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Novel Spiro-Configured PET Chromophores Incorporating 4,5-Diazafluorene Moiety as an Electron Acceptor
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Going Beyond Counting First Authors in Author Co-citation Analysis
Get PDFThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Syntheses, Properties and Applications of Organic Optoelectronic Materials
No full text中文摘要
第一章:我們成功地合成並研究三種不同系列以4,5-diaza-9-9’-spirobifluorene (SB)為主的材料。第一種是利用分子掺雜的觀念,在三聚芴的材料中引入具有高電子親和力的(SB)官能基團，而不會影響寡聚芴分子主鏈的放光行為，因此以TSBT所製備出的元件相較於使用T3的元件具有較低的操作電壓與較高的放光效率。再者，由於在分子主鏈上引入噻吩基團，增加了分子共軛長度，所以TTSBTT的頻譜行為相對於TSBT有紅移的現象。第二種材料是藉由(SB)之高電子親和力，我們將双聚芴(SBT, SBB, SB2)同時做為電子傳導層以及主體材料以簡化磷光元件的製備,結果發現利用SBT所製成的紅光磷光元件之外部量子效率(~10.3%)，幾乎達到紅光掺雜物Btp2Ir(acac)的放光極限。第三種材料是利用SB建構donor-acceptor的系統，由於Cz2SB與TPA2SB的分子構形，在空間上donor與acceptor是互相垂直的關係，造成這兩個分子在基態沒有PET而在激態時有PET作用，而且研究結果顯示PET的效率可以藉由改變分子的不同電子特性來調控。
第二章:我們順利地合成並且探討以SB為配位基的離子性銥錯合物[Ir(ppy)2(SB)]+(PF6─)(橘紅光)與[Ir(dFppy)2(SB)]+(PF6─)(綠光)作為LECs的發光材料。由於SB配位基團提供了不錯的空間阻隔性質，使得利用[Ir(ppy)2(SB)]+(PF6─)以及[Ir(dFppy)2(SB)]+(PF6─)所製備而成的單層薄膜元件具有很不錯的發光效率。再者，我們也更進一步的引入主客體(Host/Guest)的觀念，將具較低階的[Ir(ppy)2(SB)]+(PF6─)(Guest)摻雜在具較高能接的[Ir(dFppy)2(SB)]+(PF6─)(Host)中，利用這樣的概念，並且於適當摻雜濃度下，主客體系統所做出來的元件效率是單純主體或客體元件的1.5倍。
第三章:我們成功地設計且合成出具有高三重態能階的主體材料(T1Si, SP3Cz2, TPA1Si, TPA2Si, CzSi以及TRZSi)並應用於磷光元件上，藉由材料性質分析可以發現，以上這幾個材料的三重態能階(triplet energy)都大於2.61 eV，這樣的能階大小足夠用來當作綠光及藍光磷光元件中的主體材料。以上這些高能階主體材料在熱性質上也有很好的表現(Td > 370 °C, Tg > 105 °C)。研究發現，利用以上幾個高能階材料所製成的元件確實具有很高的元件效率。
第四章:我們發展出一個利用鈴木偶合反應即可簡單且順利地引入分子自組裝單元到共軛分子上的合成方法，並且設計合成出一個一邊具有分子自組裝單元另一邊有硼酯官能基的重要中間體(4-pinacolatoboronic ester-benzenebiuret)。在共聚焦螢光光譜儀的研究下，我們發現在不同摻雜濃度下，兩種材料(OPV-Ph-biuret與T2-Ph-biuret)會自組裝成不同的薄膜型態，接著在掃描式電子顯微鏡的影像中，也發現單純的T2-Ph-biuret會形成球狀的微結構，而OPV-Ph-biuret則是會形成纖維狀的微結構，當兩個材料摻雜在一起時，則發現會有不一樣的型態出現，我們也發現於不同載體的條件下，由於不同載體之表面特性不同，所以兩個材料摻雜之後所形成的微結構也會隨之而改變。Abstract
Chapter 1 : Three series of novel 4,5-diaza-9-9’-spirobifluorene (SB)-incorporated organic materials have been synthesized and characterized. For the SB-incorporated terfluorene materials, we used the molecular doping strategy to introduce 4,5-diaza-9-9’-spirobifluorene (SB) as a functional substituent spirally linked to the conjugated oligofluorene backbone. TSBT exhibits lower device turn-on voltage and higher EQE than that of using T3. Because the conjugated backbone implant with thiophene rings increase the π-conjugation, the spectra of TTSBTT show substantial red shift compared to that of TSBT. Due to the high electron affinity of 4,5-diaza-9,9’-spirobifluorene moiety, SBT, SBB and SB2 were used as the ETL and host materials to simplify the electroluminescence devices. The high EQE (~10.3%) of SBT-simplified device is close to the limit of the emission quantum yield of Btp2Ir(acac) dopant. For the spiro-bridged D-A compound Cz2SB and TPA2SB, the perpendicular arrangement of the donor and acceptor limits the degree of the donor-acceptor interaction in the ground state and allows efficient PET to occur in the excited state. The experimental results show that the efficiency of this PET process was modulated by altering the electronic characteristic of the donor groups.
Chapter 2 : We have reported the syntheses and characterization of two novel cationic iridium complexes, [Ir(ppy)2(SB)]+(PF6─) (orange-red emission) and [Ir(dFppy)2(SB)]+(PF6─) (green emission), for solid-state light-emitting electrochemical cells. The devices using single-layered neat films of [Ir(ppy)2(SB)]+(PF6─) and [Ir(dFppy)2(SB)]+(PF6─) achieve high peak external quantum efficiencies and power efficiencies of (7.1%, 22.6 lm/W) and (7.1%, 26.2 lm/W), respectively. The high efficiencies indicate that the cationic transition metal complexes containing ligands with good steric hindrance (SB) are excellent candidates for highly efficient LECs. Moreover, when we use [Ir(dFppy)2(SB)]+(PF6─) as the host and [Ir(ppy)2(SB)]+(PF6─) as the guest, the host-guest LECs show much enhanced quantum efficiencies (power efficiencies) of up to 10.4% (36.8 lm/W), representing a 1.5X enhancement compared to those of pure host and guest devices.
Chapter 3 : The host materials with high energy gap (T1Si, SP3Cz2, TPA1Si, TPA2Si, CzSi and TRZSi) were synthesized and demonstrated with remarkable properties in the electrophosphorescence. The triplet energies of these host materials were above 2.61 eV in the neat film. In other words, these host materials possessing large triplet energies are suitable for green and blue phosphorescent OLEDs. Moreover, these host materials possess high decomposition temperature above 370 °C and also have high glass transition temperature above 105 °C. The multiple layer devices fabricated with these host materials show highly external quantum efficiency.
Chapter 4 : We developed a straightforward synthesis for introducing self-assembly units into the π-conjugated materials by Suzuki coupling reaction. The novel reagent, 4-pinacolatoboronic ester-benzenebiuret, is an unprecedented building block combining the biuret moiety for recognition function and boronic ester for Suzuki coupling. From the fluorescence confocal microscopy images, the unique morphologies were observed in the mixture of T2-Ph-biuret and OPV-Ph-biuret system with different concentrations. From the scanning electron microscopic (SEM) images, we discovered that T2-Ph-biuret formed globular nanostructure, OPV-Ph-biuret formed fiber nanostructure, and the mixture of 10% doping OPV-Ph-biuret within T2-Ph-biuret gave an irregular morphology on the glass substrates. We ascribed the specific morphology was formed by hydrogen-bonding and/or π-π interactions between OPV-Ph-biuret and T2-Ph-biuret on the substrate surface. Moreover, we observed some special nanostructures on different substrates (ITO and silicon wafer). The change in different shapes could be due to the fact that the surface energies of the substrates are different. In other words, the wetting behavior is different.Contents
口試委員會審定書
謝誌 i
中文摘要 xvi
英文摘要 xviii
contents ii
Index of Figures v
Index of Schemes xiii
Index of Tables xv
Compound Index of Chapter 1 2
Compound Index of Chapter 2 56
Compound Index of Chapter 3 104
Compound Index of Chapter 4 155
Chapter 1. 4,5-Diazafluorene-incorporated Organic Materials 1
1.1 Introduction 3
1.2 Design and Synthesis of 4,5-Diazafluorene-incorporated Organic Materials 8
1.2.1 Design of 4,5-Diazafluorene-incorporated Organic Materials 8
1.2.2 Synthesis of 4,5-Diazafluorene-incorporated Organic Materials 11
1.3 Results and Discussions 19
1.3.1 Photophysical and Thermal Properties 19
1.3.2 Electrochemical Properties 26
1.3.3 Electroluminescent Properties 31
1.4 Conclusions 37
1.5 Experimental Section 38
1.6 References 51
Chapter 2. Solid-State Light-Emitting Electrochemical Cells Based on Cationic Ir(III) Complexes.55
2.1 Introduction 56
2.2 Design and Synthesis of cationic Ir(III) complexes 66
2.2.1 Design of the cationic Ir(III) complexes 66
2.2.2 Synthesis of the cationic Ir(III) complexes 68
2.3 Results and Discussions 69
2.3.1 Photophysical Properties 69
2.3.2 Electrochemical Properties 79
2.3.3 Electroluminescent Properties 81
2.3.4 Single crystal x-ray structure 92
2.4 Conclusions 94
2.5 Experimental Section 95
2.6 References 100
Chapter 3. The Host Materials with High Energy Gap 103
3.1 Introduction 105
3.2 Design and Synthesis of the host materials with high energy gap 110
3.2.1 Design of the host materials with high energy gap110
3.2.2 Synthesis of the host materials with high energy gap 112
3.3 Results and Discussions 118
3.3.1 Photophysical and Thermal Properties 118
3.3.2 Electrochemical Properties 128
3.3.3 Electroluminescent Properties 130
3.4 Conclusions 144
3.5 Experimental Section 145
3.6 References 152
Chapter 4. Biuret-contained Oligo(π-conjugated materials) 154
4.1 Introduction 156
4.2 Design and Synthesis of the materials 158
4.3 Results and Discussions 171
4.4 Conclusions 182
4.5 Experimental Section and Synthetic Procedure 182
4.6 References 188
1H NMR Spectrum 190
Index of Figures
Figure 1-1. Molecular structures of the homologous oligofluorenes. 4
Figure 1-2. Molecular structures of 9,9-spirobifluorene configured bifluorenes. 5
Figure 1-3. Molecular structures of TPPy and rubrene. 7
Figure 1-4. Molecular structures of the novel spiro-configured D-A systems. 8
Figure 1-5. Molecular structures of 4,5-diaza-9,9’-spirobifluorene-incorporated terfluorene-type materials.
10
Figure 1-6. Molecular structures of 4,5-diaza-9,9’-spirobifluorene-incorporated bifluorene-type materials.
11
Figure 1-7. Molecular structures of 4,5-diaza-9,9’-spirobifluorene moiety as an electron acceptor.
11
Figure 1-8. The retrosynthesis of 4,5-diaza-9,9’-spirobifluorene-incorporated terfluorene-type materials.
12
Figure 1-9. The retrosynthesis of 4,5-diaza-9,9’-spirobifluorene-incorporated bifluorene-type materials.
14
Figure 1-10. The retrosynthesis of 4,5-diazafluprene moiety as an electron acceptor. 18
Figure 1-11. Comparisons of absorption and photoluminescence of TSBT, BSBB, and TTSBTT in solution.
21
Figure 1-12. Absorption and photoluminescence spectra of SBT, SBB, and SB2 in solution. 22
Figure 1-13. Comparisons of absorption and photoluminescence spectra of Cz2SB and TPA2SB in solution.
23
Figure 1-14. Solvent-dependent emission spectra of Cz2SB and TPA2SB. 25
Figure 1-15. Absorption spectra of Cz2SB and TPA2SB in different solvents. 26
Figure 1-16. Cyclic voltammagrams of TS3, TTSBTT, TSBT, and T3. 28
Figure 1-17. Cyclic voltammagrams of SBT, SBB, and SB2. 29
Figure 1-18. Cyclic voltammagrams of TPA2SB. 30
Figure 1-19. L-V and I-V characteristics of TSBT. 33
Figure 1-20. External EL quantum efficiency vs current of TSBT. 33
Figure 1-21. L-V and I-V characteristics of SBT, SBB, and SB2 (LiF as EIL). 35
Figure 1-22. EQE vs current density of SBT, SBB, and SB2 (LiF as EIL). 36
Figure 1-23. L-V and I-V characteristics of SBT, SBB, and SB2 (CsCO3 as EIL). 36
Figure 1-24. EQE vs current density of SBT, SBB, and SB2 (CsCO3 as EIL). 37
Figure 2-1. The operating mechanism diagram of the solid- state light-emitting electrochemical cells. 57
Figure 2-2. The first solid-state electroluminescent device formed an ionic transition metal complexes by the MIT group. 60
Figure 2-3. Adding different alkyl substituents on the biphenyl ligands to inhibit self-quenching. 61
Figure 2-4. Efficient yellow electroluminescence from a single layer of a cyclometalated iridium (III) complex. 63
Figure 2-5. Improvement of the response time by using the ionic liquid with the green electroluminescence iridium (III) complex. 64
Figure 2-6. Blue, green and red electroluminescence devices based on cationic phenylpyrazole-based iridium (III) complexes. 65
Figure 2-7. Absorption, PL spectra in acetonitrile solution and in the neat films and EL in the neat films of [Ir(ppy)2(SB)]+(PF6─). 72
Figure 2-8. Absorption, PL spectra in acetonitrile solution and in the neat films and EL in the neat films of [Ir(dFppy)2(SB)]+(PF6─). 72
Figure 2-9. The absorption spectrum of the neat guest film and PL spectra of host-guest films with various guest concentrations (without [BMIM+(PF6─)]). 73
Figure 2-10. (a) Photoluminescence quantum yield and (b) excited-state lifetimes as a function of the guest doping concentration for host-guest films with and without [BMIM+(PF6─)] (19%). 79
Figure 2-11. Cyclic voltammograms of [Ir(ppy)2(SB)]+(PF6─) and [Ir(dFppy)2(SB)]+(PF6─) Potentials were recorded versus the reference electrode Ag/AgCl (sat’d).
81
Figure 2-12. 3D AFM micrographs of (a) neat films of [Ir(ppy)2(SB)]+(PF6─) (b) blend film of [BMIM+(PF6─)] and [Ir(ppy)2(SB)]+(PF6─) (0.75 : 1, molar ratio) (c) neat film of [Ir(dFppy)2(SB)]+(PF6─) (d) blend film of [BMIM+(PF6─)] and [Ir(dFppy)2(SB)]+(PF6─) (0.75 : 1, molar ratio). 83
Figure 2-13. The time-dependent brightness and current density of the single-layered LEC device for (a) [Ir(ppy)2(SB)]+(PF6─) driven at 2.6 or 2.5 V, and (b) [Ir(dFppy)2(SB)]+(PF6─) driven at 2.9 or 2.8 V. 85
Figure 2-14. The time-dependent EQE and the corresponding power efficiency of the single-layered LEC device for (a) [Ir(ppy)2(SB)]+(PF6─) driven at 2.6 or 2.5 V , and (b) [Ir(dFppy)2(SB)]+(PF6─) driven at 2.9 or 2.8 V. 88
Figure 2-15. (a) Brightness (solid symbols) and current density (open symbols) and (b) EQE (solid symbols) and power efficiency (open symbols) as a function of time under a constant bias voltage of 2.5-2.7 V for the host-guest LEC with host, guest and [BMIM+(PF6─)] concentration of 56, 25 and 19wt.%, respectively. 89
Figure 2-16. (a) Maximum current density vs. voltage characteristics for LECs with various guest concentration. Inset of (a): the energy level diagram of the host and guest. (b) EL spectra (at 2.8 V) for LECs with various guest concentrations. 90
Figure 2-17. Peak external quantum efficiencies and peak power efficiencies (at current densities < 0.1 mA/cm2) of gost-guest LECs as a function of the guest concentration. 91
Figure 2-18. The molecular structure of [Ir(ppy)2(SB)]+. The ellipsoids are drawn at the 50% probability. 93
Figure 2-19. Crystal packing of [Ir(ppy)2(SB)]+(PF6─) in a unit cell. The solvent molecules, counter anions (PF6─), and hydrogen atoms are omitted for clarity. 94
Figure 3-1. The chemical structure of Ir complex derivatives Ir(ppy)3, FIrpic, and FIr6. 105
Figure 3-2. The chemical structure of common host materials CBP, CDBP, mCP, and TRZ2. 107
Figure 3-3. The Carbazole-Fluorene nonconjugated hybrid host material. 108
Figure 3-4. The structure of high energy gap tetraarylsilane compounds. 110
Figure 3-5. The chemical structure of the host materials with high energy gap (T1Si, SP3Cz2, TPA1Si, TPA2Si, CzSi, and TRZSi) in this study. 112
Figure 3-6. The retrosynthesis of the SP3Cz2. 113
Figure 3-7. Absorption, fluorescence and phosphorescence spectra of the T1Si in solution and neat film. 119
Figure 3-8. Absorption, fluorescence and phosphorescence spectra of the SP3Cz2 in solution and neat film. 121
Figure 3-9. Absorption, fluorescence and phosphorescence spectra of the TPA1Si in solution and neat film. 122
Figure 3-10. Absorption, fluorescence and phosphorescence spectra of the TPA2Si in solution and neat film. 123
Figure 3-11. Absorption, fluorescence and phosphorescence spectra of the CzSi in solution and neat film. 124
Figure 3-12. Absorption, fluorescence and phosphorescence spectra of the TRZSi in solution and neat film. 125
Figure 3-13. Cyclic voltammagrams of the host materials (T1Si, SP3Cz2, TPA1Si, TPA2Si, CzSi, and TRZSi) in this study. Potentials were recorded versus the reference electrode Ag/AgCl (sat’d). 129
Figure 3-14. The chemical structure of DPAS, TCTA, Alq, TAZ, BCP and TPBI. 132
Figure 3-15. I-V-B characteristic of device A, B, and C by using T1Si as host material and Ir(ppy)3 as the guest. 132
Figure 3-16. EL quantum efficiency as a function of current density for device A, B, and C by using T1Si as host material and Ir(ppy)3 as the guest. 133
Figure 3-17. I-V-B characteristic of device A, B, and C by using T1Si as host material and FIrpic as the guest. 134
Figure 3-18. EL quantum efficiency as a function of current density for device A, B, and C by using T1Si as host material and FIrpic as the guest. 135
Figure 3-19. I-V-B characteristic of device A, B, and C by using SP3Cz2 as host material and FIrpic as the guest. 136
Figure 3-20. EL quantum efficiency as a function of current density for device A, B, and C by using SP3Cz2 as host material and FIrpic as the guest. 136
Figure 3-21. I-V-B characteristic of device A, B, and C by using TPA1Si as host material and FIrpic as the guest. 137
Figure 3-22. EL quantum efficiency as a function of current density for device A, B, and C by using TPA1Si as host material and FIrpic as the guest. 138
Figure 3-23. I-V-B characteristic of device A, B, and C by using CzSi as host material and Ir(ppy)3 as the guest. 139
Figure 3-24. EL quantum efficiency as a function of current density for device A, B, and C by using CzSi as host material and Ir(ppy)3 as the guest. 139
Figure 3-25. I-V-B characteristic of device A, B, and C by using CzSi as host material and FIrpic as the guest. 141
Figure 3-26. EL quantum efficiency as a function of current density for device A, B, and C by using CzSi as host material and FIrpic as the guest. 141
Figure 3-27. I-V-B characteristic of device A, B, and C by using TRZSi as host material and FIrpic as the guest. 142
Figure 3-28. EL quantum efficiency as a function of current density for device A, B, and C by using TRZSi as host material and FIrpic as the guest. 143
Figure 4-1. Supramolecular architectures formed by hydrogen bonding. 158
Figure 4-2. The cartoon of π-conjugated materials with self-assembly unit. 159
Figure 4-3. The structures of some self-assembly units with oligofluorene. 159
Figure 4-4. Proposed linear ribbons structure established by hydrogen bonding. 161
Figure 4-5. The proposed structure of non-self-complementary hydrogen-bonding motifs present in melamine-barbituric acid assemblies 166
Figure 4-6. The proposed structure of biuret-contained fluorene derivatives and supramolecular architectures formed by biuret units. 169
Figure 4-7. Absorption and fluorescence spectra in THF at 10-5 M concentration. 173
Figure 4-8. Fluorescence confocal microscopy image of mixtures of a donor (1a and T2-Ph-biuret) and an acceptor (2a and OPV-Ph-biuret); λex = 385 nm, APD detector in green channel (top series 1% acceptor doping in donor, bottom series 10% acceptor doping in donor). 175
Figure 4-9. Fluorescence confocal microscopy image of T2-Ph-biuret spin-coated film with different mol % OPV-Ph-biuret (1.0, 5.0, 7.5, 10.0%, respectively); λex = 385 nm (top series in blue channel, bottom series in green channel). 176
Figure 4-10. SEM images of T2-Ph-biuret on a glass subatrate. 177
Figure 4-11. SEM images of OPV-Ph-biuret on a glass substrate (more concentrated area). 178
Figure 4-12. SEM images of OPV-Ph-biuret on a glass substrate (less concentrated area). 178
Figure 4-13. SEM images of 10% doping of OPV-Ph-biuret in T2-Ph-biuret. 179
Figure 4-14. Dynamic light scattering analysis of T2-Ph-biuret and OPV-Ph-biuret. 180
Figure 4-15. SEM images of 10% OPV-Ph-biuret / 90% T2-Ph-biuret on an ITO. 181
Figure 4-16. SEM images of 10% OPV-Ph-biuret / 90% T2-Ph-biuret on silicon wafer. 181
Index of Schemes
Scheme 1-1. The synthesis of TSBT, BSBB, and TTSBTT, respectively. 14
Scheme 1-2. The synthesis of 4,5-diaza-2’-iodo-9,9’-spirobifluorene (1-16) and the corresponding pinacolato boronic ester (1.17). 16
Scheme 1-3. The synthesis of SBT, SBB, and SB2. 17
Scheme 1-4. The synthesis of Cz2SB and TPA2SB. 19
Scheme 2-1. Synthetic pathways and structure of [Ir(ppy)2(SB)]+(PF6─) and [Ir(dFppy)2(SB)]+(PF6─). 69
Scheme 3-1. The retrosynthesis and synthetic pathway of the T1Si. 112
Scheme 3-2. The synthetic pathway of the SP3Cz2. 114
Scheme 3-3. The retrosynthesis and synthetic pathway of the TPA1Si. 115
Scheme 3-4. The retrosynthesis and synthetic pathway of the TPA2Si. 116
Scheme 3-5. The retrosynthesis and synthetic pathway of the CzSi. 117
Scheme 3-6. The retrosynthesis and synthetic pathway of the TRZSi. 118
Scheme 4-1. The synthesis of fluorene derivatives. 160
Scheme 4-2. The synthesis of 4,6-diaminopyrimidine-2-thione unit. 162
Scheme 4-3. The synthesis of 4,6-diaminopyrimidine-2-thione connected with methylene group spacer.
163
Scheme 4-4. Another approach of T2 containing 4,6-diaminopyrimidine-2-thione connected with a methylene group spacer. 164
Scheme 4-5. An alternative strategy of preparing the T2 containing 4,6-diaminopyrimidine-2-thione by Suzuki coupling. 165
Scheme 4-6. The synthesis of T2 containing barbituric acid with fluorene derivatives (4.5). 167
Scheme 4-7. The synthesis of T2 containing barbituric acid with fluorene derivatives (4.18). 168
Scheme 4-8. The synthetic pathway of the key intermediate, compound (4.20). 170
Scheme 4-9. The synthetic pathway of T2-Ph-biuret, OPV-Ph-biuret and compound (4.23). 171
Scheme 4-10. The synthetic pathway of model compounds 1a and 2a. 171
Index of Tables
Table 1-1. The UV-Vis absorption spectra, fluorescent spectra, electrochemical properties and thermal properties of 4,5-diaza-9,9’-spirobifluorene-incorporated materials. 31
Table 2-1. Summary of physical properties of [Ir(ppy)2(SB)]+(PF6─) and [Ir(dFppy)2(SB)]+(PF6─). 77
Table 2-2. Summary of the LEC device characteristics based on [Ir(ppy)2(SB)]+(PF6─) and [Ir(dFppy)2(SB)]+(PF6─). 84
Table 3-1. Photophysical data for T1Si, SP3Cz2, TPA1Si, TPA2Si, CzSi and TRZSi. 127
Table 3-2. Thermal property of T1Si, SP3Cz2, TPA1Si, TPA2Si, CzSi and TRZSi. 128
Table 3-3. The electrochemical properties and energy level (LUMO/HOMO) of the host materials (T1Si, SP3Cz2, TPA1Si, TPA2Si, CzSi, and TRZSi) in this study. 130
Table 3-4. The maximum brightness and EL quantum efficiency by using the host materials with high energy gap and [Ir(ppy)3] or FIrpic as the guest. 144
Table 4-1. Photophysical parameters for compounds in THF. 17
Variations on the Author
Get PDF“Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship
Appropriate Similarity Measures for Author Cocitation Analysis
Get PDFWe provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
The Molecular Structures, Expression Patterns, and Promoter Analysis of Zebrafish Troponin I Genes
No full text抑制型肌鈣蛋白(TnnI)是位於橫紋肌細肌絲中對細肌絲的收縮提供鈣離子轉換的一個肌鈣蛋白複合體組成。臨床上在急性冠狀動脈病徵下，心臟型TnnI在脊椎動物中被當作具有高敏感性及專一性的指標。
雖然在鳥類及哺乳類中，已經確立存在三種不同異購蛋白的TnnI，分別是快肌型、心肌型、及慢肌型。但在低等脊椎動物中，對於TnnI基因的了解並未十分透徹。為了更了解在低等脊椎動物中TnnI在發育調控上所扮演的地位。首先，我們先區別了斑馬魚的TnnI基因，TnnI1及TnnI2。在脊椎動物TnnI的基因演化樹中，TnnI1及TnnI2分別相近於脊椎動物的TnnI1(slow muscle)及TnnI2(fast muscle)。在反轉錄聚合酶連鎖反應及全胚胎原位雜交法來進行觀察，結果顯示出在受精後16小時，TnnI1及TnnI2會開始表現在斑馬魚體節的部位，此外在軀幹橫切顯示出TnnI1及TnnI2是分別專一表現在慢肌及快肌，藉由這些結果來分別定義了TnnI1及TnnI2分別為斑馬魚慢肌型TnnI及快肌型TnnI。另外我們也定義了一個新的TnnI 異構型蛋白，TnnI-HC，我們觀察到TnnI-HC會表現在早期的cardiogenesis (16 hpf)，且會持續在心臟專一性表現。有趣的是，在48hpf之後便會開始在頭部肌肉及心臟表現，雖然TnnI-HC較相似於慢肌型 TnnI，但卻會在心臟及頭部肌肉中有表現，這種TnnI異構型蛋白表現情形是不同於其他高等脊椎動物。所以我們利用斑馬魚基因庫來篩選TnnI-HC大約7.6-Kb的上游片段，藉由此片段可以來分析TnnI-HC在斑馬魚中的發育調控。我們選殖了兩段斑馬魚TnnI-HC上游序列1.4-Kb (-1400/+30)及intron 1 4-Kb (+2257/+6253)，並分別構築了EGFP表現質體並進行顯微注射。我們發現到1.4-Kb的上游序列並沒有啟動子的能力，然而當注射intron 1 4-Kb，能觀察到intron 1 4-Kb能夠獨自驅動EGFP在心臟及軀幹中表現。由此我們假設在TnnI-HC其他上游序列中仍有其他位置能夠來加強頭部肌肉的表現及抑制體節的表現。利用deletion analysis來分析intron 1 4-Kb的序列後。我們可以定義在intron 1 (+2257/+4689)中，具有一個cis-element能夠來調控早期斑馬魚TnnI-HC基因在心臟中的表現。Troponin I (TnnI), a constituent of the troponin complex on the thin filament, provides a calcium-sensitive switch for striated muscle contraction. Cardiac TnnI is a highly sensitive and specific marker of myocardial injury in the acute coronary syndromes. Although TnnI gene has been identified in birds and mammals as it encodes the isoforms expressed in cardiac muscle, fast skeletal muscle and slow skeletal muscle, there is extremely little known about the developmental regulation of TnnI gene in the lower vertebrates. Firstly, we characterized zebrafish TnnI genes, TnnI1 and TnnI2. In the unrooted radial gene tree for TnnI genes among vertebrates, the zebrafish TnnI1 and TnnI2 genes we cloned correspond to the slow muscle TnnI1 gene and the fast muscle TnnI2 gene of other vertebrates, respectively. Secondly, reverse transcription-polymerase chain reaction (RT-PCR) and whole-mount in situ hybridization showed that TnnI1 and TnnI2 transcripts were expressed in the somites at 16 hours post-fertilization (hpf). In addition, we also demonstrated that the expression of TnnI1 and TnnI2 genes was slow- and fast-muscle-specific, respectively, indicating that zebrafish TnnI1 and TnnI2 proteins were slow-TnnI and fast -TnnI, respectively. Interestingly, we also identified a novel TnnI isoform, TnnI-HC (heart and craniofacial), which was expressed in the heart exclusively during early cardiogenesis at 16 hpf, but it was not only in the craniofacial muscle but also in the heart after 48 hpf. Thirdly, in order to go further understanding the regulatory mechanism of TnnI-HC gene, we cloned a 7.6-kb fragment containing a partial TnnI-HC genomic gene from the zebrafish genomic library. Thereafter, we subcloned an upstream 1.4-Kb (from -1400 to +30; -1400/+30) and an intron 1 4-Kb (from +2257 to +6253; +2257/+6253) and we fused them with GFP separately. After microinjection, we found that the -1.4 Kb fragment did not contain any promoter activity. However microinjection of an intron 1 fragment (4-Kb) alone without including -1.4 Kb enabled the expression of GFP in the heart and trunk muscle, but not in the craniofacial muscle. Thus, we speculate that other upstream regulatory segment might play a role in the enhancing the craniofacial muscle expression and repressing the trunk expression of TnnI-HC gene. Deletion analysis in +2257/+6253 segment, we also identified a cis-element located at +2257/+4689 within intron 1 that might control the cardiac expression of zebrafish TnnI-HC gene during early development.中 文 摘 要-------------------------------- 1
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Dispelling the Myths Behind First-author Citation Counts
Get PDFWe conducted a full-scale evaluative citation analysis study of scholars in the XML research field to explore just how different from each other author rankings resulting from different citation counting methods actually are, and to demonstrate the capability of emerging data and tools on the Web in supporting more realistic citation counting methods. Our results contest some common arguments for the continued
use of first-author citation counts in the evaluation of scholars, such as high correlations between author rankings by first-author citation counts and other citation
counting methods, and high costs of using more realistic citation counting methods that are not well-supported by the ISI databases. It is argued that increasingly available digital full text research papers make it possible for citation analysis studies to go beyond what the ISI databases have directly supported and to employ more
sophisticated methods
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