Monomeric Derivatives Research Articles

Preparation of Chiral Polydiacetylene Films by Using Three-Photon Polymerization.

Asymmetric polymerization of polydiacetylene (PDA) from commercially available achiral derivative of diacetylene monomer using circularly polarized pulse laser is demonstrated. Chiral source was only circularly polarized laser, and irradiation of left- and right-circularly polarized light effectively promoted the polymerization of chiral PDAs with opposite handedness. Difference between the laser wavelength and the absorption peak of monomer suggested the contribution of the multiphoton excitation to the photo-polymerization. Laser power dependence of the polymerization rate indicated the possibility of three-photon polymerization.

New organosilicon derivatives of some analytical reagents: sorbents and metallochromic agents

A synthesis of organosilicon monomeric and polymeric derivatives of 1,4-phenylenediamine, 4-aminoantipyrine, and aniline, which are analytical agents possessing sorption properties, was accomplished. The synthesized organosilicon polymers were studied as sorbents of heavy metals FeIII, HgII and noble metals AgI, AuIII, RhIII, PdII, PtIV. Poly[(3-N-silsesquioxanylpropyl-4aminoantipyrine)] exhibited high sorption activity with respect to platinum group metals in comparison with poly[N,N´-bis(3-silsesquioxanylpropyl)-1,4-phenylenediamine]. The reaction of poly[(3-N-silsesquioxanylpropyl-4-aminoantipyrine)] practically with all the elements under study was accompanied by coloring. The starting monomer exhibited similar metallochromic properties.

New pseudodimeric aurones as palm pocket inhibitors of Hepatitis C virus RNA-dependent RNA polymerase

The NS5B RNA-dependent RNA polymerase (RdRp) is a key enzyme for Hepatitis C Virus (HCV) replication. In addition to the catalytic site, this enzyme is characterized by the presence of at least four allosteric pockets making it an interesting target for development of inhibitors as potential anti-HCV drugs. Based on a previous study showing the potential of the naturally occurring aurones as inhibitors of NS5B, we pursued our efforts to focus on pseudodimeric aurones that have never been investigated so far. Hence, 14 original compounds characterized by the presence of a spacer between the benzofuranone moieties were synthesized and investigated as HCV RdRp inhibitors by means of an in vitro assay. The most active inhibitor, pseudodimeric aurone 4, induced high inhibition activity (IC50 = 1.3 μM). Mutagenic and molecular modeling studies reveal that the binding site for the most active derivatives probably is the palm pocket I instead of the thumb pocket I as for the monomeric derivatives.

Conductive polymeric ionic liquids for electroanalysis and solid-phase microextraction

Three novel electropolymerizable thiophene-based ionic liquids (ILs) were synthesized and characterized as potential candidates for developing selective extraction media for chemical analysis. Electropolymerization of the bis[(trifluoromethyl)sulfonyl]imide ([NTf2]-) analogs successfully produced uniform polymeric thin-films on macro- and microelectrode substrates from both vinyl and methylimidazolium IL monomer derivatives. The resultant conducting polymer IL (CPIL) films were characterized by electrochemical methods and found to exhibit attractive behavior towards anionic species while simultaneously providing an exclusion barrier toward cationic species. Thermogravimetric analysis of the thiophene-based IL monomers established a high thermal stability, particularly for the methylimidazolium IL, which was stable until temperatures above 350 °C. Subsequently, the methylimidazolium IL was polymerized on 125 μm platinum wires and utilized for the first time as a sorbent coating for headspace solid-phase microextraction (HS-SPME). The sorbent coating was easily prepared in a reproducible manner, provided high thermal stability, and allowed for the gas chromatographic analysis of polar analytes. The normalized response of the poly[thioph-C6MIm][NTf2]-based sorbent coating exhibited higher extraction efficiency compared to an 85 μm polyacrylate fiber and excellent fiber-to-fiber reproducibility. Therefore, the electropolymerizable thiophene-based ILs were found to be viable new materials for the preparation of sorbent coatings for HS-SPME.

Cylindrofridins A-C, Linear Cylindrocyclophane-Related Alkylresorcinols from the Cyanobacterium Cylindrospermum stagnale.

A rapid and exhaustive one-step biomass extraction as well as an enrichment and cleanup procedure has been developed for HPLC-UV detection and quantification of closely related [7.7]paracyclophanes and structural derivatives based on a two-phase solvent system. The procedure has been validated using the biomass of the carbamidocyclophane- and cylindrocyclophane-producing cyanobacterium Nostoc sp. CAVN2 and was utilized to perform a screening comprising 102 cyanobacterial strains. As a result, three new cylindrocyclophane-related alkylresorcinols, cylindrofridins A-C (1-3), and known cylindrocyclophanes (4-6) were detected and isolated from Cylindrospermum stagnale PCC 7417. Structures of 1-3 were elucidated by a combination of 1D and 2D NMR experiments, HRMS, and ECD spectroscopy. Cylindrofridin A (1) is the first naturally occurring [7.7]paracyclophane-related monomeric derivative. In contrast, cylindrofridins B (2) and C (3) represent dimers related to 1. Due to chlorination at the alkyl carbon atom in 1-3, the site of [7.7]paracyclophane macrocycle formation, the cylindrofridins represent linearized congeners of the cylindrocyclophanes. Compounds 1-3 were not toxic against nontumorigenic HaCaT cells (IC50 values >25 μM) compared to the respective cylindrocyclophanes, but 1 was the only cylindrofridin showing moderate activity against methicillin-resistant Staphylococcus aureus (MRSA) and Streptococcus pneumoniae with MIC values of 9 and 17 μM, respectively.

Dual stimuli-responsive polyamines derived from modifiedN-vinylpyrrolidones through CuAAC click chemistry

The synthesis via copper(I)-catalyzed azide alkyne cycloaddition (CuAAC) of three new monomer derivatives of N-vinyl-2-pyrrolidone (VP) carrying cyclic pyrrolidine, piperidine, and piperazine groups and the corresponding copolymers with unmodified VP is shown. The systems bearing pyrrolidine and piperidine displayed both thermo- and pH-response, which has not been reported previously for a polymer with polyvinylpyrrolidone (PVP) backbone. A broad modulation of the LCST with the copolymer composition and pH was observed in a temperature range 0–100 °C. The polymers carrying piperazine exhibited broad buffering regions and no thermosensitivity. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015

Amphiphilic block copolymer self‐assemblies of poly(NVP)‐b‐poly(MDO‐co‐vinyl esters): Tunable dimensions and functionalities

ABSTRACTFunctional, degradable polymers were synthesized via the copolymerization of vinyl acetate (VAc) and 2‐methylene‐1,3‐dioxepane (MDO) using a macro‐xanthate CTA, poly(N‐vinylpyrrolidone), resulting in the formation of amphiphilic block copolymers of poly(NVP)‐b‐poly(MDO‐co‐VAc). The behavior of the block copolymers in water was investigated and resulted in the formation of self‐assembled nanoparticles containing a hydrophobic core and a hydrophilic corona. The size of the resultant nanoparticles was able to be tuned with variation of the hydrophilic and hydrophobic segments of the core and corona by changing the incorporation of the macro‐CTA as well as the monomer composition in the copolymers, as observed by Dynamic Light Scattering, Static Light Scattering, and Transmission Electron Microscopy analyses. The concept was further applied to a VAc derivative monomer, vinyl bromobutanoate, to incorporate further functionalities such as fluorescent dithiomaleimide groups throughout the polymer backbone using azidation and “click” chemistry as postpolymerization tools to create fluorescently labeled nanoparticles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2699–2710

Synthetic, Spectroscopic, Crystallographic, and Biological Studies of Seven-Coordinated Diorganotin(IV) Complexes Derived from Schiff Bases and Pyridinic Carboxylic Acids

The synthesis and characterisation of diorganotin(iv) monomeric derivatives of pyridine Schiff bases and pyridinic carboxylic acids are reported. All complexes were characterised by mass spectrometry, elemental analyses, IR spectra, and multinuclear NMR analyses. Among them, complexes 5a, 5d, 5e, 5g, and 6a were also confirmed by X-ray crystallography diffraction analyses, which led to establishing that the tin atom is seven-coordinated and has a distorted pentagonal–bipyramidal coordination environment in the solid state and also revealed that both ligands occupy the equatorial positions and the organic substituents the axial positions. The antioxidant activity of the synthetic derivatives towards 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) as well as the thiobarbituric acid reactive substances (TBARS) assay were determined, and were compared with standard antioxidants, showing a dose-dependent activity in both cases. A prominent response was obtained depending on the substituent. The anti-inflammatory activity was also evaluated on a 12-O-tetradecanoylphorbol-13-acetate (TPA) model of induced acute inflammation. The results of the biological tests are discussed in terms of structural characteristics.

Immobilization and stretching of 5'-pyrene-terminated DNA on carbon film deposited on electron microscope grid.

The immobilization and stretching of randomly coiled DNA molecules on hydrophobic carbon film is a challenging microscopic technique, which possess various applications, especially for genome sequencing. In this report the pyrenyl nucleus is used as an anchor moiety to acquire higher affinity of double stranded DNA to the graphite surface. DNA and pyrene are joined through a linker composed of four aliphatic methylene groups. For the preparation of pyrene-terminated DNA a multifunctional phosphoramidite monomer compound was designed. It contains pyrenylbutoxy group as an anchor moiety for π-stacking attachment to the carbon film, 2-cyanoethyloxy, and diisopropylamino as coupling groups for conjugation to activated oligonucleotide chain or DNA molecule. This monomer derivative was suitable for incorporation into automated solid-phase DNA synthesis and was attached to the 5' terminus of the DNA chain through a phosphodiester linkage. The successful immobilization and stretching of pyrene-terminated DNA was demonstrated by conventional 100 kV transmission electron microscope. The microscopic analysis confirmed the stretched shape of the negatively charged nucleic acid pieces on the hydrophobic carbon film.

Acrylic Polymers with Pendant Phenylboronic Acid Moieties as "Turn-Off" and "Turn-On" Fluorescence Solid Sensors for Detection of Dopamine, Glucose, and Fructose in Water.

We report herein a fluorescence polymer membrane as a film-shaped solid sensory kit for the detection and quantification in water of saccharides, namely, fructose and glucose, and dopamine. The sensory motifs are phenylboronic acids, which are chemically incorporated in the polymer network in the radically initiated bulk polymerization process. The sensory membrane is fluorescent. The interaction of the sensory motifs with dopamine "turn-off" the fluorescence due to a dynamic quenching, while stable complexes are formed with saccharides giving rise to a fluorescence "turn-on". The variation of the fluorescence intensity and the wavelength of the maxima permitted the titration of the species with a detection limit of 3-4 × 10-4 M. The hydrophilic membrane allowed for the detection in water in spite of the lack of solubility in this medium of the sensory phenylboronic acid derivative monomer.

Improving the stability of peptidic radiotracers by the introduction of artificial scaffolds: which structure element is most useful?

Peptidic radiotracers are highly potent substances for the specific in vivo imaging of various biological targets with Single Photon Emission Computed Tomography and Positron Emission Tomography. However, some radiolabeled peptides such as bombesin analogs were shown to exhibit only a limited stability, hampering a successful target visualization. One option to positively influence the stability of radiolabeled peptides is the introduction of certain artificial molecular scaffolds. In order to comparatively assess the influence of different structure elements on the stability of radiolabeled peptides and to identify those structure elements being most useful for peptide radiotracer stabilization, several monomeric and dimeric bombesin derivatives were synthesized, exhibiting differing molecular designs and the chelator NODAGA for (68) Ga-labeling. The radiolabeled peptides were evaluated regarding their in vitro stability in human serum to determine the influence of the introduced molecular scaffolds on the peptides' serum stabilities. The results of the evaluations showed that the introduction of scaffold structures and the overall molecular design have a substantial impact on the stabilities of the resulting peptidic radiotracers. But besides some general trends found using certain scaffold structures, the obtained results point to the necessity to empirically assess their influence on stability for each susceptible peptidic radiotracer individually.

Synthesis, characterization, and investigation of thermal stability of two derivatives of polybithiophene

The polymerization of bithiophene in the presence and in the absence of 3-hexylthiophene was carried out by chemical oxidation methods. Dichloromethane and acetonitrile, containing thiophene derivative monomers and oxidant, were adopted as a binary organic solvent for oxidative synthesis of polybithiophene and poly[(2,2′-bithienyl)-co-(3-hexylthiophene)]. The polymers show different thermal stability properties owing to a hexyl group on repeat unit.

Functional Degradable Polymers by Radical Ring-Opening Copolymerization of MDO and Vinyl Bromobutanoate: Synthesis, Degradability and Post-Polymerization Modification.

The synthesis of vinyl bromobutanoate (VBr), a new vinyl acetate monomer derivative obtained by the palladium-catalyzed vinyl exchange reaction between vinyl acetate (VAc) and 4-bromobutyric acid is reported. The homopolymerization of this new monomer using the RAFT/MADIX polymerization technique leads to the formation of novel well-defined and controlled polymers containing pendent bromine functional groups able to be modified via postpolymerization modification. Furthermore, the copolymerization of vinyl bromobutanoate with 2-methylene-1,3-dioxepane (MDO) was also performed to deliver a range of novel functional degradable copolymers, poly(MDO-co-VBr). The copolymer composition was shown to be able to be tuned to vary the amount of ester repeat units in the polymer backbone, and hence determine the degradability, while maintaining a control of the final copolymers’ molar masses. The addition of functionalities via simple postpolymerization modifications such as azidation and the 1,3-dipolar cycloaddition of a PEG alkyne to an azide is also reported and proven by 1H NMR spectroscopy, FTIR spectroscopy, and SEC analyses. These studies enable the formation of a novel class of hydrophilic functional degradable copolymers using versatile radical polymerization methods.

New monomeric and dimeric uridinyl derivatives as inhibitors of chitin synthase

This study described the synthesis and in vitro evaluation of eight new derivatives of uridine as antifungal agents and inhibitors of chitin synthase. Dimeric uridinyl derivatives synthesized by us did not exhibit significant activity. One of the studied monomeric derivative, 5′-(N-succinyl)-5′-amino-5′-deoxyuridine methyl ester (compound 7) showed activities against several fungal strains (MIC range 0.06–1.00mg/mL) and inhibited chitin synthase from Saccharomyces cerevisiae (IC50=0.8mM). Moreover compound 7 exhibited synergistic interaction with caspofungin against Candida albicans (FIC index=0.28).

Selective oxidation of benzyl alcohol on poly(4-(3-(pyrrol-1-yl)propionamido)-2,2,6,6-tetramethylpiperidin-1-yloxy) electrode

The derivative monomer of pyrrole with the side chain nitroxyl radical, 4-(3-(pyrrol-1-yl)propionamido)-2,2,6,6-tetramethylpiperidin-1-yloxy (PyATEMPO) was synthesized. Its corresponding polymer PPyATEMPO was successfully prepared by cyclic voltammetry on Pt electrode in NaClO4/CH3CN solution. The PPyATEMPO electrode showed high electrocatalytic activity for oxidation of benzyl alcohol in the presence of the Lewis base 2,6-lutidine. To further investigation, in situ Fourier transform infrared (FTIR) spectroscopy technique was applied to study the possible electrochemical oxidation mechanism of benzyl alcohol on PPyATEMPO electrode. It showed that the benzyl alcohol was selectively oxidized to benzaldehyde in the action of PPyATEMPO film.

Eco-paints from bio-based fatty acid derivative latexes

Abstract A series of fatty acid derivative latexes has been incorporated as binders in waterborne paints: methacrylated oleic acid (MOA) and methacrylated linoleic acid (MLA) homopolymers and copolymers of the petroleum derivative monomer methyl methacrylate and its structurally analogous renewable resource monomer α-methylene-γ-butyrolactone. The performance of the resulting paints has been evaluated in terms of hardness, gloss, rheological behaviour and open time and the final properties have been compared with a commercial waterborne paint. Most of the prepared paints showed good performance properties, making these compounds good candidates for their use in the production of sustainable waterborne paints.

Ligustrazine monomer against cerebral ischemia/reperfusion injury.

Ligustrazine (2,3,5,6-tetramethylpyrazine) is a major active ingredient of the Szechwan lovage rhizome and is extensively used in treatment of ischemic cerebrovascular disease. The mechanism of action of ligustrazine use against ischemic cerebrovascular diseases remains unclear at present. This study summarizes its protective effect, the optimum time window of administration, and the most effective mode of administration for clinical treatment of cerebral ischemia/reperfusion injury. We examine the effects of ligustrazine on suppressing excitatory amino acid release, promoting migration, differentiation and proliferation of endogenous neural stem cells. We also looked at its effects on angiogenesis and how it inhibits thrombosis, the inflammatory response, and apoptosis after cerebral ischemia. We consider that ligustrazine gives noticeable protection from cerebral ischemia/reperfusion injury. The time window of ligustrazine administration is limited. The protective effect and time window of a series of derivative monomers of ligustrazine such as 2-[(1,1-dimethylethyl)oxidoimino]methyl]-3,5,6-trimethylpyrazine, CXC137 and CXC195 after cerebral ischemia were better than ligustrazine.

Effect of monomers’ structure on self-acid-assisted polycondensation for the synthesis of poly(3,4-ethylenedioxythiophene) and homopolythiophene

PEDOT and homopolythiophene were synthesized by self-acid-assisted polycondensation (SAAP) based on mono-halogen substituted thiophene derivative monomers. Our results reveal that substituted halogen (bromo or iodo) positions play an important role in SAAP.

Fluorescence enhancement of covalently linked 1-cyano-1,2-diphenylethene chromophores with naphthalene-1,8-diyl linker units: analysis based on kinetic constants.

The fluorescence enhancement effect of covalently fixed fluorescent chromophores has been investigated by means of kinetic analysis of decay rate constants and theoretical calculations. Derivatives of 1-cyano-1,2-diphenylethene dimer have a distorted cyclic structure when both ends are clipped with two naphthalene-1,8-diyl linker units. In contrast to the reference monomer derivative, which exhibits only slight fluorescence in solution (Φf < 0.01, τf < 0.1 ns), the dimer derivative shows high fluorescence quantum yield (Φf = 0.55) and long lifetime (τf = 20.6 ns) in dilute solution owing to suppression of the nonradiative decay process (knr = 0.022 ns(-1)). A V-shaped derivative with a covalent linker on one side showed moderate quantum yield and lifetime (Φf = 0.12, τf = 4.9 ns). According to the wavelength shifts of the absorption/fluorescence bands and theoretical calculations by time-dependent density functional theory (TD-DFT), we propose an H-aggregate-type excimer interaction.

New Fullerene-Based Polymers and Their Electrical Memory Characteristics

Covalent incorporations into polymers of fullerene were achieved via the Cu(I)-catalyzed azide–alkyne click polymerizations of a fullerene derivative monomer functionalized with 5-(trimethylsilyl)pent-4-yn-1-yl groups and a comonomer functionalized with azidomethyl groups, producing the novel fullerene polymers P1-C60 and P2-C60. Despite their extremely high fullerene loading levels, the polymers were soluble in common organic solvents and exhibited no aggregation of fullerene units in films. Moreover, devices containing these fullerene polymers were easily fabricated with common coating processes that exhibit excellent unipolar and bipolar flash memory characteristics as well as unipolar permanent memory characteristics, with high ON/OFF current ratios, long retention times, and low power consumption. These electrical switching behaviors were favorably operated by electron injection. Overall, these devices are the first n-type bipolar and unipolar digital polymer memory devices which can be operated in flash and write-once-read-many-times modes.