Synthesis and conformation of poly(L-azetidine-2-carboxylic acid-L-proline) and poly([L-proline]3-L-azetidine-2-carboxylic acid)

The synthesis, characterization, and conformational assessment of poL y(L -Aze-L -Pro) and poly[(L -Pro)₃-L -Aze] are reported. The polymers were prepared by using the pentachlorophenol active ester as the polymerizable tetrapeptide derivatives. The copolymer, poly(L -Aze-L -Pro), assumes a Form II helix in polar solvents, and is converted into a form I-like helix at a critical solvent composition of ethanol to trifluoroethanol. The CD spectrum of this Form I-like conformation of poly(L -Aze-L -Pro) is similar to that of poly(trans-5-isopropyl-L -proline), indicating that the rigid four-membered ring at the alternating position can lock in the structure by a mechanism similar to that of a bulky substituent at the trans-5-position of proline. The helix conformation of this copolymer was unfolded in a 0.2M CaCl₂ aqueous solution. In contrast to poly(L -Aze-L -Pro), the copolymer of poly[(L -Pro)₃-L -Aze] contains both cis and trans peptide bond geometry when dissolved in a 90:10 ETOH-H₂O mixture. The conversion of the mixed conformation of poly[(L -Pro)₃-L -Aze)] into a polyproline Form II-like structure occurred in highly polar solvent environments such as water.     

Synthesis and properties of carbamate‐ and amine‐containing poly(phenylacetylenes)

The 3‐ and 4‐aminophenylacetylenes protected by t‐butoxycarbonyl (t‐Boc) and 9‐fluorenylmethoxycarbonyl (Fmoc) groups ( 3a – 6a ) were synthesized and polymerized using [(nbd)RhCl]₂ ( 1 ) and [(nbd)Rh⁺‐η⁶‐PhB^?Ph₃] ( 2 ) catalysts. The t‐Boc‐containing polymers [poly( 3a ) and poly( 4a )] were obtained in high yield (82–91%). Among the Fmoc‐protected monomers, the para‐derivative polymerized well [poly( 6a ); yield = 85–94%], whereas its meta‐substituted analogue did not afford high molecular weight polymer in good yield [poly( 5a ); yield = 10–15%]. The use of KN(SiMe₃)₂ as a cocatalyst in conjunction with 1 led to a dramatic increase in the molecular weight of the polymers. The acid‐ and base‐catalyzed removal of the t‐Boc and the Fmoc groups, respectively, generated primary amine‐containing polymers [poly( 3b )–poly( 6b )] which cannot be obtained directly by the polymerization of the corresponding monomers. The solubility characteristics of the polymers bearing protected amino groups were quite different from those of the unprotected ones, the former being soluble in polar solvents, whereas the latter displayed poor solubility even in polar protic or highly polar aprotic solvents. The attempts to accomplish the free‐standing membrane fabrication by solution casting were successful only for poly( 3a ), and an augmentation in the gas permeability and CO₂/N₂ permselectivity was discerned in comparison with the unsubstituted poly(phenylacetylene) and poly(m‐t‐butyldimethylsiloxyphenylacetylene). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1853–1863, 2009     

α‐Propargyl amino acid‐derived optically active novel substituted polyacetylenes: Synthesis,secondary structures,and responsiveness to ions

Novel optically active substituted acetylenes HC? CCH₂CR¹(CO₂CH₃)NHR² [(S)‐/(R)‐ 1 : R¹ = H, R² = Boc, (S)‐ 2 : R¹ = CH₃, R² = Boc, (S)‐ 3 : R¹ = H, R² = Fmoc, (S)‐ 4 : R¹ = CH₃, R² = Fmoc (Boc = tert‐butoxycarbonyl, Fmoc = 9‐fluorenylmethoxycarbonyl)] were synthesized from α‐propargylglycine and α‐propargylalanine, and polymerized with a rhodium catalyst to provide the polymers with number‐average molecular weights of 2400–38,900 in good yields. Polarimetric, circular dichroism (CD), and UV–vis spectroscopic analyses indicated that poly[(S)‐ 1 ], poly[(R)‐ 1 ], and poly[(S)‐ 4 ] formed predominantly one‐handed helical structures both in polar and nonpolar solvents. Poly[(S)‐ 1a ] carrying unprotected carboxy groups was obtained by alkaline hydrolysis of poly[(S)‐ 1 ], and poly[(S)‐ 4b ] carrying unprotected amino groups was obtained by removal of Fmoc groups of poly[(S)‐ 4 ] using piperidine. Poly[(S)‐ 1a ] and poly[(S)‐ 4b ] also exhibited clear CD signals, which were different from those of the precursors, poly[(S)‐ 1 ] and poly[(S)‐ 4 ]. The solution‐state IR measurement revealed the presence of intramolecular hydrogen bonding between the carbamate groups of poly[(S)‐ 1 ] and poly[(S)‐ 1a ]. The plus CD signal of poly[(S)‐ 1a ] turned into minus one on addition of alkali hydroxides and tetrabutylammonium fluoride, accompanying the red‐shift of λ_max. The degree of λ_max shift became large as the size of cation of the additive. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Poly[(3-hydroxypropyl) oxirane] and poly[(4-hydroxybutyl)oxirane]: New hydrophilic polyether elastomers

Preparations of poly[(3-hydroxypropyl)oxirane] and poly[(4-hydroxybutyl)oxirane] are described. Three routes to poly[(3-hydroxypropyl)oxirane] are discussed, each of which involves the methanolysis of a polymeric ester. (3-Acetoxypropyl)oxirane, [3-(m-chlorobenzoyloxy)propyl]oxirane, and (3-chloropropyl)oxirane were polymerized using the AIEt₃/H₂O/AcAc initiator system. Poly[(3-acetoxypropyl)oxirane] and poly{[3-(m-chlorobenzoyloxy)propyl]oxirane} were converted directly to poly[(3-hydroxypropyl)oxirane] by methanolysis, the former under either acidic or basic conditions only. Poly[(3-chloropropyl)oxirane] was first converted to poly[(3-benzoyloxypropyl)oxirane] by treatment with tetrabutylammonium benzoate; subsequent basic methanolysis then afforded poly[(3-hydroxypropyl)oxirane]. Poly[(3-hydroxypropyl)oxirane] is a colorless elastomer which can be cast into tough, clear films from water or methanol. Poly[(4-hydroxybutyl)oxirane] was prepared from poly[(4-chlorobutyl)oxirane] by benzoyloxylation and subsequent methanolysis. Poly[(4-hydroxybutyl)oxirane] is insoluble in water, but is hydrophilic and can be cast into tough films from methanol or dimethylsulfoxide.     

Polymerization of optically active disubstituted acetylene monomers by Pd catalyst bearing bulky phosphine ligand

Chloro- and aryl-substituted acetylene monomers having an optically active group were polymerized by a Pd catalyst [(^tBu₃P)PdMeCl] bearing a bulky phosphine ligand, and by MoCl₅ for comparison. The corresponding disubstituted acetylene polymers with M_n's = 2000–19,500 and 6900–10,800 were obtained in 29–83% and 11–62% yields when the Pd and Mo catalysts were used, respectively. The formation of polyacetylenes, poly[(R)- 1p ], poly[(R)- 1m ], and poly[(S)- 2p ] were confirmed by SEC and the presence of a Raman scattering peak based on the alternating double bonds of the main chain. Pd-based poly[(R)- 1m ] exhibited CD signals around 350 nm assignable to a certain secondary structure, while Mo-based poly[(R)- 1m ] did not. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3011–3016     

Synthesis,hydrophilicity, and oxygen permeability of poly[(trimethylsilyl)propyne]-gr-poly(N,N-dimethylacrylamide)

N,N-dimethylacrylamide (DMAA) was graft copolymerized on poly[(trimethylsilyl)propyne] (PTMSP) by single electron reduction of PTMSP with potassium naphthalenide (K-Naph), followed by anion polymerization of DMAA from the carbanion formed in the reduction. A hard and practically non-water-swelling PTMSP-gr-poly(DMAA) was obtained under the conditions using controlled amount of K-Naph and DMAA. The graft copolymer was characterized with regard to structure, number-averaged molecular weight, and the amount of grafting poly(DMAA) determined by the relative absorbance of the IR absorption band assigned to the CO and SiC H functionalities (A_CO/A_{SiC H}). The oxygen permeability and water contact angle (θ) of the graft copolymer were evaluated while varying the amount of grafting poly(DMAA). The graft copolymer proved to be highly oxygen permeable (165 Barrers) and hydrophilic (θ = 27°). Its transparency was also elucidated with UV–vis spectra. This graft copolymer was proposed as a promising candidate for use as a hard contact lens material. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 603–610, 1998     

Poly(β-Amino acids). VI. Synthesis and conformational properties of poly[(r)-3-pyrrolidinecarboxylic acid]

Racemic and optically active 3-pyrrolidinecarboxylic acids (β-proline) were synthesized, and their polymers, poly[(RS)-β-proline] and poly[(R)-β-proline], were prepared by the polycondensation reaction of the p-nitrophenyl esters. Model compounds, N-cyclopentylcarboxylic acid pyrrolidide and N-cyclopentylcarbonyl-(R)-3-pyrrolidinecarboxylic acid pyrrolidide, were synthesized to elucidate the conformation of the polymer. The solution properties of poly[(R)-β-proline] and the model compounds were investigated by means of circular dichroism (CD) and NMR spectroscopy. The spectral patterns of the polymer and model compounds were similar in various solvents. Poly[(R)-β-proline] and poly[(RS)-β-proline] showed identical NMR spectra. These results suggest that poly[(R)-β-proline] may exist in a random conformation consisting of mixtures of cis and trans amide bonds. The conformational study of cyclopentanecarboxylic acid pyrrolidide by NMR spectroscopy with a shift reagent, Eu(fod)₃, in CDCl₃ implied that the plane containing the amide group bisects the cyclopentane ring. This suggests that each amide plane in the polymer in chloroform may also bisect the pyrrolidine ring.     

Asymmetric anionic polymerization of optically active N-1-cyclohexylethylmaleimide

Chiral (S)-(−)-N-1-cyclohexylethylmaleimide [(S)-CEMI] and (R)-(+)-N-1-cyclohexylethylmaleimide [(R)-CEMI] were synthesized successfully and then polymerized with chiral complexes of (−)-sparteine or (S,S)-(1-ethylpropylidene)bis(4-benzyl-2-oxazoline) [(S,S)-Bnbox] and organometal as initiators in toluene or tetrahydrofuran to obtain optically active polymers. The effects of the polymerization conditions on the optical activity and structure of poly(N-1-cyclohexylethylmaleimide)s were investigated with gel permeation chromatography, circular dichroism, specific rotation, and ¹³C NMR measurements. Poly[(R)-CEMI] obtained with dimethylzinc (Me₂Zn)/(S,S)-Bnbox had the highest specific rotation ([α]₄₃₅ = +323.7°). Complexes of Bnbox and diethylzinc or Me₂Zn were used very effectively as chiral initiators for the asymmetric anionic polymerization of (S)-CEMI and (R)-CEMI. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4682–4692, 2004     

Photochemical Properties and Activity of Water‐Soluble Polymer/C60 Nanohybrids for Photodynamic Therapy

Water‐soluble star‐like poly(vinyl alcohol)/C₆₀ and poly{[poly(ethylene glycol) acrylate]‐co‐(vinyl acetate)}/C₆₀ nanohybrids are prepared by grafting macroradicals onto C₆₀ and are assessed as photosensitizers for photodynamic therapy. The photophysical and biological properties of both nanohybrids highlight key characteristics influencing their overall efficiency. The macromolecular structure (linear/graft) and nature (presence/absence of hydroxyl groups) of the polymeric arms respectively impact the photodynamic activity and the stealthiness of the nanohybrids. The advantages of both nanohybrids are encountered in a third one, poly[(N‐vinylpyrrolidone)‐co‐(vinyl acetate)]/C₆₀, which has linear grafts without hydroxyl groups, and shows a better photodynamic activity.

     

Charge transport study of semiconducting polymers and their bulk heterojunction blends by capacitance measurements

We use frequency dependent capacitance measurements to probe carrier mobilities and transport parameters of six representative semiconducting polymers and some of their bulk heterojunction (BHJ) blends. With a suitable choice of a hole injection layer, well-defined signals for hole transport characterization can be obtained for the pristine polymers [J. Appl. Phys. 99, 013706 (2006)]. However, ill-defined signals with negative capacitances, arising from undesirable electron leakages, are obtained for the BHJ blends. The problem of electron leakage can be circumvented by inserting an electron blocking and trapping layer under the cathode. As a result, hole transport properties of BHJ blends can be obtained. For the BHJ of poly(3-hexylthiophene) blended with [6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PC₆₁BM), the hole mobilities seem to be insensitive to the composition of the BHJ, indicating the P3HT component in the BHJ is well connected. On the other hand, for poly[N-9“-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadia zole)] doped with [6,6]-phenyl-C71-butyric acid methyl ester (PCDTBT:PC₇₁BM), a clear reduction of the hole mobility is observed as the polymer composition is reduced. Temperature dependent experiments were performed. The data are analyzed by the Gaussian Disorder Model. We found that the energetic disorder is independent of the composition of the BHJ. Organic photovoltaic performances of BHJ blends are also measured in this contribution. The correlation between device performance and energetic disorder of the BHJ will be discussed. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Synthesis,structural, and retrostructural analysis of helical dendronized poly(1‐naphthylacetylene)s

Structural and retrostructural analysis of chiral, nonracemic ( poly [(3,4,5)dm8G1‐1EN] ), and achiral ( poly[(3,4,5)12G1‐1EN] ) poly(1‐naphthylacetylene)s demonstrates new design principles for helical dendronized polyarylacetylenes. The oblate cylindrical dendronized polymers self‐organize in a c2mm centered rectangular columnar (Φ_r‐c) lattice. An all cis‐polyene backbone microstructure with very high cisoid character is introduced to rationalize features from small‐ and wide‐angle X‐ray diffraction experiments. More compact helical conformations are ideal for efficient communication or amplification of chirality over long distances. Peripheral chiral tails select a preferred helical screw sense of the polyene backbone. In solution, the preferred helical conformation persists over a wide temperature range. In bulk, the naphthyl moiety facilitates a longer correlation length for helical order compared to an analogous minidendritic poly(phenylacetylene). These attributes suggest that the naphthyl moiety may be better suited for expressing helical chirality in monolayer domains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4974–4987, 2007     

Synthesis of optically active polynucleotide analogs with poly(vinyl alcohol)s as backbones and adenine and 5-bromouracil derivatives as pendants

The optically active polynucleotide analogs were prepared by grafting nucleic acid base derivatives onto poly(vinyl alcohol). The (R)-ethyl 2-(5-bromouracil-1-yl)propanoate was obtained either by reaction of 5-bromouracil sodium salt with (S)-ethyl 2-[(methylsulfonyl)oxy]propanoate or reaction of 5-bromouracil with (S)-ethyl lactate in the presence of triphenyl phosphine and diethyl azodicarboxylate. Subsequent hydrolysis of the ester is aqueous acid provided the optically pure (R)-bromouracilypropanoic acid. The monomer model compounds were prepared by an esterification reaction of the pendant groups with 3-pentyl alcohol in the presence of dicyclohexylcarbodiimide and a catalytic amount of 4-pyrrolidinopyridine. Poly(vinyl alcohol) underwent reaction with the (R)-bromouracilylpropanoic acid or the (R)-adeninylpropanoic acid in the presence of dicyclohexylcarbodiimide and a catalytic amount of 4-pyrrolidinopyridine. The resulting polymers were optically active and percents grafting were almost quantitative.     

Non‐centrosymmetric CuSCN Based Coordination Polymers with Substituted Pyrazine and Pyrimidine Ligands

Non‐centrosymmetric one‐ to three‐dimensional CuSCN‐based coordination polymers with substituted pyrazine or pyrimidine spacer ligands can be prepared by self‐assembly in acetonitrile solution at 100 °C. Both [CuSCN(2 NCpyz)₂] ( 1 ) (2 NCpyz = 2‐cyanopyrazine) and [CuSCN(4 HOpym)₂] ( 3 ) (4 HOpym = 4‐hydroxypyrimidine) contain single zigzag CuSCN chains as their central backbone and crystallise in polar space groups (monoclinic Cm and orthorhombic Ama2). In [(CuSCN)₂(μ‐2 Mepyz)] ( 2 ) (2 Mepyz = 2‐methylpyrazine), [(CuSCN)₂] staircase double chains are connected by bridging 2 Mepyz ligands to afford a lamellar polymer (triclinic P 1). Whereas [CuSCN(5 Brpym)] ( 4 ) (5 Brpym = 5‐bromopyrimidine) with its honeycomb [CuSCN] layers is chiral (monoclinic P2₁), both 3 D polymers [(CuSCN)₂(μ‐pym)] ( 5 ) and [(CuSCN)₃(μ‐4 Mepym)] ( 6 ) (4 Mepym = 4‐methylpyrimidine) contain polar coordination networks (orthorhombic Fdd2 and monoclinic Pc). The CuSCN framework in ( 5 ) consists of thiocyanate bridged [CuS] chains, that in 6 of interlocked [CuSCN] and [Cu₂S(SCN)] sheets.     

Synthesis and molecular properties of new poly(naphthalene-1, 3, 4-oxadiazole)s

Poly[(1, 4-naphthalene)-2, 5-diyl-1, 3, 4-oxadiazole] and poly[(2, 6-naphthalene)-2, 5-diyl-1, 3, 4-oxadiazole] have been synthesized and investigated in conc. H₂SO₄, by the flow birefringence method, in comparison with poly[(1, 4-phenylene)-2, 5-diyl-1, 3, 4-oxadiazole]. Changes in conformation parameters and optical anisotropy of a chain unit induced by incorporation of the naphthalene groups into the macromolecule backbone have been evaluated.     

Solvent‐Dependent Structure of Iridium Dihydride Complexes: Different Geometries at Low and High Dielectricity of the Medium

The hydride iridium pincer complex [(PCyP)IrH₂] (PCyP=cis‐1,3‐bis[(di‐tert‐butylphosphino)methyl]cyclohexane, 1 ) reveals remarkably solvent‐dependent hydride chemical shifts, isotope chemical shifts, J_HD and T₁(min), with r_HH increasing upon moving to more polar medium. The only known example of such behaviour (complex [(POCOP)IrH₂], POCOP=2,6‐(tBu₂PO)₂C₆H₃) was explained by the coordination of a polar solvent molecule to the iridium (J. Am. Chem. Soc. 2006 , 128, 17114). Based on the existence of an agostic bond between α‐C?H and iridium in 1 in all solvents, we argue that the coordination of solvent can be rejected. DFT calculations revealed that the structures of 1 and [(POCOP)IrH₂] depend on the dielectric permittivity of the medium and these compounds adopt trigonal‐bipyramidal geometries in non‐polar media and square‐pyramidal geometries in polar media.     

Hydrolysis of Peptide Bonds in Protein Micelles Promoted by a Zirconium(IV)-Substituted Polyoxometalate as an Artificial Protease

The development of artificial proteases is challenging, but important for many applications in modern proteomics and biotechnology. The hydrolysis of hydrophobic or unstructured proteins is particularly difficult due to their poor solubility, which often requires the presence of surfactants. Herein, it is shown that a zirconium(IV)-substituted Keggin polyoxometalate (POM), (Et₂NH₂)₁₀[Zr(α-PW₁₁O₃₉)₂] ( 1 ), is able to selectively hydrolyze β-casein, which is an intrinsically unstructured protein at pH 7.4 and 60 °C. Four surfactants (sodium dodecyl sulfate (SDS), N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (ZW3-12), 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate (CHAPS), and polyethylene glycol tert-octylphenyl ether (TX-100)), which differ in the nature of their polar groups, were investigated for their role in influencing the selectivity and efficiency of protein hydrolysis. Under experimental conditions, β-casein forms micellar structures in which the hydrophilic part of the protein is water accessible and able to interact with 1 . Identical fragmentation patterns of β-casein in the presence of 1 were observed through SDS poly(acrylamide) gel electrophoresis both in the presence and absence of surfactants, but the rate of hydrolysis varied, depending on the nature of surfactant. Whereas TX-100 surfactant, which has a neutral polar head, caused only a slight decrease in the hydrolysis rate, stronger inhibition was observed in the presence surfactants with charges in their polar heads (CHAPS, ZW3-12, SDS). These results were consistent with those of tryptophan fluorescencequenching studies, which showed that the binding between β-casein and 1 decreased with increasing repulsion between the POM and the polar heads of the surfactants. In all cases, the micellar structure of β-casein was not significantly affected by the presence of POM or surfactants, as indicated by circular dichroism spectroscopy.     

Solubility of carbon dioxide,methane, and propane in silicone polymers. Effect of polymer backbone chains

The solubility of carbon dioxide, methane, and propane in poly(dimethyl silmethylene) [(CH₃)₂SiCH₂]_x and poly(tetramethyl silhexylene siloxane) [(CH₃)₂Si (CH₂)₆Si (CH₃)₂O]_x was measured in the temperature range from 10.0 to 55.0°C and at elevated pressures. The present results are compared with similar measurements made with other silicone polymers. At a given temperature and pressure, the solubility of the above three gases is highest in poly(dimethyl siloxane) (Me₂SiO)_x. The gas solubility is decreased by either backbone-chain or side-chain substitutions of functional groups in (Me₂SiO)_x which increase the stiffness of the polymer chains and decrease the specific or fractional free volume of the polymers. It is conjectured that a decrease in the free volume of silicone polymers has a greater effect in decreasing the gas solubility than differences in gas/polymer interactions [with the exception of specific interactions (e.g., between CO₂ and polar groups in the polymer)]. © 1993 John Wiley & Sons, Inc.     

Water soluble amino grafted silicon nanoparticles and their use in polymer solar cells

Stable aqueous amino-grafted silicon nanoparticles(SiNPs-NH2) were prepared via one-pot solution method. By grafting amino groups on the particle surface, the dispersion of SiNPs in water became very stable and clear aqueous solutions could be obtained. By incorporating SiNPs-NH2 into the hole transport layer of poly(3,4-ethylenedioxythiophene)/polystyrene sulfonic acid(PEDOT:PSS), the performance of polymer solar cells composed of poly[2-methoxy,5-(2'-ethylhexyloxy)-1,4-phenylene vinylene](MEH-PPV):[6,6]-phenyl-C61-butyric acid methyl ester(PCBM) as active layer can be improved. SiNPs-NH2 are dispersed uniformly in the PEDOT:PSS solution and help form morphologies with small-sized domains in the PEDOT:PSS film. SiNPs-NH2 serve as screens between conducting polymer PEDOT and ionomer PSS to improve the phase separation and charge transport of the hole transport layer. As a result, the sheet resistance of PEDOT:PSS thin films is decreased from(93 ± 5) × 105 to(13 ± 3) × 105 ?/□. The power conversion efficiency(PCE) of polymer solar cells was thus improved by 9.8% for devices fabricated with PEDOT:PSS containing 1 wt% of SiNPs-NH2, compared with the devices fabricated by original PEDOT:PSS.     

Design of molecular architectures for polymeric mesophase formation

Based on the tendency of low molar mass liquid crystals composed of extended mesogens symmetrically disubstituted with long n-alkoxy substituents to exhibit smectic C mesophases, we have proposed that SCLCPs with laterally attached (vs. terminally attached) mesogens offer an ideal architecture for obtaining s_C* mesophases. In particular, mesogens that typically form the desirable s_C*-n phase sequence can be laterally attached to the polymer backbone through a chiral spacer, which should result in high values of spontaneous polarization. Not only are we using mesogens which exhibit s_C*-n phase sequences, we are also attempting to induce smectic layering into systems which typically form nematic mesophases by using immiscible hydrocarbon/fluorocarbon components and electron-donor-acceptor interactions. Thus far, the thermotropic behavior of poly{5-[[[2', 5'-bis[(3″-fluoro-4″-dimethoxyphenyl)ethynyl]benzyl]oxy]carbonyl[2.2.1]hept-2-ene]s and poly(5-[[[2',5'-bis[(3″-fIuoro-4″-methoxybenzoyl)oxy]benzyl]oxy]carbonyl]-bicyclo[2.2.1]hept-2-ene)s correspond to that of their low molar mass analogs. Preliminary results demonstrate that smectic layering is successfully induced in 2,5-bis[(4'-n-alkoxybenzoyl)oxy]toluenes and polynorbornenes with laterally attached 2,5-bis[(4'-n-alkoxybenzoyl)oxy]benzyl mesogens by terminating the n-alkoxy substituents with perfluorinated segments.     

Green,rapid, and highly efficient syntheses of α,α′-bis[(aryl or allyl)idene]cycloalkanones and 2-[(aryl or allyl)idene]-1-indanones as potentially biologic compounds via solvent-free microwave-assisted Claisen–Schmidt condensation catalyzed by MoCl5

A new, green, and highly efficient protocol for the expeditious preparation of some α,α′-bis[(aryl or allyl)idene]cycloalkanones and 2-[(aryl or allyl)idene]-1-indanones via a simple microwave-assisted Claisen–Schmidt condensation reaction catalyzed by MoCl₅ was successfully developed. Outstanding features of the current methodology include the use of solvent-free conditions, simple operation, use of a very inexpensive and available catalyst, low catalyst loading, short reaction times, high yields of the pure products, no harmful by-products, easy workup, and also the applicability of microwave irradiation as a clean source of energy. Furthermore, a gram-scale reaction was successfully conducted, proving the scalability of this current Claisen–Schmidt condensation reaction.