Soluble complexes in aqueous mixtures of low charge density comb polyelectrolyte and oppositely charged surfactant probed by scattering and NMR

A low charge density polyelectrolyte with a high graft density of 45 units long poly(ethylene oxide) side-chains has been synthesized. In this comb polymer, denoted PEO(45)MEMA:METAC-2, 2 mol% of the repeating methacrylate units in the polymer backbone carry a permanent positive charge and the remaining 98 mol% a 45 unit long PEO side-chain. Here we describe the solution conformation of this polymer and its association with an anionic surfactant, sodium dodecylsulfate, SDS. It will be shown that the polymer can be viewed as a stiff rod with a cross-section radius of gyration of 29 A. The cross section of the rod contracts with increasing temperature due to decreased solvency of the PEO side-chains. The anionic surfactant associates to a significant degree with PEO(45)MEMA:METAC-2 to form soluble complexes at all stoichiometries. A cooperative association is observed as the free SDS concentration approaches 7 mM. At saturation the number of SDS molecules associated with the polymer amounts to 10 for each PEO side-chain. Two distinct populations of associated surfactants are observed, one is suggested to be molecularly distributed over the comb polymer and the other constitutes small micellar-like structures at the periphery of the aggregate. These conclusions are reached based on results from small-angle neutron scattering, static light scattering, NMR, and surface tension measurements.     

Order in poly(N-(10-n-alkyloxycarbonyl-n-decyl)-maleimides)

Wide-angle and small-angle x-ray diffraction patterns of 11 poly(N-(10-n-alkyloxycarbonyl-n-decyl)maleimides) (PEMI) (including only even members of the series) have been obtained on unoriented samples. They show major maxima at two diffraction angles. The one at the larger angles is due to the interaction of neighboring n-alkyl side-chains. The smaller one (which shows second and third orders of diffraction in higher members of the series, n = 14 to n = 22, where n is the number of methylene groups in the external n-alkyl sequence in the side chain) is related to the distance between lamellar planes formed by the main chains. In all cases, the measured layer separation d_i is higher than the structural unit length L of the side-chain in the most extended conformation, and lower than the length corresponding to two side-chains. On the basis of the experimental results reported here, a model is proposed for the packing of these comblike polymers in the solid state. The mode of packing is also supported by infrared spectra in the 720 cm^?1 region for the ? CH₂? rocking mode of vibration of the n-alkyl side-chain.     

Stoffwechsel-Endprodukte von PhyllochinonMenachinon-4, Ubichinon-9 und Hexahydroplastochinon-4 (Phytylplastochinon)

Phylloquinone, menaquinone-4, ubiquinone-9 and hexahydroplastoquinone-4, i.e. compounds with isoprenoid side-chains which differ by their length and degrees of unsaturation, are degraded in the rat in the same way as tocopherols. After oxidative shortening of the side-chain to seven C-atoms, the metabolites are excreted in the urine as conjugates, presumably glucuronides, which, after hydrolysis, can be isolated as γ-lactones.     

Synthesis and characterization of liquid crystalline copolymethacrylates,copolyacrylates, and copolysiloxanes containing 4-methoxy-4′-hydroxy-α-methylstilbene and 4-hydroxy-4′-methoxy-α-methylstilbene constitutional isomers as side-groups

The synthesis of methacrylates and acrylates containing 4-methoxy-4′-hydroxy-α-methylstilbene and 4-hydroxy-4′-methoxy-α-methylstilbene constitutional isomers attached to the polymerizable group through flexible spacers containing 11, 8, 6, 3, and respectively 2 methylenic units is described. The radical copolymerization of a 1/2 or 2/1 mole ratio of the two constitutional isomeric monomers led to thermotropic side-chain liquid crystalline polymers in all cases. The synthesis of copolysiloxanes based on the same constitutional isomeric mesogens as side groups, and flexible spacers containing 11, 8, 6, 5, and respectively 3 methylenic units is also described. All polymers were characterized by differential scanning calorimetry and optical polarization microscopy. The polymers containing 11 methylenic units in the spacer exhibit S_c mesomorphism, while the other polymers are nematic. Copolymethacrylates do not undergo side-chain crystallization. Only the copolyacrylate containing 11 methylenic units in the spacer exhibits side-chain crystallization. All the copolysiloxanes display side-chain crystallization. The number of melting transitions seen for these polymers decreases with increasing spacer length. Copolysiloxanes containing dissimilar spacer length were also prepared. Only the copolymer synthesized with highly dissimilar spacer lengths, i.e., containing 3 and 11 methylenic units, does not undergo side-chain crystallization. These results have demonstrated that while the type of mesophase is dictated only by the spacer length, the degree of decoupling of the motion of the side-groups from the motion of the main chain is strongly dependent on the nature of the polymer backbone. For the same mesogenic unit and spacer length, the thermal stability of the mesophase is also dictated by the nature of the polymer backbone. The use of constitutional isomers of mesogenic units as side groups in liquid crystalline polymers provides at least qualitative information on the degree of decoupling of the side groups from the polymer main chain.     

Side-chain crystallinity,heat of melting,and thermal transitions in poly[N-(10-n-alkyloxycarbonyl-n-decyl)maleimides] (PEMI)

The heat of melting, the melting temperature T_m, and the sub-T_g transition temperature have been studied from –120°C to above T_m in a series of 11 poly[N-(10-n-alkyloxycarbonyl-n-decyl)]-maleimides (PEMI). Side-chains from ethyl to n-docosyl with n even have been included. The contribution to the heat of melting per methylene group shows that the hexagonal paraffin crystal modification is present in these poly(N-maleimides), in agreement with x-ray data for the same compounds. The enthalpy data show that only a part of the outer methylene groups are present in the crystalline aggregates. Furthermore, DSC traces exhibit a typical distribution of crystallite sizes, which become narrower as the side-chains become longer. The critical chain length needed to form a stable nucleus includes nine methylene groups in the outer part of the n-alkyl side-chain. The influence of the side-chain length and crystallinity on the γ-transition temperature of these polymers was also investigated. In the range where these polymers are essentially amorphous the sub-T_g transition temperature decreases continuously as the number of methylene groups in the side-chain increases. This transition is attributed to internal motion within the external side-group without any interaction with the main chain. This is presumably made possibly by the partial rotation of the oxycarbonyl group. We suggest that this transition is similar to the well known γ transition which has been attributed to various segmental motions in all ethylene copolymers and in all homopolymers containing a determined number of? CH₂? units in the main-chain or in the side-chain. Estimates based on the chemical structure, yield a value for the γ transition of ? CH₂? similar to that measured by other methods in polyethylene and related materials.     

Modeling the effect of molecular architecture of comb polymers on the behavior of Al2O3 dispersions using charge/composition factors (CCF)

In this work, we study the effect of periodicity and PEO side-chain length in four PMAA-PEO (sodium salt) comb polymers with known molecular architecture on Al₂O₃ colloidal dispersions in DI water. We introduce here charge composition factors (CCF) representing charge density of the comb polymers defined as (number of charged units in a repeating unit)/(molecular weight of a repeating unit). We find, for the first time to our knowledge, that the CCF can be used along with dispersant dosage to obtain explicit functions predicting the conductivity of the dispersants in solution, the zeta potential behavior during dispersant titrations, and the isoelectric point (IEP) of the dispersions. In addition, the dosage normalized by the CCF provides a basis for comparison for the dispersants to elucidate the trends found in adsorption and potentiometric titrations. Thus, the CCF can be used as a tool for the design of improved and new comb polymer molecular architectures.     

Topologically unique side-chain polyrotaxanes based on triacetyl-β-cyclodextrin and a poly(ether sulfone) main chain

The synthesis and NMR-spectroscopical characterization of the topological arrangements of new side-chain polyrotaxanes (3a) bearing about 80% of peracetylated cyclodextrins in the side-chains of a functionalized poly(ether sulfone) is described. The characterizations have been conducted in relation to a similar model compound bearing no cyclodextrins (3b) . The results strongly indicate that the cyclodextrins are uniformly located on the side chains, with the bigger opening over the aromatic anilide components of the barrier group. The glass transition temperature (T_g) of the polyrotaxane 3a is in the region of 143°C, which is significantly higher than that of the model polymer 3b having a value of 111°C.     

NMR Conformational Study of Aminoalkylbenzamides,Aminoalkyl-o-anisamides,and Metoclopramide,a Dopamine Receptor Antagonist

The conformational behaviour of metoclopramide, a neuroleptic benzamide, and model compounds was investigated byt ¹ H-NMR spectroscopy. An intramolecular amide-methoxy H-bond is shown to exist in CDCl₃-solution, but not in D₂O-solution, independently of the length and protonation state of the basic side-chain. This H-bond creates a virtual cycle which may be a key feature for the binding of neuroleptic benzamides to the dopamine receptor. The conformational behaviour of the aminoethyl side-chain is shown to be markedly condition-dependent. For metoclopramide and its analogues in their protonated form, the gauche- and trans- rotamers have identical energies in D₂O-as well as in CDCl₃-solutins. For the non-protonated molecules, the trans-rotamer is favoured in D₂O-solutin, while the gauche-rotamer is favoured in CDCl₃-solution (ΔG°?|0.5|kcal/mol in both cases). The side-chain conformation of neuroleptic benzamides is discussed in terms of receptor affinity.     

Synthesis, characterization and photovoltaic properties of thiophene copolymers containing conjugated side-chain

Five side-chain conjugated polythiophene derivatives, P1-P5, were synthesized by Stille coupling reaction. The effects of side-chain structures, bearing CC double bond, CC triple bond as well as different number of methoxy substituents on the benzene ring of the side-chains, on the optical, electrochemical, and photovoltaic properties of the polymers were investigated. From P1 to P3, the effect of CC triple bond and CC double bond was compared. The results indicate that the content of the thiophene units with the CC triple bond in their conjugated side-chains not only influences the absorption shape and intensity, but also influences the energy bandgap and the photovoltaic properties of the polymers. From P3 to P5, the effect of methoxy substituents on the benzene ring of the conjugated side-chains was compared. On increasing the number of the methoxy groups on the benzene ring of the conjugated side chains, the visible π-π^∗ absorption of the conjugated polymer backbone become stronger both in solution and in film. Electron-donating ability of the methoxy groups decreased the bandgap of the polymers. The best polymer solar cell based on P5 with a structure of ITO/PEDOT:PSS/Polymer:PCBM (1:1 wt/wt)/Mg/Al showed a power conversion efficiency of 1.45% under the illumination of AM1.5, 80 mW/cm².     

The Influence of the Amino Acid Side Chains on the Raman Optical Activity Spectra of Proteins

The Raman optical activity (ROA) spectra of proteins show distinct patterns arising from the secondary structure. It is generally believed that the spectral contributions of the side-chains largely cancel out because of their flexibility and the occurrence of many side-chains with different conformations. Yet, the influence of the side-chains on the ROA patterns assigned to different secondary structures is unknown. Here, the first systematic study of the influence of all amino acid side-chains on the ROA patterns is presented based on density functional theory (DFT) calculations of an extensive collection of peptide models that include many different side-chain and secondary structure conformations. It was shown that the contributions of the side-chains to a large extent average out with conformational flexibility. However, specific side-chain conformations can have significant contributions to the ROA patterns. It was also shown that α-helical structure is very sensitive to both the exact backbone conformation and the side-chain conformation. Side-chains with χ₁≈−60° generate ROA patterns alike those in experiment. Aromatic side-chains strongly influence the amide III ROA patterns. Because of the huge structural sensitivity of ROA, the spectral patterns of proteins arise from extensive conformational averaging of both the backbone and the side-chains. The averaging results in the fine spectral details and relative intensity differences observed in experimental spectra.     

Antifouling poly(vinylidene fluoride) ultrafiltration membranes containing amphiphilic comb polymer additive

An amphiphilic comb polymer consisting of poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) [P(VDF‐co‐CTFE)] main chains and poly(oxyethylene methacrylate) (POEM) side chains was synthesized using direct initiation of the chlorine atoms in CTFE units through atom transfer radical polymerization, as confirmed by ¹H NMR and FTIR spectroscopy. The P(VDF‐co‐CTFE)‐g‐POEM comb polymer was introduced as an additive to prepare poly(vinylidene fluoride) antifouling ultrafiltration membranes. As the contents of comb polymer increased, the mechanical properties of membranes slightly decreased due to the decreased crystallinity of the membranes, as revealed by universal testing machine and X‐ray diffraction. However, water contact angle measurement and X‐ray photoelectron spectroscopy showed that the hydrophilic POEM segments spontaneously segregated on the membrane surfaces. As a result, the antifouling property of the membranes containing P(VDF‐co‐CTFE)‐g‐POEM comb polymer was considerably improved with a slight change of water flux. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 183–189, 2010     

Optimization of anionic conductivity through the coexistence of ionomer cluster and backbone-backbone morphologies in anion exchange membranes

Random copolymers of poly(4-vinylpyridine) and polyisoprene were synthesized, and subsequently quaternized with 1-alkylbromides. The number of carbons on the pendant side-chain of the resultant comb-shaped polymer, n, ranged from 2–8. The comb-shaped polymers were crosslinked employing thiol-ene chemistry to give mechanically robust ion conducting membranes. Analysis by wide and medium-angle X-ray scattering show three morphology regimes that are dependent on the number of carbons on the pendant side-chains. When n = 2, ionomer cluster morphology was dominant, when n = 8 backbone-backbone morphology was dominant, and when n = 3–6, the membrane showed a coexistence of both ionomer cluster and backbone-backbone morphologies. Evaluation of the water uptake of the membranes showed a maximum water uptake per cation of 9.5 when n = 5 at 95% relative humidity (RH) and 60°C. Conductivity of the samples characterized by electrochemical impedance spectroscopy showed bromide conductivity as high as 110 mS/cm when n = 3 at 95% RH and 90°C.     

13C NMR spectra and structure of mono-, di- and trimethoxyphenylethylamines and amphetamines

Carbon-13 and proton chemical shifts of mono-, di- and trimethoxylated phenylethylamines (PEAs) and their hydrochlorides were determined and the signals were assigned and are reported. The data are interpreted to indicate that the side-chains of PEA derivatives and amphetamine salts have the amino and aromatic moieties predominantly trans (antiperiplanar), that ‘sandwiched’ OCH₃ groups and side-chains are forced out of the ring plane and that planar ortho-OCH₃ groups have their electron lone pairs oriented toward the side-chain and partially stabilize gauche rotamers. It is suggested that the location and density of electronic charges just outside the aromatic ring will significantly affect interactions with putative receptors.     

The NMR spectra of porphyrins. 27—proton NMR spectra of chlorophyll-a and pheophytin-a

The 500 MHz proton NMR spectra of chlorophyll-a in several non-aggregating solvents, at high dilution, are given and that of pheophytin-a in CDCl₃ at 360 MHz and at high dilution is reported. Under these conditions, the dispersion is such that separate resonances are observed and can be assigned for all protons in the molecules, except P-5 to P-15 in phytyl side-chain. The complex spin systems of the C-7 propionic ester side-chains, and of the P-1/P-2 fragment, are analysed and the couplings obtained are interpreted in terms of possible conformations of the side-chain.     

Conformational investigations of cyclic dipeptides: Cyclo-glycyl-L-methionyl,cyclo-glycyl-D,L-norleucyl and cyclo-glycyl-D,L-norvalyl

The E₀ rotamer of c-Gly-Met has been found to be almost as equally populated as the F rotamer at low temperatures, whereas in c-Gly-D ,L -Nle and c-Gly-D ,L -Nvl the F rotamer predominates. The increase of the E₀ rotamer population parallels the increase of the boat diketopiperazine (DKP) ring conformation, in which Med side-chain occupies a pseudoaxial position. Thermodynamic parameters for DKP ring inversion and for conformational transitions in the side-chains were experimentally determined for each cyclic dipeptide investigated.     

Tunable Electrochemical Peptide Modifications: Unlocking New Levels of Orthogonality for Side-Chain Functionalization

Electrochemical transformations provide enticing opportunities for programmable, residue-specific peptide modifications. Herein, we harness the potential of amidic side-chains as underutilized handles for late-stage modification through the development of an electroauxiliary-assisted oxidation of glutamine residues within unprotected peptides. Glutamine building blocks bearing electroactive side-chain N,S-acetals are incorporated into peptides using standard Fmoc-SPPS. Anodic oxidation of the electroauxiliary in the presence of diverse alcohol nucleophiles enables the installation of high-value N,O-acetal functionalities. Proof-of-principle for an electrochemical peptide stapling protocol, as well as the functionalization of dynorphin B, an endogenous opioid peptide, demonstrates the applicability of the method to intricate peptide systems. Finally, the site-selective and tunable electrochemical modification of a peptide bearing two discretely oxidizable sites is achieved.     

Surface characteristics of polysulfoalkyl methacrylates

Coated hydroxyethyl methacrylate-sodium sulfoalkyl methacrylate copolymer films were surface characterized. The contact angle hysteresis increases and the receding angle decreases with increasing alkyl side-chain length, while the advancing angle decreases with hydration time. It was found that the buoyancy slopes of the advancing (r_a) and receding (r_r) process determined by the Wilhelmy plate method were not parallel. The ratio of r_a to r_r was greater than 1, and increases with the alkyl side-chain length and the hydration time, contrary to that of polyhydroxyethyl methacrylate, where r_a/r_r was less than 1. The slope ratio would be suppressed in solution with added salt, revealing that the reorientation and expansion of the polymer chain in water is being suppressed. X-ray photoelectron spectroscopy (XPS) analysis of the surface of these copolymers showed a striking enrichment of the sulfonate groups in the surface. The zeta potential was between −40 and −50 mV as measured by the streaming potential method. During dehydration, along with a decrease in sulfur and sodium concentration in the surface, the carbon 1s peak at the high binding energy decreased and the alkyl carbon main peak increased. The surface tension of aqueous solutions of sulfoalkyl methacrylate monomers and homopolymers decreases with increasing alkyl side-chain length, which may contribute to the decrease in water-polymer film interfacial tension and thus the increase in the slope ratio.     

Side-chain engineering of high-efficiency conjugated polymer photovoltaic materials

In recent years,conjugated polymers have attracted great attention in the application as photovoltaic donor materials in polymer solar cells(PSCs).Broad absorption,lower-energy bandgap,higher hole mobility,relatively lower HOMO energy levels,and higher solubility are important for the conjugated polymer donor materials to achieve high photovoltaic performance.Side-chain engineering plays a very important role in optimizing the physicochemical properties of the conjugated polymers.In this article,we review recent progress on the side-chain engineering of conjugated polymer donor materials,including the optimization of flexible side-chains for balancing solubility and intermolecular packing(aggregation),electron-withdrawing substituents for lowering HOMO energy levels,and two-dimension(2D)-conjugated polymers with conjugated side-chains for broadening absorption and enhancing hole mobility.After the molecular structural optimization by side-chain engineering,the2D-conjugated polymers based on benzodithiophene units demonstrated the best photovoltaic performance,with powerconversion efficiency higher than 9%.     

Preparation and characterization of side-chain liquid crystalline polymers containing chenodeoxycholic acid residue

A series of new side-chain liquid crystalline polymers containing chenodiol residue derived from 24-[4′-hydroxybiphenyl-4-yl-4-(allyloxy)benzoyloxy]-3α,7α-di{n-[4′-(4-ethoxybenzoyloxy)biphenyl-4-yloxy]-n-oxoalkanoyloxy}-5β-cholane was designed and prepared. The chemical structures of the monomer and polymer were confirmed by Fourier transform infrared and ¹H NMR spectra. The mesomorphic properties of monomer and polymer were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X-ray diffraction. The side-chain liquid crystalline polymers revealed wide mesophase temperature range and high thermal stability, and they showed nematic liquid crystalline phase. The influence of flexible space group length on thermal properties and specific rotation was examined.