Adsorption of hydrophobically modified polyelectrolytes at the n-octane/water interface

The interfacial activity of polyelectrolytes carrying alkyl side chains of different length has been studied. Potassium salts of poly(maleic acid-co-1-olefins), PA-n K2 with n=12 , 14, 16, 18, were synthesized, and the interfacial tension at the aqueous solution/n -octane interface was measured as a function of the length of the alkyl side chain. The results show that the interfacial tension lowering, the limiting excess concentration Gamma (m), and the efficiency of adsorption pC (20) depend on the number of methylene groups in the alkyl side chain. According to Rosen the last two parameters define two different contributions to the standard free energy of adsorption: one arises from the distribution of the polymer between the bulk of the solution and the interface Delta G (dist )(0), and another comes from the configuration adopted at the interface Delta G (int )(0). These free energies were plotted as a function of the number of carbon atoms in the alkyl side chain and a linear relation was found for both of them. From these plots contributions of 0.83 and -0.58 per methylene group were determined for Delta G (0)(dist ) and Delta G (0)(int ), respectively. The positive value for the incremental free energy of distribution is attributed to the formation of a polymer micelle which is stabilized by longer alkyl side chains. On the other hand, the negative value for Delta G (0)(int ) indicates that at the interface the polymer adopts a configuration where the hydrocarbon tail is interacting with the octane molecules.     

Low molecular weight organogels based on long-chain carbamates

Thermoreversible organogels were prepared from carbamates with alkyl side chains of different lengths. Gelation was possible only up to an alkyl side chain length of 12 carbons, beyond which crystallization occurs, due to the dominant van der Waals interaction between the alkyl chains. This is in contrast to other alkane-based organogels, in which gelating efficiency increased with the length of the alkane chain (see Abdallah, D. J.; Weiss, R. G. Adv. Mater. 2000, 12, 1237). The critical concentration for gelation decreases drastically with an increase in the side chain length. Xerogels of these show birefringent fibers with uniform cross section and unlimited growth in one direction. The extent of this unlimited growth is affected by the length of the alkyl side chain in the carbamate, which finally ceases the gel formation ability of the carbamate. Cryogenic scanning electron microscopy images of the gels are similar to those of xerogels. From X-ray diffraction of the fibers, we propose that the growth direction is along the plane of hydrogen bonds between the carbamate molecules. The thickness of the fibers depends on the length of the alkyl side chain. Morphological differences are seen between gels prepared by slow cooling and quenching of the solution. Thus, the morphology of the fibrous xerogels of the carbamates can be tailored for specific applications, by the choice of the alkyl side chain length and the rate of cooling the solution.     

Vinyl‐Type Polymerization of Norbornene Dicarboxylic Acid Dialkyl Esters

Summary: Poly(cis‐norbornene‐exo‐2,3‐dicarboxylic acid dialkyl esters) (alkyl = Me, Et, Pr, Bu, Pen, and Hex) are synthesized as a vinyl‐type with a palladium(II ) catalyst in high yield from easily prepared, pure exo‐monomers. The polymers show good solubility in common organic solvents and excellent thermal stability up to 330 °C. The polymers with alkyl groups larger than methyl exhibit a two‐step thermal degradation profile of an initial thermal degradation of side‐chains starting at 350 °C, followed by thermal degradation of the norbornene backbone starting at ca. 430 °C. The glass transition temperature decreases and the mechanical flexibility increases as the alkyl length of the side‐chain increases.

Normalized loss shear modulus (G″) versus temperature for polynorbornene dicarboxylic acid dialkyl esters.     

Limited Fraction of Crystallized Side Chains in Bottlebrush Poly(n-alkyl methacrylate)s

Crystallinity of bottlebrush polymers due to side chain crystallization has been considered to be related to the length of the side chains only under the assumption of complete participation of crystallization by all side chains.Recent experimental results revealed that in poly(n-alkyl methacrylate)s a fraction of side chains could not crystallize due to constraints imposed by the trapped main chain entanglements and required expansion of main chain-main chain distance.This result renders the original simplified consideration of the origin of crystallinity in bottlebrush polymers questionable.In this work,we introduce a new parameter fc,the fraction of crystallizable side chains,to better describe the crystallinity of bottlebrush polymers.A linear relationship between the melting enthalpy and the number of alkyl groups in side chains for bottlebrush polymers reported repeatedly indicates that fc remains essentially unchanged when bottlebrush polymers had the same main chain structure and grafting degree but different side chain lengths.The slope of the above-mentioned linear relationship is thus AHCH2×fc,where AHCH2 stands for the melting enthalpy of one mole alkyl group packed into the crystal.With a known value of fc,it is possible to estimate the value of AHCH2.In case of poly(n-alkyl methacrylate)s,we estimated AHCH2 of hexagonal crystal being at most 5.74 kJ/mol with the knowledge of possibly smallest fc of 0.67 obtained from small angle X-ray scattering data.Therefore,the crystallinity of bottlebrush polymer would be calculated based on the equation Xc = fc×Nc/N with N and Nc being the number of alkyl groups in a side chain and those packed in the crystalline structure,respectively.Both chemical structure and grafting degree of bottlebrush polymers affect fc.     

A Simple Post-Polymerization Modification Method for Controlling Side-Chain Information in Digital Polymers

A three-step post-polymerization modification method was developed for the design of digitally encoded poly(phosphodiester)s with controllable side groups. Sequence-defined precursors were synthesized, either manually on polystyrene resins or automatically on controlled pore glass supports, using two phosphoramidite monomers containing either terminal alkynes or triisopropylsilyl (TIPS) protected alkyne side groups. Afterwards, these polymers were modified by stepwise copper-catalyzed azide–alkyne cycloaddition (CuAAC). The terminal alkynes were first reacted with a model azide compound, and after removal of the TIPS groups, the remaining alkynes were reacted with another organic azide. This simple method allows for quantitative side-chain modification, thus opening up interesting avenues for the preparation of a wide variety of digital polymers.     

N-烷基化聚对苯二甲酰对苯二胺梳状高分子中烷基侧链对刚性主链堆积行为的影响

基于聚对苯二甲酰对苯二胺(PPTA), 采用N-烷基化方法制备了系列PPTACns(烷基侧链碳原子数n=8, 10, 12, 14, 16, 18)刚性主链梳状高分子, 利用DSC, XRD和FTIR等方法研究了其主链堆积行为、 分子链构象及热性能等与烷基侧链长度及结晶特性之间的关系. XRD和DSC结果表明, 当烷基侧链碳原子数达到14时, 烷基侧链发生结晶. XRD结果显示, PPTACns具有层状结构, 烷基侧链长度对主链层间距影响显著. FTIR研究发现, 烷基侧链的聚集状态对PPTACns分子链的构象产生较大影响, 伴随着烷基侧链结晶的熔融, PPTACns的分子链构象发生显著改变. 烷基侧链处于熔融状态的PPTACns的ν_C=O和γ_C-H谱带峰位与烷基侧链不结晶的PPTACn接近.     

Theoretical investigation of carboranylpyrrole structures and the thermal resistance and conducting properties of carboranylpyrrole polymers

The carboranylpyrrole polymers are functional materials with superior thermal resistance and conducting performances. The carboranylpyrrole structures and Laplacian bond order (LBO) of carborane moiety, as well as the thermal resistance and conducting properties of carboranylpyrrole dimers or polymers, were investigated theoretically. The ¹¹B NMR chemical shifts of 3-(2-methyl-o-carboranyl)alkyl-1H-pyrrole monomers (CP-1 to CP-5) were calculated and analyzed. The average LBO values of some characteristic chemical bonds in the carborane cages of CP-1 to CP-5 molecules were calculated. It is found that the average LBO values of carborane moieties change slightly with the increase in alkyl chain length. The temperature resulting in about 15–20 % weight loss for CP-1, CP-3, CP-4 and CP-5 polymers is predicted to be more than 700 °C. Apart from the C–C bonds in carborane moieties of 3-(2-R-o-carboranyl)propyl-1H-pyrrole (R = CH₂OH, CH₂OCH₃, CN, COCl, Ph) substituents, the LBO values of other bonds in these cages change slightly relative to that in the molecule of 3-(2-methyl-o-carboranyl)propyl-1H-pyrrole (CP-3). The C–C bond LBO values in the carborane cages of these substituents with electron-donating groups (R = CH₂OH, CH₂OCH₃) are bigger than that in CP-3, while those values in those substituents with electron-withdrawing groups (R = CN, COCl, Ph) are smaller than that in CP-3. The polymerization activity calculated for CP-1 to CP-5 monomers increases with the increase in alkyl chain length. The calculated orbital energy gap (?E _LUMO?HOMO) of CP-1 to CP-5 dimers decreases with the increase in alkyl chain length, and accordingly, the electronic conductivity has the potential to increase. In addition, the calculated band gaps of CP-1 to CP-5 dimers cell models also decrease with the increase in alkyl chain length.     

Side‐Chain Modification and “Grafting Onto” via Olefin Cross‐Metathesis

Olefin cross‐metathesis is introduced as a versatile polymer side‐chain modification technique. The reaction of a poly(2‐oxazoline) featuring terminal double bonds in the side chains with a variety of functional acrylates has been successfully performed in the presence of Hoveyda–Grubbs second‐generation catalyst. Self‐metathesis, which would lead to polymer–polymer coupling, can be avoided by using an excess of the cross‐metathesis partner and a catalyst loading of 5 mol%. The results suggest that bulky acrylates reduce chain–chain coupling due to self‐metathesis. Moreover, different functional groups such as alkyl chains, hydroxyl, and allyl acetate groups, as well as an oligomeric poly(ethylene glycol) and a perfluorinated alkyl chain have been grafted with quantitative conversions.     

聚[甲基丙烯酸（磺酸钠烷基酯）]高分子溶致液晶

溶致液晶是两亲分子有序组合体的一种形式.与表面活性剂相比,高分子溶致液晶的研究开展较少,其中以主链型溶致液晶为主,而侧挂型支链高分子溶致液晶报导极少[1-3],但含有离子的不同烷基侧链的高聚物在溶液中自织组成液晶的规律性和性质的研究,在基础理论和应用方面皆有重?..     

The photophysical properties and morphology of fluorene-alt-benzene based conjugated polymer

A series of fluorene-alt-benzene based conjugated main chain polymers chemically attached with alkyl side chains of different lengths on phenylene rings were designed and synthesized by a palladium catalyzed Suzuki coupling reaction. The UV-vis absorption and fluorescence spectra, thermal stability of spectral property, phase transition behavior and morphology of the synthesized polymers were investigated. With increasing the length of the alkyl side chain, the UV and fluorescence spectra exhibit an obvious blue shift compared with those of the unsubstituted polymer. The alkyl substitution improves the thermal spectral stability of the polymers due to the steric hindrance of the alkyl side chains, thus leading to efficient separation of the main chain backbones. The phase transition behavior is closely related to the length of the alkyl side chains attached on the phenylene rings. The annealed films of the polymers display characteristic nematic liquid crystalline texture. TEM observations indicate that solvent-cast thin deposits of all the polymers show typical fibrillar morphology.     

Photoinduced Copper-Catalyzed Asymmetric Decarboxylative Alkynylation with Terminal Alkynes

We describe a photoinduced copper-catalyzed asymmetric radical decarboxylative alkynylation of bench-stable N-hydroxyphthalimide(NHP)-type esters of racemic alkyl carboxylic acids with terminal alkynes, which provides a flexible platform for the construction of chiral C(sp³)−C(sp) bonds. Critical to the success of this process are not only the use of the copper catalyst as a dual photo- and cross-coupling catalyst but also tuning of the NHP-type esters to inhibit the facile homodimerization of the alkyl radical and terminal alkyne, respectively. Owing to the use of stable and easily available NHP-type esters, the reaction features a broader substrate scope compared with reactions using the alkyl halide counterparts, covering (hetero)benzyl-, allyl-, and aminocarbonyl-substituted carboxylic acid derivatives, and (hetero)aryl and alkyl as well as silyl alkynes, thus providing a vital complementary approach to the previously reported method.     

具有氟烷基边链和手性中心液晶化合物的合成及液晶性研究

本文设计合成了十个含氟烷基边链和手性中心的液晶化合物，并通过DSC和偏光显微镜对它们的液晶性进行了研究。其中二环系液晶化合物不显示液晶相或仅显示单边近晶A相。三环系液晶化合物中较长的氟烷基边链有利于近晶相的形成，且当液晶核另一端的烷氧基链的长度适中时，在氟烷基边链和液晶核之间具有手性中心的液晶分子显示了手性近晶C相和其它液晶相。     

Alkyl modified anionic siloxanes as pseudostationary phases for electrokinetic chromatography. I. Synthesis and characterization

Anionic water soluble siloxane polymers have been synthesized and characterized for electrokinetic chromatography. Siloxane polymers are of interest in electrokinetic chromatography because of the wide variety of chemistries that can be developed based on these backbones, including much of the stationary phase chemistry developed in the last 30 years. The siloxanes in this study have a sulfonate functional group. The siloxanes have different length alkyl chains (C8, C12, C18) attached to the backbone in differing densities. The methylene selectivity generally increases with increasing alkyl chain length and with increasing alkyl chain density. The electrophoretic mobility appears to pass through a maximum as more alkyl chain is added to the siloxane backbone. The efficiency also would seem to pass through a maximum as more alkyl chain is added. The chemical selectivities of the siloxane polymers are very different from sodium dodecyl sulfate but are similar to each other.     

Synthesis and antibacterial activities of water‐soluble methacrylate polymers containing quaternary ammonium compounds

New water‐soluble methacrylate polymers with pendant quaternary ammonium (QA) groups were synthesized and used as antibacterial materials. The polymers with pendant QA groups were obtained by the reaction of the alkyl halide groups of a previously synthesized functional methacrylate homopolymer with various tertiary alkyl amines containing 12‐, 14‐, or 16‐carbon alkyl chains. The structures of the functional polymer and the polymers with QA groups were confirmed with Fourier transform infrared and ¹H and ¹³C NMR. The degree of conversion of alkyl halides to QA sites in each polymer was determined by ¹H NMR to be over 90% in all cases. The number‐average molecular weight and polydispersity of the functional polymer were determined by size exclusion chromatography to be 32,500 g/mol and 2.25, respectively. All polymers were thermally stable up to 180 °C according to thermogravimetric analysis. The antibacterial activities of the polymers with pendant QA groups against Staphylococcus aureus and Escherichia coli were determined with broth‐dilution and spread‐plate methods. All the polymers showed excellent antibacterial activities in the range of 32–256 μg/mL. The antibacterial activity against S. aureus increased with an increase in the alkyl chain length for the ammonium groups, whereas the antibacterial activity against E. coli decreased with increasing alkyl chain length. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5965–5973, 2006     

含偶氮苯基元联酰胺衍生物的有机凝胶和光响应性质

设计合成了具有不同末端烷基链长度的偶氮苯类联酰胺衍生物N-(3,4-n-氧基苯基)-N'-4-(偶氮苯基)苯甲酰肼(Dn,n=7,8,10).Dn可以形成稳定的有机凝胶,末端烷基链增加有利于提高凝胶能力和热力学稳定性.凝胶形成的驱动力主要为联酰胺基团间的分子间氢键以及偶氮苯基团间的π-π相互作用和烷基链间的范德华力.在紫外光照射下,Dn中的反式偶氮苯向顺式转化,并且在溶液中的光响应性非常显著,但凝胶态下偶氮苯的光致顺反异构不能诱导凝胶-溶胶的转变.     

New liquid-crystalline polymers with chiral phases

Liquid-crystalline polyesters with cholesteric and probably chiral smectic C* phases were prepared using combined liquid-crystalline polymers (that is polymers with the mesogenic groups in the main chain as well as in the side groups). Copolyesters of these polymers and polymers with olefinic double bonds could be cross-linked retaining the liquid-crystalline phases. This resulted in cross-linked polymers with elastic properties.     

Azide telechelics chain extended by click reaction: Synthesis,characterization, and cross‐linking

Azide telechelics of poly(dimethylsiloxane) (PDMS), polypropylene oxide (PPO), and polyethylene oxide (PEO) were synthesized from the corresponding epoxy telechelics and characterized. These oligomeric azides were chain extended by reaction with bispropargyl ether of bisphenol A (BPEBA) through a copper‐catalyzed azide‐alkyne cycloaddition (CuAAC) reaction. PDMS manifested a faster reaction in contrast to PPO or PEO. The chain‐extended polymers underwent cross‐linking above 170°C through thermal cleavage of residual (terminal) azide groups. This was manifested in their rheograms and was further substantiated by FTIR and NMR spectroscopic analyses. Dynamic mechanical analyses of the cross‐linked polymers exhibited characteristic transitions of hard and soft segments, implying microphase separation in the system. Microscopic evaluation of the thermally cross‐linked sample revealed a porous morphology with microsized to nanosized pores.     

Photoinduced Copper‐Catalyzed Asymmetric Decarboxylative Alkynylation with Terminal Alkynes

We describe a photoinduced copper‐catalyzed asymmetric radical decarboxylative alkynylation of bench‐stable N‐hydroxyphthalimide(NHP)‐type esters of racemic alkyl carboxylic acids with terminal alkynes, which provides a flexible platform for the construction of chiral C(sp³)?C(sp) bonds. Critical to the success of this process are not only the use of the copper catalyst as a dual photo‐ and cross‐coupling catalyst but also tuning of the NHP‐type esters to inhibit the facile homodimerization of the alkyl radical and terminal alkyne, respectively. Owing to the use of stable and easily available NHP‐type esters, the reaction features a broader substrate scope compared with reactions using the alkyl halide counterparts, covering (hetero)benzyl‐, allyl‐, and aminocarbonyl‐substituted carboxylic acid derivatives, and (hetero)aryl and alkyl as well as silyl alkynes, thus providing a vital complementary approach to the previously reported method.     

Synthesis,Anti-Proliferative Evaluation and Mechanism of 4-Trifluoro Methoxy Proguanil Derivatives with Various Carbon Chain Length

Among the known biguanide drugs, proguanil has the best antiproliferative activity. In contrast, newly synthesized biguanide derivatives containing fluorine atoms have excellent biological activity, among which trifluoromethoxy compounds show the strongest ability. Preliminary work in our laboratory exhibited that n-heptyl containing proguanil derivatives on one alkyl chain side have better biological activity than those with a shorter carbon chain. However, the relationship between the length of the carbon chain and the activity of the compounds is unknown. In this study, we synthesized 10 new trifluoromethoxy-containing proguanil derivatives with various carbon chain lengths. The phenyl side is fixed as the trifluoromethoxy group with change of carbon chain length in alkyl chain side. It was found that the anti-cancer abilities of 5C–8C with n-pentyl to n-octyl groups was significantly better than that of proguanil in the five human cancer cell lines. The colony formation assay demonstrated that 6C–8C at 0.5 to 1.0 μM significantly inhibited the colony formation of human cancer cell lines, much stronger than that of proguanil. Pharmacologically, 8C activates AMPK, leading to inactivation of the mTOR/p70S6K/4EBP1 pathway. Thus, these novel compounds have a great potential for developing new anti-cancer candidates.     

Synthesis and thermal behavior of side-chain liquid crystalline polymethacrylates containing tolane-based mesogenic side groups

The synthesis and characterization of nine polymethacrylates containing 4-alkoxy-4′-trifluoromethyltolane, 4-alkoxy-4′-cyanotolane, and 4-alkoxy-4′-nitrotolane side groups were described in this study. The phase behavior of the prepared monomers and polymers was characterized by differential scanning calorimetry, optical polarizing microscopy, and x-ray diffraction. All of the obtained monomers exhibit no mesophase, while most of the synthesized polymers reveal enantiotropic mesomorphism. The polymethacrylate containing 4-propanyloxy-4′-nitrotolane side groups was the only one which shows no mesomorphic behavior. Both the spacer length and the nature of terminal groups have profound influence on the phase transition temperatures and thermal stability of the mesophase. The polymers with longer spacers tend to form a more ordered mesophase with a wider temperature range. Among three polymers with the same spacer length, the polymer with a trifluoromethyl terminal end group is inclined to form a more ordered mesophase than the other two polymers. No side chain crystallization occurred for all obtained polymers. © 1994 John Wiley & Sons, Inc.