超支化聚(酯-胺)分子结构及固化涂层性能研究

近年来,颜德岳等基于A2型单体二丙烯酸酯及BB2′型单体二胺化合物合成了多种端胺基超支化聚(酯-胺),并对反应机理及聚合物结构进行了系统研究[1,2],结果表明,由于B与B′活性差异,反应首先生成AB2′型和B4′型中间体,进一步聚合得到可溶性产物.我们基于A3型单体三丙烯酸酯与B2型单体二胺化合物合成了端丙烯酸酯基超支化聚(酯-胺)[3,4].在这些体系中,由于官能团反应活性高,难以控制反应程度.另外,由于超支化聚合物不能直接用作结构材料,其在涂料、粘合剂等领域的应用多基于末端官能团的固化反应[5].但通常由于官能团在分子表面密集分布,部…     

由苯-1，2，4-三羧酸-1，2—酐和羟乙基哌嗪合成酰胺键、叔氨和酯键交替排列的水溶性超支化聚合物

基于官能团非等活性原理，由商品化多组分单体一步法合成了超支化聚合物． 用苯—1，2，4-三羧酸—1，2酐(BTAA)与羟乙基哌嗪(HEPZ)为原料，利用氨基和羟 基反应活性不同，制备了结构非对称超支化聚酰胺—酯．分别用红外、核磁共振确 定了所得聚合物的结构．该聚合物分子骨架中含有交替排列的酰胺键、叔氨和酯键 ，易溶于水．本合成方法原料易得、工艺简单，适合大量制备超支化聚合物．     

蓖麻油基巯烯基紫外光固化胶粘剂的研制与性能研究

以异佛尔酮二异氰酸酯(IPDI)、蓖麻油(CO)、丙烯酸羟丙酯(HPA)为原料,采用熔融缩聚法合成出端丙烯酸酯基预聚体;同时以CO和3-巯基丙酸(3-MPA)为原料采用酯化反应合成出端巯基光引发单体。将端不饱和双键聚氨酯丙烯酸酯预聚体与所制备巯基丙酸酯按一定比例复合,加入光引发剂,在紫外光照射下,预聚体中双键与光引发单体中巯基发生巯基-烯点击反应,制得聚氨酯丙烯酸酯固化膜。采用核磁共振氢谱(1 HNMR)、红外光谱(FT-IR)、热重分析(TG)和光量热系统(Photo-DSC)等手段对合成预聚体、巯基丙酸酯及固化膜结构和性能进行了分析表征。结果表明:在紫外光辐照下,预聚体中不饱和双键与巯基化合物中巯基间发生了自由基加成反应,固化时间在60s以内,且所制备UV固化膜具有良好的机械性能和热稳定性。     

不饱和端基超支化聚合物/丙烯酸酯共聚乳液的研究

利用Si—H加成反应制得了以CC为端基的超支化含硅聚合物,并将其与丙烯酸酯类单体进行乳液共聚,对聚合反应机理及所得聚合物的性能进行了测试分析.结果表明,含有大量CC端基的超支化含硅聚合物能与丙烯酸酯类单体稳定聚合,制得了平均粒径小于100nm高度交联的乳胶粒子.共聚物的红外光谱证实,超支化聚合物的不饱和端基已全部反应,形成了以超支化聚合物为多臂交联点的交联型乳胶粒子.随聚合体系中超支化聚合物用量的增加,乳液聚合反应速率增大,乳胶粒粒径减小,共聚物热稳定性显著提高.     

巯基丙烯酸酯树脂的合成及自引发光聚合反应

以4,4'-二巯基苯硫醚和1,6-己二醇二丙烯酸酯通过"巯基-双键"反应合成了4,4'-二巯基苯硫醚己酯二丙烯酸酯(TBHDA)及苯硫酚改性双三羟甲基丙烷四丙烯酸酯(TP-DiTMP4A)和超支化丙烯酸酯预聚物(TP-P1000As). 采用 ¹H NMR和FTIR谱对产物结构进行了表征. 采用Photo-DSC方法对产物的自引发光聚合反应活性进行了研究, 结果表明, TBHDA本体及与EB605的混合体系均显示出较高的自引发光聚合反应活性, 而TP-DiTMP4A和TP-P1000As的自引发光聚合反应活性较低; 相对TP-P1000As而言, TP-DiTMP4A具有较高的光聚合反应活性是由于其较高的硫醚键和丙烯酸酯双键浓度所致.     

含乙烯基超支化聚(酯-酰胺)大单体的合成

以顺丁烯二酸酐、二乙醇胺、邻苯二甲酸酐等为原料,利用官能团活性的差异,通过逐步展开的方法合成了含有双键和端羟基的聚（酯-酰胺）型分子结构的超支化大单体（3）。IR分析表明：3的分子末端为大量伯羟基,具有较高的反应活性;3含有可供聚合的乙烯基,将3与其它乙烯基单体共聚可以获得含超支化结构的共合物。     

通过大分子单体的“点击”反应合成超支化聚苯乙烯

用一端带有一个叠氮基,另一端带有两个炔基的聚苯乙烯(PSt)大分子单体,通过"点击"化学反应,成功制备了结构规整的超支化聚苯乙烯。首先,L-天冬氨酸经过溴化和酯化两步反应得到含有两个炔基的原子转移自由基聚合(ATRP)引发剂——2-溴代琥珀酸双炔丙基酯(BPBS),然后引发苯乙烯的ATRP,并通过NaN3的取代反应把末端溴转化为叠氮基,得到AB2型大分子单体(CH≡C)2-PS-N3。这种大分子单体通过"点击"反应聚合得到超支化聚苯乙烯,根据多角度激光光散射(MALLS)测试结果,最终产物重均聚合度DPw可达53,分子量分布Mw/Mn=1.53。     

巯基/(甲基)丙烯酸(甲基)烯丙酯光固化特性

通过对羧酸盐法改进后合成同时含有高活性的丙烯酸酯型C=C和低自由基活性的烯丙基型C=C的烯类单体(甲基)丙烯酸(甲基)烯丙酯,以实现(甲基)丙烯酸酯类紫外光固化与巯/烯光聚合结合在二元体系中;并以1173为光引发剂,利用实时红外(RT-IR)跟踪此类烯烃与三羟甲基丙烷三(3-巯基丙酸酯)(TMMP)光固化过程,探究烯烃结构、光强和引发剂用量对含有两类碳碳双键的烯类单体与巯基化合物二元体系的光固化行为的影响.研究发现,这类二元巯-烯光聚合反应中均有(甲基)丙烯酸酯双键的反应活性最大,(甲基)烯丙基次之,巯基的反应活性最小;甲基取代在烯烃的不同C=C上,对巯-烯光固化特性影响不同,甲基取代在烯丙基C=C上比甲基取代在丙烯酸基C=C上对巯-烯光固化行为影响更大;巯基最终转化率随甲基取代基数目增多而减少;丙烯酸甲基烯丙酯体系中两类双键(丙烯酸型/甲基烯丙基型)反应活性几乎相同且均具有高的转化率.     

基于超支化聚硫醚构建非水相生物黏合剂

以2-(丙烯酰氧基)乙基甲基丙烯酸酯为AA'单体,三羟甲基丙烷三(3-巯基丙酸酯)为B3单体,通过硫醇-(甲基)丙烯酸酯迈克尔加成聚合反应,制备了富含硫醇基团、室温为液态的超支化聚硫醚(HBP).将HBP与聚乙二醇二丙烯酸酯(PEGDA)混合制备了黏合剂.利用小瓶倾斜法、流变测试、拉伸搭接剪切测试、溶胀-降解测试和体外...     

5,6-苯并-2-亚甲基-1,3-二氧环庚烷的活性自由基开环聚合反应

活性 (或称可控 )自由基聚合研究是目前高分子科学的研究热点之一[1～ 8] .活性自由基聚合制备的聚合物具有分子量随转化率提高而线性增加、分子量分布窄和聚合反应为一级反应动力学等特点 .自由基开环聚合所得产物体积收缩小 ,某些含有不饱和双键的螺环单体发生双开环聚合时甚至发生体积膨胀 ;开环聚合还可在聚合物主链上引入各种官能团 ,如酯基、碳酸酯基、酮基等 [9～ 12 ] .因此 ,用活性聚合的方法对自由基开环聚合的分子量和分子量分布进行控制 ,可以制备出具有各种不同结构和性能的新聚合物 . Wei等 [13] 报道了利用稳定自由基法实现…     

D-l-A分子修饰罗丹明底环及对其激发态的影响

通过乙基桥把供电子基团1,8-萘酰亚胺与罗丹明底环羧酸基相连,得到了两种以D-l-A(Donor-Acceptor-Line alkanes compounds)分子修饰罗丹明底环的化合物,并就合成中间体D-π-A(Donor-Acceptor-π-conjugated compounds)分子中哌嗪供电子基取代溴对1,8-萘酐母体基态和激发态的影响,以及对D-l-A分子修饰罗丹明底环对罗丹明母体D-π-A分子紫外可见吸收光谱和激发态的影响进行了研究。结果表明:用D-l-A分子修饰罗丹明底环时,D(Donor compound)的给电子能力越强,其吸收强度越大,其吸收紫外光而激发能力越强;在激发态下D-l-A体系发生了分子内能量传递,萘酰亚胺基团发生强烈的荧光猝灭,罗丹明底环接收能量激发罗丹明母体(D-π-A分子)发射特征荧光,D的给电子能力越强,其荧光强度越高。     

抗菌肽SAMP1及其类似肽的构效关系

以人工合成抗菌肽1(Synthetic antimicrobial peptide 1, SAMP1)为研究模板, 采用氨基酸序列重排、 不同的带正电荷氨基酸残基和疏水性氨基酸残基取代等方法, 设计合成了8条SAMP1类似肽. 利用生物信息学软件预测了SAMP1及其类似肽的理化性质; 采用圆二色光谱(CD)技术测定其在不同环境下二级结构的变化; 采用噻唑蓝(MTT)法测定其抗菌活性; 通过红细胞溶血实验评估了这些多肽的溶血性. 结果表明, 大部分类似肽具有较低的溶血毒性和较高的广谱抗菌活性. CD光谱分析结果显示, 大部分类似肽二级结构以α螺旋和无规则卷曲为主, 在体积分数为50%的2,2,2-三氟乙醇(TFE)溶液中, α螺旋结构比例增加. 与母肽SAMP1相比, 经序列重排后得到的SAMP1-A1, SAMP1-A2和SAMP1-A3的抗菌活性变化不大, 但序列中正电荷氨基酸残基均匀分布的类似肽SAMP1-A2的溶血毒性增加. 用精氨酸(Arg)取代SAMP1序列中的赖氨酸(Lys)得到的类似肽SAMP1-A4的抗菌活性增强, 同时溶血毒性降低. 用疏水性较强的异亮氨酸(Ile)和缬氨酸(Val)取代SAMP1中的疏水性氨基酸残基, 得到的类似肽SAMP1-A5和SAMP1-A7的抗菌活性急剧降低; 用疏水性较弱的色氨酸(Trp)取代SAMP1中的疏水性氨基酸残基, 得到的类似肽SAMP1-A8的抗菌活性增强, 同时溶血毒性提高.     

Structure of the complex monolayer of gemini surfactant and DNA at the air/water interface

The properties of the complex monolayers composed of cationic gemini surfactants, [C(18)H(37)(CH(3))(2)N(+)-(CH(2))(s)-N(+)(CH(3))(2)C(18)H(37)],2Br(-) (18-s-18 with s = 3, 4, 6, 8, 10 and 12), and ds-DNA or ss-DNA at the air/water interface were in situ studied by the surface pressure-area per molecule (π-A) isotherm measurement and the infrared reflection absorption spectroscopy (IRRAS). The corresponding Langmuir-Blodgett (LB) films were also investigated by the atomic force microscopy (AFM), the Fourier transform infrared spectroscopy (FT-IR), and the circular dichroism spectroscopy (CD). The π-A isotherms and AFM images reveal that the spacer of gemini surfactant has a significant effect on the surface properties of the complex monolayers. As s ≤ 6, the gemini/ds-DNA complex monolayers can both laterally and normally aggregate to form fibril structures with heights of 2.0-7.0 nm and widths of from several tens to ~300 nm. As s > 6, they can laterally condense to form the platform structure with about 1.4 nm height. Nevertheless, FT-IR, IRRAS, and CD spectra, as well as AFM images, suggest that DNA retains its double-stranded character when complexed. This is very important and meaningful for gene therapy because it is crucial to maintain the extracellular genes undamaged to obtain a high transfection efficiency. In addition, when s ≤ 6, the gemini/ds-DNA complex monolayers can experience a transition of DNA molecule from the double-stranded helical structure to a typical ψ-phase with a supramolecular chiral order.     

Fast photodriven electron spin coherence transfer: a quantum gate based on a spin exchange j-jump

Photoexcitation of the electron donor (D) within a linear, covalent donor-acceptor-acceptor molecule (D-A(1)-A(2)) in which A(1) = A(2) results in sub-nanosecond formation of a spin-coherent singlet radical ion pair state, (1)(D(+?)-A(1)(-?)-A(2)), for which the spin-spin exchange interaction is large: 2J = 79 ± 1 mT. Subsequent laser excitation of A(1)(-?) during the lifetime of (1)(D(+?)-A(1)(-?)-A(2)) rapidly produces (1)(D(+?)-A(1)-A(2)(-?)), which abruptly decreases 2J 3600-fold. Subsequent coherent spin evolution mixes (1)(D(+?)-A(1)-A(2)(-?)) with (3)(D(+?)-A(1)-A(2)(-?)), resulting in mixed states which display transient spin-polarized EPR transitions characteristic of a spin-correlated radical ion pair. These photodriven J-jump experiments show that it is possible to use fast laser pulses to transfer electron spin coherence between organic radical ion pairs and observe the results using an essentially background-free time-resolved EPR experiment.     

Exploring the potential of tetraazaacene derivatives as photovoltaic materials with enhanced photovoltaic parameters

A series of D-π-A type molecules have been designed for their potential use in organic photovoltaic devices. Photovoltaic and optoelectronic properties of newly designed molecules have been explored by comparing with a reference molecule R comprising of the central core (2,3,8,9-tetrakis(thiophen-2-ylethynyl)-5,7,10,12-tetrakis((trimethylsilyl)ethynyl)pyrazino[2,3-b]phenazine) and π-bridge (thiophene). The end groups are (2-(2-ethylidene-3-oxo-2,3-dihydro-1H-inden-1 ylidene)malononitrile), (2-ethylidenemalonitrile), (methyl 2-cyanoacrylate) and (3-methyl-5-methylene-2-thioxothiazolidin-4-one) in the newly designed molecules. Among the investigated molecules M1 and M2 exhibit a broad absorption range of 627 and 626 nm with respect to the reference. All the designed molecules exhibited a lower bandgap as compared to R which indicates a better transfer of electron density from highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO). The reorganization energy values show that all designed molecules have efficient charge transport capability. This study proves that end-capped acceptor modification is an effective strategy for designing optimistic molecule for high performance future organic solar cells fabrication.     

D-1-A分子修饰罗丹明底环及对其激发态的影响

通过乙基桥把供电子基团1,8-萘酰亚胺与罗丹明底环羧酸基相连,得到了两种以D-1-A（Donor-Acceptor-Linealkanescompounds）分子修饰罗丹明底环的化合物,并就合成中间体D-π-A（Donor-Acceptor-Tt-conjugatedcompounds）分子中哌嗪供电子基取代溴对1,8-萘酐母体基态和激发态的影响,以及对D-1-A分子修饰罗丹明底环对罗丹明母体D-π-A分子紫外可见吸收光谱和激发态的影响进行了研究。结果表明：用D-1-A分子修饰罗丹明底环时,D（Donorcompound）的给电子能力越强,其吸收强度越大,其吸收紫外光而激发能力越强;在激发态下D-1-A体系发生了分子内能量传递,萘酰亚胺基团发生强烈的荧光猝灭,罗丹明底环接收能量激发罗丹明母体（D-π-A分子）发射特征荧光,D的给电子能力越强,其荧光强度越高。     

First total syntheses of aeruginosin 298-A and aeruginosin 298-B, based on a stereocontrolled route to the new amino acid 6-hydroxyoctahydroindole-2-carboxylic acid

The first total syntheses of aeruginosin 298-A (1) and aeruginosin 298-B (3) are described. The syntheses of the alternative putative structures 2 and 4 were also accomplished. The key common strategic element is the stereo-controlled synthesis of (2S,3aS,6R,7aS)-6-hydroxyoctahydroindole-2-carboxylic acid (L-Choi, 5) from L-tyrosine. The synthesis of this new bicyclic alpha-amino acid, which is the core of aeruginosins, involves Birch reduction of O-methyl-L-tyrosine (6) and aminocyclization of the resulting dihydroanisole 7 in acid medium, followed by N-benzylation to give the diastereoisomers 12 and 13. Upon acid treatment with HCl-MeOH, the last two produce an equilibrium mixture in which the endo isomer 13 significantly predominates. Hydrogenation of 13 in the presence of (Boc)2O gives 16, which on reduction with LS-Selectride furnishes the alcohol 22, a protected L-Choi. Successive couplings of 22 with D-leucine, protected (R)-(4-hydroxyphenyl)lactic acid, and L-arginine fragments, followed by reduction to the argininol level and a deprotection end step complete the synthetic sequence to produce aeruginosin 298-A (1). Spectral comparison showed that peptide 2, with the structure previously proposed for aeruginosin 298-A, was different from the natural product. However, synthetic 1 was found to be identical to the isolated natural sample of aeruginosin 298-A. These results unequivocally establish that the absolute stereochemistry of aeruginosin 298-A, formerly assigned incorrectly, is D-Hpla-D-Leu-L-Choi-L-Argol, as shown by structure 1. Aeruginosin 298-B was also synthesized and shown to be a mixture of rotamers of D-Hpla-D-Leu-L-ChoiNH2 (3), rather than an epimeric mixture of 3 and the L-Leu-incorporating 4.     

Laser-induced fluorescence spectra of 4-methylcyclohexoxy radical and perdeuterated cyclohexoxy radical and direct kinetic studies of their reactions with O2

The laser-induced fluorescence (LIF) excitation spectra of the 4-methylcyclohexoxy and d11-cyclohexoxy radicals have been measured for the first time. LIF intensity was used as a probe in direct kinetic studies of the reaction of O(2) with trans-4-methylcyclohexoxy and d11-cyclohexoxy radicals from 228 to 301 K. Measured rate constants near room temperature are uniformly higher than the Arrhenius fit to the lower-temperature data, which can be explained by the regeneration of cyclic alkoxy radicals from the product of their beta-scission and the effect of O(2) concentration on the extent of regeneration. The Arrhenius expressions obtained over more limited ranges were k(O2) = (1.4(+8)(-1)) x 10(-13) exp[(-810 +/- 400)/T] cm(3) molecule(-1) s(-1) for trans-4-methylcyclohexoxy (228-292 K) and k(O2) = (3.7(+4)(-1)) x 10(-14) exp )[(-760 +/- 400) /T] cm(3) molecule(-1) s(-1) for d11-cyclohexoxy (228-267 K) independent of pressure in the range 50-90 Torr. The room-temperature rate constant for the reaction of trans-4-methylcyclohexoxy radical with O2 (obtained from the Arrhenius fit) is consistent with the commonly recommended value, but the observed activation energy is approximately 3 times larger than the recommended value of 0.4 kcal/mol and half the value previously found for the reaction of normal cyclohexoxy radical with O2.     

Kinetics and products of the gas-phase reactions of divinyl sulfoxide with OH and NO3 radicals and O3

Using relative rate methods, rate constants for the gas-phase reactions of divinyl sulfoxide [CH 2CHS(O)CHCH 2; DVSO] with NO 3 radicals and O 3 have been measured at 296 +/- 2 K, and rate constants for the reaction with OH radicals have been measured over the temperature range of 277-349 K. Rate constants obtained for the NO 3 radical and O 3 reactions at 296 +/- 2 K were (6.1 +/- 1.4) x 10 (-16) and (4.3 +/- 1.0) x 10 (-19) cm (3) molecule (-1) s (-1), respectively. For the OH radical reaction, the temperature-dependent rate expression obtained was k = 4.17 x 10 (-12)e ((858 +/- 141)/ T ) cm (3) molecule (-1) s (-1) with a 298 K rate constant of (7.43 +/- 0.71) x 10 (-11) cm (3) molecule (-1) s (-1), where, in all cases, the errors are two standard deviations and do not include the uncertainties in the rate constants for the reference compounds. Divinyl sulfone was observed as a minor product of both the OH radical and NO 3 radical reactions at 296 +/- 2 K. Using in situ Fourier transform infrared spectroscopy, CO, CO 2, SO 2, HCHO, and divinyl sulfone were observed as products of the OH radical reaction, with molar formation yields of 35 +/- 11, 2.2 +/- 0.8, 33 +/- 4, 54 +/- 6, and 5.4 +/- 0.8%, respectively, in air. For the experimental conditions employed, aerosol formation from the OH radical-initiated reaction of DVSO in the presence of NO was minor, being approximately 1.5%. The data obtained here for DVSO are compared with literature data for the corresponding reactions of dimethyl sulfoxide.     

尼龙1010异常光性球晶的旋转观察

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