四氟乙烯等离子体聚合反应的基础研究

[I] 等离子体聚四氟乙烯的ESCA表征 本研究采用外部电容耦合式聚合装置，频率为13.56MHz，合成了等离子体聚四氟乙烯（PPTFE）。应用ESCA表征了辉光压和非辉光压产物的结构，同时应用CNDO进到了理论计算。结果表明，在辉光压上非辉光压中制得的PPTFE结构差别很大。非辉光内淀积物结构亦现差异。辉光压内的PPTFE是高度支化交联的，在本实验的典型反应条件下，PPTFE的F/C比为1.42，Gs区五个峰确定归属后，各主要对应基团的相对组成约为：CF_3－21%、CF_2－32%、CF－22%、－C from | to | of — 20%，其余为少量的CFH、CH_2（II）、CH_2（I）。在非辉光压内可得到近於线线型的PPTFE，其F/C为2.08，端基CF_3约占15%，CF_2占78%，代表支化交联的基团CF、－C from | to | of －皆为零，另外应用X射线衍射法证实，在非辉光压中形成的PPTFE具有类似于聚四氟乙烯的（PTFE）结晶，这一实验结果至今未见文献报导。深入分析这一结果，并运用ESR、MS、~(19)F－NMR等表征手段，进一步提出四氟乙烯等离子体聚合反应机理。这方面在[II]中论述。本工作提出五类十三种模型化合物，并运用Siegbahn的电荷电位模型同时结合使用CNDO/2电子计算机程序；还运用Pauling价键模型，分别应用这两种理论方法，计算了PPTFE中ClS结合能位移（ΔEi），所得结果相近，从而为ClS区五个峰的归属提供理论依据。五个峰归属为：(1) 284.7(ev) － CH_2(I)，(2) 287.0(ev) － －C from | to | of －、CH_2(II)，(3) 289.0(ev) －CF、CFH，(4) 291.5(ev) － CF_2，(5) 293.6(ev) － CF_3。通过对模型化合物中ClS的ΔEi计算结果，推导出F作为α、β、γ位碳上的取代基对α位碳上IS电子结合能位移影响所产生的效应值，并初步总结出表达这种效应的经验式：ΔEi ＝ aα ＋ bβ ＋ cγ式中α、β、γ分别为2.23 ± 0.08(ev)、0.27 ± 0.02(ev)、0.20 ± 0.02(ev)，a、b、c为取代基F的个数。实验结果还证明，淀积位置、功率、压力、等离子气体如Ar、He、N_2等反应条件对PPTFE膜结构有影响，并应用能量梯度解释这种影响；另外发现，同功率、同压力但不同淀积位置上以及同淀积位置但不同功率或不同压力时的PPTFE膜结构所受能量梯度的影响。本工作根据等离子体聚四氟工烯结构的表征结果，并结合ESR、MS等有关分析数据，提出了PPTFE的结构模型。[II] 等郭子体聚四氟乙烯的反应机理 鉴于等离子体聚合反应的复杂性，目前对等离子体聚合反应机理争论较大，其焦点是：反应的活性中心是离子还是自由基；反应地点是在气相还是在反应体系的固体表面。本工作通过对等离子体聚四氟乙烯气相产物的研究证实：等离子体聚合反就是通过自由基历程，引发和初级链增长主要在气相，脱F和支化交联反应在表面上进行。聚合反应装置同[I]中所述，聚合条件是功率60瓦，压力1 * 10~(-1)乇。通过液氟冷阱收集气相生成物，然后制备成有机溶液和本体溶液。气相生成物的ESR分析结果表明，PPTFE膜中存在自由基浓度约在10~(18)自旋数／克，峰形为一条反对称吸收线，宽为175G，g值是2.005。气相生成物的丙酮、苯、环已烷、已烷等有机溶液的ESR谱相同，皆为20条精细结构分裂谱线。另外，通过一系列实验，检测了桔黄色本体溶液的ESR谱，终于得到具有160条超精细结构的分裂谱线，自由基浓度高达10~(20)自旋数／克。初步认为是几种自由基的混合物，固谱图十分复杂，目前解谱尚有困难，需进一步研究。等高子体气相生成物中有大量自由基并且得到其精细和超精细分裂谱线，这一实验结果至今未见文献报导。这个结果进一步证实了聚合反应的活性中心主要是自由基。考察了PPTFE膜的自由基在90 ℃时随时间变化的ESR谱，发现一开始衰减很快；研究了PPTFE膜的自由基在不同气氛下常温衰减情况，结果指出：辉光压和非辉光压的PPTFE膜中自由基在空气中衰减快，辉光压的PPTFE膜中自由基在真空中及单体气氛中衰减缓慢。气相生成物的有机溶液在90 ℃时随时间变化的ESR谱表明，各峰衰减速率不同，证实并非一种自由基，溶液的自由基能与吡啶反应生成棕红色物质，可能是吡啶盐。本实验用GC－MS联用对气相冷凝物本体溶液进行了分析，比文献上只用MS与聚合反应体系联用分析气相混合物的方法，对分析反应机理提供更为有说服力的实验结果。结果表明，四氟乙烯等离子体聚合的气相生成物是直链的全氟烷烃（分子中碳原子数为C_3－C_8），还有含碳原子数为C_4、C_5、C_6、C_8全氟环烷烃，也可能是括分子链两端是自由基的直链全氟烷烃，还有二氟卡宾。从TFE等离子体聚合的气相中产生齐聚物及其结构特征，可以推断气相中发生了链引发反应和初级增长反应，引发反应的历程首先是TFE单体分子中π键断裂，其次是C~σ-C的σ键均裂，然后通过自由基的复合或诱导反应进行链的初级增长反应。还进行了气相生成物有机溶液的~(19)F－NMR分析，其结果初步看来与GC－MS的结果相一致。还探索了不同条件下在非辉光压内得到的PPTFE膜，进一步表明，在顺着气流方向的淀积位置上的膜结构是接近线型的。这个结果与用质谱、核磁的表征结果相符：从不用方面证实了上述反应历程。此外，通过对PPTFE及PTFE在Ar等离子体系中的刻蚀实验，表明了聚合膜上发生六量脱F反应。由这个结果并结合PPTFE膜及气相产物的结构表征，可以推测到PPTFE膜的支化，交联是通过表面反应进行的。综合四氟乙烯等离子体聚合反应机理的讨论，本论文建议了TFE的等离子体聚合反应历程模型。

Synthesis of nickel(II) complexes of alpha-isoxazolylazo-beta-diketones and their absorption of spin-coating films and thermal properties for HD-DVD-R

Three kinds of new nickel(II) complexes of alpha-isoxazolylazo-beta-diketones with blue-violet light absorption were synthesized. Their structures were postulated based on elemental analysis, MS and FT-IR spectra. Smooth films on K9 glass substrates were prepared using the spin-coating method. The absorption properties and thermal stability of these complexes were discussed. The static optical recording test for high density digital versatile disc-recordable (HD-DVD-R) system was also studied. (c) 2005 Elsevier B.V. All rights reserved.

Spectroscopic and thermal properties of short wavelength metal (II) complexes containing alpha-isoxazolylazo-beta-diketones as co-ligands

Two new azo dyes of alpha-isoxazolylazo-beta-dilcetones and their Ni(II) and Cu(II) complexes with blue-violet light wavelength were synthesized using a coupling component, different diazo components and metal (II) ions (Ni2+ and Cu2+). Based on the elemental analysis, MS spectra and FT-IR spectral analyses, azo dyes were unequivocally shown to exist as hydrazoketo and azoenol forms which were respectively obtained from the solution forms and from the solid forms. The action of sodium methoxide (NaOMe) on azo dyes in solutions converts hydrazoketo form into azoenol form, so azo dyes are coordinated with metal (II) ions as co-ligands in the azoenol forms. The solubility of all the compounds in common organic solvents such as 2,2,3,3-tetrafluoro-1-propanol (TFP) or chloroform (CHCl3) and absorption properties of spin-coating thin films were measured. The difference of absorption maxima from the complexes to their ligands was discussed. In addition, the TG analysis of the complexes was also determined, and their thermal stability was evaluated. It is found that these new metal (II) complexes had potential application for high-density digital versatile disc-recordable (HD-DVD-R) system due to their good solubility in organic solvents, reasonable and controllable absorption spectra in blue-violet light region and high thermal stability. (c) 2004 Elsevier B.V. All rights reserved.

Synthesis, spectroscopic and thermal properties of nickel (II)-azo complexes with blue-violet light wavelength

A novel azo dye containing isoxazole ring and beta-diketone derivative (TIAD) and its two nickel (II) complexes (Ni (II)-ETIAD and Ni (II)-HTIAD) were synthesized in order to obtain a blue-violet light absorption and better thermal stability as a promising organic storage material for next generation of high density digital versatile disc-recordable (HD-DVD-R) systems that uses a high numerical aperture of 0.85 at 405 nm wavelength. Their structures were confirmed on the basis of elemental analysis, MS, FT-IR, UV-Vis and magnetic data. Their solubility in 2,2,3,3-tetrafluoro-1-propanol (TFP) and absorption properties of thin film were measured. The difference of absorption maximum from the complexes to their ligands was discussed. In addition, the TG analysis of the complexes was also determined, and their thermal stability was evaluated. (C) 2004 Elsevier Ltd. All rights reserved.

Synthesis, spectroscopic properties and thermal stability of metal(II) tetraazaporphyrin complexes with two strong wavelength absorption

Three kinds of metal(II) tetraazaporphyrin complexes with blue-violet and red light wavelength absorption were synthesized by refluxing tetraazaporphyrin ligand and different metal(II) ions, respectively. Their structures were confirmed by elemental analysis, LDI-TOF-MS, FT-IR and UV-Vis. The solubility of metal(II) tetraazaporphyrin complexes in organic solvents and absorption properties of their chloroform solution and films on K9 glass in the region 250-800 nm were measured. The influence on the difference of absorption maximum from metal(II) tetraazaporphyrin complexes to tetraazaporphyrin ligand by different metal(II) ions was studied. In addition, the thermal stability of the complexes was also evaluated. (c) 2006 Elsevier Ltd. All rights reserved.

Synthesis, spectral, and thermal characterizations of Ni(II) and Cu(II) beta-diketone complexes with thenoyltrifluoroacetone ligand

Two kinds of nickel(II) and copper(II) P-diketone complexes derived from thenoyltrifluoroacetone ligand with blue-violet light absorption were synthesized by reacting free ligand and different metal(II) ions in sodium methoxide solution. Their structures were postulated based on elemental analysis, ESI-MS, FT-IR spectra and UV-vis electronic absorption spectra. Smooth films on K9 glass substrates were prepared using the spin-coating method. Their solubility in organic solvents, absorption properties of thin film and thermal stability of these complexes were evaluated. (c) 2006 Elsevier B.V. All rights reserved.

Spectroscopic, and thermal studies of some new binuclear transition metal(II) complexes with hydrazone ligands containing acetoacetanilide and isoxazole

A new chelating ligand, 2-(2-(5-tert-butylisoxazol-3-yl)hydrazono)-N-(2,4-dimethylphenyl)-3-oxobutanamide (HL), and its four binuclear transition metal complexes, M-2(L)(2) (mu-OCH3)(2) [M = Ni(II), Co(II), Cu(II), Zn(II)], were synthesized using the procedure of diazotization, coupling and metallization. Their structures were postulated based on elemental analysis, H-1 NMR, MALDI-MS, FT-IR spectra and UV-vis electronic absorption spectra. Smooth films of these complexes on K9 glass substrates were prepared using the spin-coating method and their absorption properties were evaluated. The thermal properties of the metal(II) complexes were investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC. Different thermodynamic and kinetic parameters namely activation energy (E

Nickel(II) and copper(II) complexes containing 2-(2-(5-substitued isoxazol-3-yl)hydrazono)-5,5-dimethylcyclohexane-1,3-dione ligands: Synthesis, spectral and thermal characterizations

Two new hydrazone chelating ligands, 2-(2-(5-methylisoxazol-3-yl)hydrazono)-5,5-dimethylcyclohexane-1,3-dione (HL1) and 2-(2-(5-tert-butylisoxazol-3-yl)hydrazono)-5,5-dimethylcyclohexane- 1,3-dione (HL2), and their nickel(II) and copper(II) complexes were synthesized using the procedure of diazotization, coupling and metallization. Their structures were postulated based on elemental analysis, H-1 NMR, ESI-MS, FT-IR spectra and UV-vis electronic absorption spectra. Smooth films of these complexes on K9 glass substrates were prepared using spin-coating and their absorption properties were evaluated. The thermal properties of the metal(II) complexes were investigated by thermogravimetry (TG) and differential thermogravimetry (DTG). Different thermodynamic and kinetic parameters namely activation energy (E

高温胁迫对螺旋藻光系统II影响的研究

高温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。光系统II（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。高温胁迫对螺旋藻PSII的研究相对较少，对PSII受体侧的研究更加少了。我们借助热致发光及QA-再氧化动力学，这两种检测完整光合生物PSII供体侧和受体侧电子传递的有效、简单、无损伤的方法，为高温胁迫如何影响供体侧和受体侧的电子传递提供更直接的依据，获得高温胁迫对PSII功能影响的更精确的消息。另外，有关螺旋藻在高温胁迫下的能量传递过程研究较少，希望在荧光光谱研究的结果上探求其对高温胁迫的适应机理。主要研究结果如下： 1.高温胁迫抑制螺旋藻PS II的活性， PSII原初光能转化效率Fv/Fm随处理温度的提高而下降。高温去除后Fv/Fm可以得到部分恢复（5-15%）。 2.高温胁迫对闪光诱导的可变荧光衰减动力学有显著影响，分别代表QA-到QB 的直接电子传递和PQ分子扩散到空的QB位点后QA-到QB电子传递的快相(半衰期160 ms)和中相(半衰期2 ms)占整个可变荧光的比例，随处理温度的升高显著降低，而代表S2QA- 电荷重组的慢相（半衰期约4s）显著增加。显示高温导致QA到QB的电子传递以及PQ与QB位点的结合受阻，从而促进了QA-与放氧复合体S2态的重组过程。同时我们发现，经过5分钟的恢复，这些光系统II还原侧电子传递的功能抑制能够大部分得到恢复，显示高温胁迫对受体侧电子传递的影响具有可逆性。 3. 通过采用77K低温荧光光谱等手段，我们研究了高温胁迫对螺旋藻细胞光合能量传递的影响。研究显示，高温胁迫对580nm和436nm激发的低温荧光光谱都有显著影响。高温胁迫对PS I的发射峰F725和F751没有显著影响，显示高温没有影响藻胆体到光系统I的激发能传递。而高温胁迫引起了PBS对PS II荧光发射比值的上升，说明高温抑制了藻胆体到光系统II之间的激发能传递。但藻蓝蛋白的发射峰643nm在高温处理后基本没有变化，显示高温抑制PBS到PS II的能量传递不是由于藻蓝蛋白到别藻蓝蛋白之间的能量传递受阻造成的。结果还显示，高温胁迫对藻胆体到光系统II能量传递的抑制也不是由于藻胆体与光系统II发生分离，而是抑制了别藻蓝蛋白到CP43和CP47的能量传递，原因可能是由于藻胆体内部结构的改变引起的。 ４.热致发光（TL）和荧光衰减动力学的测定和分析结果显示，高温胁迫改变了S2QA-和S2QB-重组体的稳定性，其中S2QA-的稳定性降低，S2QB-的稳定性升高。根据具有异质性的TL信号，我们推测有活性PSII中有可能存在对高温胁迫敏感度不同的两种亚基，它们具有不同的QB/QB-氧化还原势能。当高温胁迫造成相当数量的反应中心失活，QA到QB正常的电子传递受阻时，光系统有可能通过保存更多的具有较高能量的反应中心亚基，达到促进QA到QB的电子传递的目的。 5. OJIP荧光瞬态上升曲线在高温胁迫后出现标志性K峰，说明螺旋藻的放氧复合物受到伤害，放氧S态引起的多次闪光下的TL振荡，显示这个高温处理对S1→S2的转变没有影响，却抑制了S2→S3的转变，这同OJIP荧光瞬态上升曲线的结果相一致，说明高温对螺旋藻放氧复合体造成了伤害。

Synthesis, electrochemistry, and photophysics of a novel binuclear polypyridyl Ru ( II ) complex with an 1,8-adipoylamido-bis(1, 10-phenanthroline-5-yl) ligand

The present paper covers the syntheses of 1,8-adipoylamido-bis(1,10-phenanthroline-5-yl)(bphaa) and its binuclear complex {[(bpy)(2)Ru](2)(bphaa)} (PF6)(4), where bpy is 2,2'-bipyridine. The two novel compounds were confirmed by means of elemental analysis, IR, and LD-MS and H-1 NMR, and H-1 NMR spectra were completely assigned in virtue of H-1-H-1 COSY. chemical behavior of the binuclear Ru (I) complex was obtained using cyclic and voltammetry. Its photophysical property was investigated by electronic absorption, excitation and emission spectra.

Synthesis and properties of three tris(1,10-phenanthroline) ruthenium (II) derivatives

Three new asymmetrical ruthenium (II) complexes: [Ru(phen)(2){phen-NHCO(CH2)(4)Br}](PF6)(2), [Ru(phen)(2){phen-NHCO(CH2)(5)Br}](PF6)(2) and [Ru(phen)(2){phen-NHCO(CH2)(10)Br}](PF6)(2) were synthesized, which were confirmed by the technique of FT-IR, H-1 NMR and ESI-MS. The electrochemical and fluorescent properties of three Ru (II) complexes were investigated with cyclic voltammetry and fluorometry.

Four novel screw-like tris(1,10-phenanthroline) ruthenium(II) bishexafluorophosphate derivatives

Four novel screw-like Ru(II) complexes, tris(5-lauramide-1,10-phenanthroline)Ru(II) bishexafluorophosphate, tris(5-myristamide-1,10-phenanthroline)Ru(II) bishexafluorophosphate, tris(5-palmitamide-1,10-phenanthroline)Ru(II) bishexafluorophosphate and tris (5-stearamide-1,10-phenanthroline)Ru(II) bishexafluorophosphate have been efficiently synthesized. They are confirmed by the techniques of IR, H-1 NMR, H-1-H-1 COSY and ES-MS. Also, their electrochemistry, fluorescence and electrochemiluminescence are reported.

A mechanistic study of electrochemical oxidation processes of (OEP)Mg(II) in the presence of anions

In the presence of F-, OH-, Cl-, electrochemical redox of (OEP)Mg(II) [2,3, 7,8,12,13,17,18 octaethyl-21H, 23H-porphine magnesium (II)] are investigated in DCE/0.1 mol/L solution by cyclic voltammetry and spectroelectrochemistry, In the presence of anions, anions are axially coordinated to (OEP)Mg(II) generate (OEP)Mg(II)Y, the E-1/2 of (OEP)MS(II)Y oxidation are negatively shifted. A chemical reaction following the second oxidation step is observed, the E-1/2 of the reaction product is obtained. Mechanism of (OEP)Mg(II) in the halogen and OH- anions titration process has been proposed.