柱內徑為2.1 mm，其最佳流速為0.6 mL/min，此流速下可提供較佳的管柱效能及解析度，並有更快的分析速度。本研究將超高效能液相層析電灑質譜法操作在最佳線性流速，結合管柱後分流 (post column splitting) 的方式，使進入電灑質譜法的移動相流速為最佳噴灑的流速，達到低流速的感度及高流速的解析度與快速分析的訴求。 本實驗以七種乙型受體素化合物進行分析，在超高效能液相層析以0.6 mL/min的移動相流速進行沖提，結合管柱後分流以分流比3：1，使移動相以0.2 mL/min的流速進入游離源進行氣化、離子化。 解析度部分，藉由改變數據取點數量，使流速為0.6 mL/min未分流之解析度比0.2 mL/min的流速佳，且0.6 mL/min經過分流後仍可維持良好之解析度。感度部分，沖提流速為0.6 mL/min分流進入電灑質譜法偵測的感度比未分流佳，但未能達到沖提流速為0.2 mL/min未分流之感度，推測是由於質譜偵測器於高流速偵測下，離子由離子源傳送入質譜儀速度之限制，導致分流方法達不到預期感度。Part 1 Aminoglycosides are highly polar compounds. Usually, the analysis of aminoglycoside is performed by reversed phased liquid chromatography (RPLC) with haptafluorobutyric acid (HFBA) as ion pairing reagent. HFBA reagent can improve resolution, but it results in suppression of analytes by unstable spray and decreasing ionizing effect. In this study, an integrated electrophoretic mobility control (EMC) device was developed to increase the sensitivity of aminoglycosides on the liquid chromatography-electrospray ionization mass spectrometry (LC-EMC-ESI-MS). By applying a positive electric field, HFBA anion is retained in the junction reservoir and aminoglycosides cation is able to move forward into mass spectrometry interface. A gap is between LC transfer and connecting capillary for retaining HFBA to avoid flowing into connecting capillary with the flow rate of 0.2 mL/min. The integrated electrophoretic mobility control device with a gap, 300 μm and the electric field , 1500 V/cm, is able to enhance S/N ratio without losing resolution. Therefore, EMC device successfully alleviate ion suppression caused by HFBA. The recoveries range from 86% to 105 %, and the limit of quantitation, LOQ, were found in the range of 2-4 ppb for milk sample. Part 2 The particle size of ultra performance liquid chromatography (UPLC) column packing is 1.7 μm. According to the Van Deemter equation, it is able to work at higher flow rate (0.6 mL/min) with the 2.1 mm I.D. column. The flow rate is critical for high speed and separation efficiency. However, high flow rate will decrease the ionization efficiency. In this study, seven β-agonists were analyzed by UPLC. The flow rate of mobile phase was 0.6 mL/min. Using post column splitting (split ratio3:1), a flow rate of 0.2 mL/min was introduced into the ESI-MS system for detection. The elution flow rate of 0.6 mL/min was better than 0.2 mL/min by increasing sampling rate. UPLC-ESI-MS/MS with post column splitting (0.2 mL/min) provided better sensitivity that of the flow rate 0.6 mL/min without splitting. However, post column splitting did not achieve the sensitivity under 0.2 mL/min without splitting. One possible reason is the limitation in the rate of transferring the ions from ESI source to the mass spectrometer
Fluorescence Red-Shifting of GFP-like Chromophores by Enhancing Electronic Donor-Acceptor Strength
No full text本實驗室過去已發表一系列間位胺基取代類綠螢光蛋白發光團能有效地提高螢光量子產率(m-DMABDI，Φf = 0.46 in n-Hex)，且具有在質子性溶劑中螢光被淬滅的特性，具有潛力應用在即時細胞顯影，這一類的發光團也被成功的應用至人類乳腺上皮細胞(MCF-10A)做細胞顯影，在細胞中呈現綠色螢光。 現階段紅色螢光的類綠螢光蛋白仍相當少見，然而紅色螢光應用在細胞顯影上更具有優勢，本論文的研究動機即為將m-DMABDI做修飾使其放光更加紅移，在結構設計上保留了間位胺基取代效應來提高螢光量子產率以及在非質子、質子性環境中具有螢光量子產率的高度對比差異，期望能得到放光紅移卻且具有高亮度的發光團以利應用於即時細胞顯影。本論文所採用的三個策略分別為：(1)利用互變異構物之放光，在鄰位接上羥基(o-OH)，希望藉由ESIPT(excited-state intramolecularproton transfer)所致的互變異構物使放光紅移；(2)為增強施予體與授體的強度，在鄰位和對位上引入甲氧基(o-OMe及p-OMe)；(3)則是結合延長共軛及加強施予體與授體的強度的方式，以dicyanomethylene此拉電子基團來增強授體的強度且延長共軛(m-DMABDI-2CN)。目前的研究結果顯示出(1) o-OH的放光並非ESIPT造成的互變異構物放光，且其氫鍵會引致螢光焠熄。(2) o-OMe由於具有較強的charge transfer能力，可有效達到紅移的效果，比起m-DMABDI大約紅移50-60 nm。(3)由於p-OMe的基態結構具有明顯meta-amino扭轉的現象，使得meta-amino effect效用降低，以致放光波長紅移效應不佳且螢光量子產率相對較低。Meta-Amino substituted green fluorescence protein chromophores (GFPc) such as m-DMABDI display strong fluorescence in non-polar aprotic solvent (Φf = 0.46 in n-Hex)as a result of “meta-amino substituent effect” but undergo fluorescence quehching in protic solvents due to solvent–solute H-bond interactions. This type of chromophore has been applied on bioimaging, which showed green fluorescence in human mammary epithelial cells.However, fluorescent dyes with green emission maybe interfered by autofluorescence of biological sample. In order to avoid this probleme, developing chromophores of red-shifted emission is necessary. In this thesis, we have three strategies to red-shift the emission of m-DMABDI :(1) introducingo-hydroxyl group into m-DMABDI, to induce tautomer emission throughexcited-state intramolecularproton transfer(ESIPT)(o-OH); (2) introducing strong electron-donating(methoxy)groupinto the donor of m-DMABDIto enhance the push-pull strength of chromophore (o-OMe and p-OMe); (3) introducingelectron-accepting(dicyanomethylene)groupinto the acceptor moiety of m-DMABDIto not only enhance the donor-acceptorstrength but also to extend the conjugation length (m-DMABDI-2CN). Our results show that the emission maximum of o-OMe is red-shifted as compared with that of m-DMABDIby 50-60 nm
The Association between Self and Overgeneral Memory in Individuals with Interpersonal Trauma: Cognitive Coping Style as Moderator
No full text遭遇創傷者常會面臨到自我（即基模）與自傳式記憶的議題。在自我的議題方面，從創傷認知理論的基模觀點，創傷後正向基模被撼動、或負向基模被驗證是PTSD的脆弱因子。而且，過往研究顯示，經歷人際創傷事件對個體的自我衝擊遠較非人際創傷事件大，PTSD症狀也更嚴重。在自傳式記憶的議題方面，遭遇創傷者容易有過度概化記憶的現象。過度概化記憶為提取自傳式記憶時，記憶資訊搜尋提取的階層停留在較抽象、泛化的概念式資訊，難以提取具體特定資訊。根據自我-記憶系統，記憶提取受到自我調控，傾向觸接自我相符的記憶資訊，抑制與自我不相符、或威脅自我的特定資訊。然而，少有實徵研究檢驗過度概化記憶與自我的關聯性。此外，CaR-FA-X模式假設影響過度概化記憶的兩大認知因應風格包括功能性逃避與反芻風格。綜上，本研究以自我-記憶系統為架構，從創傷認知理論的基模觀點及CaR-FA-X模式的認知機制，檢驗人際創傷者之自我與過度概化記憶的關聯性，及反芻與功能性逃避對兩者關係的調節效果。此外，本研究也比較有無人際創傷者在基模與過度概化記憶之差異。本研究參與者包括94名人際創傷者與70名無人際創傷者，以自陳式量表測量正負向基模、反芻、和功能性逃避，並以簡化指導語版自傳式記憶測驗測量過度概化記憶。結果顯示，人際創傷者的正向基模與記憶特定程度呈顯著負相關，功能性逃避對自我與過度概化記憶關係具有調節效果，但反芻風格則無顯著調節效果。比較人際創傷者與無人際創傷者，人際創傷者的正向基模較弱、負向基模較強烈，但兩組的記憶特定程度無顯著差異。額外分析也顯示，無人際創傷者的正向基模與正向記憶特定程度有正相關傾向，負向基模與正向記憶特定程度則有顯著負相關。無人際創傷者的功能性逃避也對自我與過度概化記憶具調節效果。上述結果部分支持自我-記憶系統、創傷認知理論、及CaR-FA-X模式的論述。Trauma survivors may face the disturbance of self (i.e. schema) and autobiographical memory (AM). With regard to the disturbance of self, according to the cognitive theories of PTSD, the shattered self as a result of traumatic events is the risk factor of PTSD. Past studies have showed that the impact of self and PTSD severity may be stronger in interpersonal trauma (IPT) survivors than non-IPT survivors. With regard to AM disturbance, overgeneral memory (OGM) refers to an ability to retrieve AM at the abstract level of AM, but hardly reach at the event-specific level of AM. According to Self-Memory System, the self may guide the retrieval of AM by inhibiting the specific information that is self-incoherent or threatening. However, very few studies have examined the relationship between self and OGM. Additionally, two cognitive coping styles, i.e. rumination and functional avoidance, may play important roles in the development of OGM based on the CaR-FA-X model. Therefore, the aims of the present study were, firstly, to examine the relationship between self and OGM in IPT survivors; secondly, to investigate the moderating effects of rumination and functional avoidance between the above relationship; thirdly, to examine the differences of self and OGM between individuals with and without IPT. There were 94 participants with IPT and 70 participants without IPT in this study. All participants completed self-report measures assessing schema, rumination, and functional avoidance, and autobiographical memory test measuring OGM. Results indicate a negative correlation between the positive schema and specificity of AM in participants with IPT. Functional avoidance, not rumination, moderated the relationship between self and OGM. Furthermore, compared with participants without IPT, participants with IPT had weaker positive schema and stronger negative schema. There was no difference in the level of OGM between those who with and without IPT. Interestingly, additional analysis in participants without IPT showed a marginal positive correlation between positive schema and specificity of positive memory, and a negative correlation between negative schema and specificity of positive memory. Functional avoidance also moderated the relationship between the self and OGM in participants without IPT. The overall results demonstrated the effects of self and cognitive coping styles on OGM in district ways among participants with and without IPT
