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1.
RSC Adv ; 14(11): 7850-7857, 2024 Feb 29.
Artículo en Inglés | MEDLINE | ID: mdl-38449826

RESUMEN

Four amino acid-bearing acrylamides, N-acryloyl-l-threonine (AThrOH), N-acryloyl-l-glutamic acid (AGluOH), N-acryloyl-l-phenylalanine (APheOH), and N-acryloyl-l, l-diphenylalanine (APhePheOH), were selected for copolymerization with n-butyl acrylate (nBA) to develop amino acid-based self-healable copolymers. A series of copolymers comprising amino acid-bearing acrylamides and nBA with tunable comonomer compositions and molecular weights were synthesized by free radical and reversible addition-fragmentation chain-transfer copolymerization. Self-healing and mechanical properties originated from the noncovalent bonds between the carboxyl, hydroxyl, and amide groups, and π-π stacking interactions among the amino acid residues in the side chains were evaluated. Among these copolymers, P(nBA-co-AGluOH) with suitable comonomer compositions and molecular weights (nBA : AGluOH = 82 : 18, Mn = 18 300, Mw/Mn = 2.58) exhibited good mechanical properties (modulus of toughness = 17.3 MJ m-3) and self-healing under ambient conditions. The multiple noncovalent bonds of P(nBA-co-AGluOH)s were also efficient in improving the optical properties with an enhanced refractive index and good transparency.

2.
Soft Matter ; 19(43): 8403-8412, 2023 Nov 08.
Artículo en Inglés | MEDLINE | ID: mdl-37877167

RESUMEN

Manipulation of the properties of aggregation-induced emission luminogens (AIEgens) by combining self-assembling motifs has attracted significant interest as a promising approach to developing various advanced materials. In this study, pendant diphenylalanine-tetraphenylethylene (TPE) copolymers exhibiting the ability for self-assembly and AIE properties were synthesized via reversible addition-fragmentation chain-transfer (RAFT) copolymerization. The resulting anionic and non-ionic amphiphilic copolymers with a carbon-carbon main chain bearing diphenylalanine-TPE through-space interactions self-assembled into nanorods and nanofibers, showing blue emissions originating from the aggregation of TPE side chains in the assembled structures. Suitable tuning of the comonomer composition, monomer structure, and environmental conditions (e.g., solvent polarity) enables manipulation of the self-assembled structures, AIE properties, and aggregation-induced circular dichroism by achiral TPE units via through-space interactions with diphenylalanine moieties.

3.
Cureus ; 15(3): e36373, 2023 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-36945236

RESUMEN

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is a novel coronavirus that is causing a worldwide pandemic since the spring of 2020. In Osaka, the second biggest prefecture in Japan, we identified a novel SARS-CoV-2 variant from a coronavirus disease 2019 (COVID-19) patient that was detected by polymerase chain reaction (PCR) using E primers, but not by real-time quantitative reverse transcription polymerase chain reaction (RT-qPCR) using the N1 and N2 primer-probe sets recommended by CDC. We analyzed the S and N gene regions by reverse-transcription and nested PCR using the S and N specific primers, and DNA sequencing, and found that this BA.5 variant contained point mutations in the probe sequences of both the N1 and N2 primer-probe regions. This finding led us to affirm the importance of monitoring the genome sequence of the SARS-CoV-2 variants continuously.

4.
Polymers (Basel) ; 14(7)2022 Mar 27.
Artículo en Inglés | MEDLINE | ID: mdl-35406233

RESUMEN

Stimuli-responsive polymeric nanoparticles (NPs) exhibit reversible changes in the dispersion or aggregation state in response to external stimuli. In this context, we designed and synthesized core-shell NPs with threonine-containing weak polyelectrolyte shells and fluorescent cross-linked cores, which are applicable for the detection of pH changes and amine compounds in aqueous solution. Stable and uniform NP(dTh) and NP(Fl), consisting of fluorescent symmetric diphenyl dithiophene (dTh) and diphenyl fluorene (Fl) cross-linked cores, were prepared by site-selective Suzuki coupling reactions in self-assembled block copolymer. NP(Fl) with the Fl unit in the core showed a high fluorescence intensity in different solvents, which is regarded as an aggregation-induced emission-type NP showing strong emission in aggregated states in the cross-linked core. Unimodal NPs were observed in water at different pH values, and the diameter of NP(Fl) changed from 122 (pH = 2) to 220 nm (pH = 11). Furthermore, pH-dependent changes of the fluorescence peak positions and intensities were detected, which may be due to the core aggregation derived from the deprotonation of the threonine-based shell fragment. Specific interactions between the threonine-based shell of NP(Fl) and amine compounds (triethylamine and p-phenylenediamine) resulted in fluorescence quenching, suggesting the feasibility of fluorescent amine detection.

5.
Langmuir ; 37(10): 3001-3014, 2021 03 16.
Artículo en Inglés | MEDLINE | ID: mdl-33650430

RESUMEN

Two series of poly(vinyl amine) (PVAm)-based block copolymers with zwitterionic and thermoresponsive segments were synthesized by the reversible addition-fragmentation chain transfer polymerization. A mixture of the two copolymers, poly(N-acryloyl-l-lysine) (PALysOH) and poly(N-isopropylacrylamide) (PNIPAM), which have the same cationic PVAm chain but different shell-forming segments, were used to prepare mixed polyplex micelles with DNA. Both PVAm-b-PALysOH and PVAm-b-PNIPAM showed low cytotoxicity, with characteristic assembled structures and stimuli-responsive properties. The cationic PVAm segment in both block copolymers showed site-specific interactions with DNA, which were evaluated by dynamic light scattering, zeta potential, circular dichroism, agarose gel electrophoresis, atomic force microscopy, and transmission electron microscopy measurements. The PVAm-b-PNIPAM/DNA polyplexes showed the characteristic temperature-induced formation of assembled structures in which the polyplex size, surface charge, chiroptical property of DNA, and polymer-DNA binding were governed by the nitrogen/phosphate (N/P) ratio. The DNA binding strength and colloidal stability of the PVAm-b-PALysOH/DNA polyplexes could be tuned by introducing an appropriate amount of zwitterionic PALysOH functionality, while maintaining the polyplex size, surface charge, and chiroptical property, regardless of the N/P ratio. The mixed polyplex micelles showed temperature-induced stability originating from the hydrophobic (dehydrated) PNIPAM chains upon heating, and remarkable stability under salty conditions owing to the presence of the zwitterionic PALysOH chain on the polyplex surface.

6.
Phys Chem Chem Phys ; 22(16): 8853-8863, 2020 Apr 29.
Artículo en Inglés | MEDLINE | ID: mdl-32285884

RESUMEN

Deep eutectic solvents (DESs) have recently attracted significant attention as inexpensive materials with similar characteristics to ionic liquids. For practical applications of DESs in electrochemical devices such as lithium-ion batteries (LIBs), the manipulation of the melting point and electrochemical stability is important as they are important parameters that determine device performance. In this study, we investigated a family of Li-salt/amide-based electrolytes (DEEs) comprised of five amide derivatives (urea, acetamide, N,N'-dimethylpropyleneurea, 2-imidazolidinone and tetramethylurea) and two representative Li-salts (LiCl and LiTFSI), in terms of thermal and electrochemical properties. To verify the effect of the coordination state on the melting point, the coordination state between lithium salt and amide was calculated by a molecular dynamics simulation using four representative DEEs. Regarding electrochemical stability, the HOMO and LUMO were calculated by density functional theory and the correlation with the experimental result of cyclic voltammetry was verified. Hydrogen bonding donor (HBD)-free DEEs comprised of amides without any N-H bonds (e.g. 1,1,3,3-tetramethylurea and 1,3-dimethyl-2-imidazoline) were found to be superior to those containing HBDs derived from amides having N-H bonds (e.g. urea, acetamide and 2-imidazolidinone), in terms of reduction stability. Among various DEEs evaluated in this study, the DEE derived from LiTFSI : 1,1,3,3-tetramethylurea = 1 : 5 mol% was the best electrolyte in terms of melting point, electrochemical stability and ionic conductivity. The results of this study provide important guidelines for designing DESs as LIB electrolytes.

7.
ACS Omega ; 5(7): 3678-3688, 2020 Feb 25.
Artículo en Inglés | MEDLINE | ID: mdl-32118183

RESUMEN

Herein, we present an industrially applicable strategy to enhance the heat resistance and adhesive properties of ABA triblock copolymer-based elastomers composed of styrene (St) and n-butyl acrylate (nBA) by incorporating acrylic acid (AA) at different segments. Three types of triblock copolymers, namely, poly(St-r-AA)-b-poly(nBA)-b-poly(St-r-AA), poly(St)-b-poly(nBA-r-AA)-b-poly(St), and poly(St)-b-poly(nBA)-b-poly(St), were synthesized by reversible addition-fragmentation chain-transfer (RAFT) polymerization. Large-scale RAFT polymerization afforded industrially applicable AA-containing triblock copolymers with moderate molecular weights and predetermined comonomer compositions (St/nBA/AA = 15/83/2-24/73/3, number-average molecular weight (M n) = 30,000-110,000, and resulting product > 200 g). The heat resistance and pressure-sensitive adhesive properties of the triblock copolymers were evaluated. Among them, poly(St-r-AA)-b-poly(nBA)-b-poly(St-r-AA), having poly(nBA) as the middle soft segment and poly(St-r-AA) as hard segments at both ends, exhibited excellent heat creep resistance and increased adhesiveness to stainless steel. The feasibility to manipulate the heat resistance and adhesive properties by incorporating AA units into hard and soft segments, in addition to the ease of operation, high block efficiency, and metal-free nature owing to the RAFT process, is highly beneficial for practical applications of these copolymers.

8.
ACS Omega ; 4(19): 18234-18247, 2019 Nov 05.
Artículo en Inglés | MEDLINE | ID: mdl-31720524

RESUMEN

Tertiary sulfonium-containing zwitterionic block copolymers consisting of N-acryloyl-l-methionine methyl sulfonium salt (A-Met(S+)-OH) and n-butyl acrylate (BA) were newly synthesized to develop a novel protein stabilizer. The zwitterionic block copolymers were prepared by reversible addition-fragmentation chain-transfer (RAFT) polymerization of BA using a hydrophilic macro-chain-transfer agent (CTA) obtained from N-acryloyl-l-methionine (A-Met-OH) and subsequent postmodification. RAFT polymerization of A-Met-OH using poly(BA) macro-CTA, followed by postmodification, also afforded the target poly(A-Met(S+)-OH)-b-poly(BA). The block copolymers stabilized horseradish peroxidase (HRP) during storage at 37 °C for 5 days, and the protein-stabilizing effect was enhanced with increase in the A-Met(S+)-OH content. In particular, the block copolymer with ∼85% A-Met(S+)-OH content showed a significant protein-stabilizing effect at a temperature (37 °C) higher than the room temperature, which is highly desirable for practical and industrial applications. The addition of sucrose into the block copolymer-protein solution led to a considerable increase in the HRP activity under the same conditions. Excellent alkaline phosphatase stabilization at 37 °C for 12 days was also achieved using the block copolymers. The zwitterionic block copolymers with the optimal hydrophilic/hydrophobic balance were found to serve as efficient protein-stabilizing agents, in comparison with the corresponding homopolymer and random copolymers. Dynamic light scattering, zeta potential, transmission electron microscopy, and circular dichroism measurements revealed that the zwitterionic block copolymer stabilizes an enzyme by wrapping with a slight change in the size, whereas the secondary and ordered structures of the enzyme are maintained.

9.
Macromol Rapid Commun ; 40(12): e1900115, 2019 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-31021501

RESUMEN

Donor-acceptor crosslinked poly[poly(ethylene glycol) methyl ether-methacrylate]-block-poly[1,1'-bis(2-ethylpentyl)-6-methyl-6'-(5-methyl-3-vinylthiophen-2-yl)-[3,3'-biindoline]-2,2'-dione] (poly(PEGMA)m -b-poly(VTIID)n ) nanoparticles with various vinylthiophene donor/isoindigo acceptor ratios are synthesized successfully. The prepared nanoparticles have uniform sizes and well-defined core-shell nanostructures. The intramolecular charge transfer is effectively enhanced due to the incorporation of acceptor groups after the crosslinking reaction. A transistor memory device is assembled using the synthesized polymer and has nonvolatile flash-type memory and amphiphilic trapping behavior. The optimized devices exhibit a significant memory window of approximately 38 V, a retention ability of over 104 s, and an endurance of at least 100 cycles. This study examines multiple applications of crosslinked core-shell nanoparticles, which demonstrates their promise as charge-storage dielectric materials for use in organic memory devices.


Asunto(s)
Reactivos de Enlaces Cruzados/química , Nanopartículas/química , Polímeros/química , Transistores Electrónicos , Reactivos de Enlaces Cruzados/síntesis química , Estructura Molecular , Tamaño de la Partícula , Polímeros/síntesis química , Propiedades de Superficie
10.
Langmuir ; 35(13): 4646-4659, 2019 04 02.
Artículo en Inglés | MEDLINE | ID: mdl-30845801

RESUMEN

A series of anionic, zwitterionic, and cationic lysine-based block copolymers with a thermoresponsive segment were synthesized by the reversible addition-fragmentation chain transfer (RAFT) polymerization of N-acryloyl- N-carbobenzoxy-l-lysine [A-Lys(Cbz)-OH], which contains a carboxylic acid and a protected amine-functionality in the monomer unit. Carboxylic acid-containing homopolymers, poly(A-Lys(Cbz)-OH), with predetermined molecular weights with relatively low polydispersities were initially synthesized by RAFT polymerization of A-Lys(Cbz)-OH. The chain extension of the dithiocarbamate-terminated poly(A-Lys(Cbz)-OH) to N-isopropylacrylamide (NIPAM) via the RAFT process and subsequent deprotection afforded the zwitterionic block copolymer composed of thermoresponsive poly(NIPAM) and poly(A-Lys-OH), which exhibited switchability among the zwitterionic, anionic, and cationic states by pH change. The assembled structures and thermoresponsive and chiroptical properties of these block copolymers were evaluated by dynamic light scattering, circular dichroism, and turbidity measurements. Finally, the cationic block copolymer, poly(A-Lys-OMe)- b-poly(NIPAM), was obtained by the methylation of the carboxylic acid group in the zwitterionic poly(A-Lys-OH) segment. Selective interactions of DNA with the cationic poly(A-Lys-OMe) segment in the lysine-based block copolymer were further evaluated by agarose gel electrophoresis and atomic force microscopy measurements, which revealed characteristic assembled structures and temperature-responsive properties of the polyplexes.


Asunto(s)
Cationes/química , Polímeros/química , Acrilamidas/química , Ácidos Carboxílicos/química , Microscopía de Fuerza Atómica
11.
Biomacromolecules ; 20(2): 904-915, 2019 02 11.
Artículo en Inglés | MEDLINE | ID: mdl-30566330

RESUMEN

The present study demonstrates the controlled synthesis and biological potential of poly( N-acryloyl-l-methionine methyl sulfonium salt)s (poly(A-Met(S+)-OH)s), which mimic dimethylsulfoniopropionate (DMSP), a compound produced by marine algae to protect their proteins. The novel sulfonium-containing zwitterionic polymers were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization of the amino acid-based monomer N-acryloyl-l-methionine (A-Met-OH) followed by a postmodification process in which the sulfide groups were reacted with iodomethane. The DMSP-mimic zwitterionic macromolecules were shown for the first time to exhibit low cytotoxicity and the ability to stabilize proteins. By adding the resulting poly(A-Met(S+)-OH)s to horse radish peroxidase (HRP) solution, the activity of HRP was maintained even after storage at 4 °C for several days. In addition, the protein activities were tested using peroxidase-labeled antibody to mouse immunoglobulin G (IgG-HRP) and alkaline phosphatase (ALP) after storage and for HRP after freeze-thaw cycles. Amphiphilic random copolymers, poly(A-Met(S+)-OH- co-BA)s, also exhibited excellent properties for protein stabilization.


Asunto(s)
Polímeros/síntesis química , Proteínas/química , Compuestos de Sulfonio/química , Fosfatasa Alcalina/química , Aminoácidos/química , Animales , Línea Celular , Peroxidasa de Rábano Silvestre/química , Hidrocarburos Yodados/química , Inmunoglobulina G/química , Metionina/química , Ratones , Polimerizacion
12.
ACS Appl Mater Interfaces ; 10(51): 44741-44750, 2018 Dec 26.
Artículo en Inglés | MEDLINE | ID: mdl-30488691

RESUMEN

In this study, a series of alcohol-soluble cross-linked block copolymers (BCPs) consisting of poly( n-butyl acrylate) (poly( nBA)) and poly( N-vinyl-1,2,4-triazole) (poly(NVTri)) blocks with different individual functions and lengths are designed and developed. These presynthesized cross-linked BCPs (PBA n-Tri m) were, for the first time, revealed to exhibit many advantages in serving as the electron-extraction layer (EEL) for organic photovoltaics (OPVs). The cross-linked BCPs possessed intense ionic functionality, showing well capability to form effective interfacial dipoles at the indium tin oxide interface to facilitate the charge extraction at the corresponding interface. Furthermore, it also consisted a core-shell structure, wherein the polar poly(NVTri) core was well protected by the poly( nBA) shell to endow improved robustness against solvent erosion and thermal/photo inputs. Consequently, the PBA70-Tri30 device yielded a decent power conversion efficiency of 8.03% with a Voc of 0.83 V, much exceeding the performance of the control device without using any EEL. Moreover, this device showed superior thermal stability/photostability. More than 80% of its initial performance was retained after being heated at 60 °C for 1000 h or exposed under continuous illumination (1 sun) for 1000 h, greatly surpassing the lifetime of the control device and the reference device using a common poly[(9,9-bis(3'-( N, N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) EEL. The results revealed the merit of using cross-linked BCPs in improving the long-term stability of OPVs.

13.
Polymers (Basel) ; 10(7)2018 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-30960646

RESUMEN

Synthesis of novel block and random copolymers, containing a carbazole unit and (di)phenylanthracene moiety in the side chains, has been described in this paper. Block and random copolymers composed of 4-bromophenyl vinyl sulfide (BPVS) and N-vinylcarbazole (NVC) were initially prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization. Then, anthracene-based groups were introduced on the bromophenyl unit in the carbazole-containing copolymers by Pd-catalyzed coupling to yield functional copolymers with additional (di)phenylanthracene units. The resulting copolymers, having two distinct electronic functionalities, exhibited characteristic fluorescence resonance energy transfer, as confirmed by UV-vis and fluorescence spectra.

14.
ACS Macro Lett ; 7(3): 341-346, 2018 Mar 20.
Artículo en Inglés | MEDLINE | ID: mdl-35632909

RESUMEN

Conditional variations can lead to micellar transformations resulting in various (equilibrium) morphologies. However, creating differently shaped assemblies under the same final conditions (same ingredients, composition, temperature, etc.) is challenging. We present a thermoresponsive polyelectrolyte system allowing a pathway-dependent preparation of kinetically stable spherical star-like or cylindrical micelles. In more detail, a temperature-induced structure switch is used to generate equilibrated interpolyelectrolyte complex (IPEC) micelles of different morphologies (templates) below and above the lower critical solution temperature in the presence of plasticizer (salt). Then, lowering the salt concentration at a specific temperature kinetically freezes the formed IPECs, keeping the respective microstructural information encoded in the frozen IPEC also at other temperatures. Hence, different nonequilibrium morphologies at the same final conditions are provided. The salt-triggered transition from nonequilibrium to equilibrium micelles can be repeated for the same sample, highlighting a system with an on-demand changeable and restorable structure.

15.
Sci Rep ; 7(1): 6688, 2017 07 27.
Artículo en Inglés | MEDLINE | ID: mdl-28751737

RESUMEN

In plants, cis-jasmone (CJ) is synthesized from α-linolenic acid (LA) via two biosynthetic pathways using jasmonic acid (JA) and iso-12-oxo-phytodienoic acid (iso-OPDA) as key intermediates. However, there have been no reports documenting CJ production by microorganisms. In the present study, the production of fungal-derived CJ by Lasiodiplodia theobromae was observed for the first time, although this production was not observed for Botrytis cinerea, Verticillium longisporum, Fusarium oxysporum, Gibberella fujikuroi, and Cochliobolus heterostrophus. To investigate the biosynthetic pathway of CJ in L. theobromae, administration experiments using [18,18,18-2H3, 17,17-2H2]LA (LA-d5), [18,18,18-2H3, 17,17-2H2]12-oxo-phytodienoic acid (cis-OPDA-d5), [5',5',5'-2H3, 4',4'-2H2, 3'-2H1]OPC 8:0 (OPC8-d6), [5',5',5'-2H3, 4',4'-2H2, 3'-2H1]OPC 6:0 (OPC6-d6), [5',5',5'-2H3, 4',4'-2H2, 3'-2H1]OPC 4:0 (OPC4-d6), and [11,11-2H2, 10,10-2H2, 8,8-2H2, 2,2-2H2]methyl iso-12-oxo-phytodienoate (iso-MeOPDA-d8) were carried out, revealing that the fungus produced CJ through a single biosynthetic pathway via iso-OPDA. Interestingly, it was suggested that the previously predicted decarboxylation step of 3,7-didehydroJA to afford CJ might not be involved in CJ biosynthesis in L. theobromae.


Asunto(s)
Ascomicetos/metabolismo , Vías Biosintéticas , Ciclopentanos/metabolismo , Oxilipinas/metabolismo , Acetatos/química , Acetatos/metabolismo , Ciclopentanos/química , Deuterio/metabolismo , Ácidos Grasos Insaturados/metabolismo , Metaboloma , Oxilipinas/química
16.
J Phys Chem B ; 121(27): 6739-6748, 2017 07 13.
Artículo en Inglés | MEDLINE | ID: mdl-28661146

RESUMEN

The kinetics of interpolyelectrolyte complexation involving architecturally complex (star-like) polymeric components is addressed. Specifically, the spontaneous coupling of branched cationic star-shaped miktoarm polymers, i.e., quaternized poly(ethylene oxide)114-(poly(2-(dimethylamino)ethyl methacrylate)17)4 (PEO114-(qPDMAEMA17)4), and temperature-sensitive linear anionic diblock copolymers poly(vinyl sulfonate)31-b-poly(N-isopropylacrylamide)27 (PVS31-b-PNIPAM27) and further rearrangements of the formed complexes were investigated by means of stopped-flow small-angle X-ray scattering (SAXS). Colloidally stable micelles were obtained upon mixing both polymers at a 1:1 charge molar ratio in saline solutions. The description of the time-resolved SAXS data with appropriate form factor models yielded dimensions for each micellar domain and detailed the picture of the time-dependent size changes and restructuring processes. A fast interpolyelectrolyte coupling and structural equilibration were observed when mixing occurs below the lower critical solution temperature (LCST) of PNIPAM, resulting in small spherical-like assemblies with hydrated PNIPAM coronal blocks. Above the LCST, the collapsed PNIPAM decelerates equilibration, though temperature as such is expected to boost the kinetics of complex formation: after a fast initial interpolyelectrolyte coupling, different nonequilibrium structures of spherical and worm-like shape are observed on different time scales. This study illustrates how a thermoresponsive component can modulate the influence of temperature on kinetics, particularly for rearrangement processes toward equilibrium structures during interpolyelectrolyte complexation.

17.
Polymers (Basel) ; 9(11)2017 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-30965921

RESUMEN

Ionic liquid-based block copolymers composed of ionic (solubility tunable)⁻nonionic (water-soluble and thermoresponsive) segments were synthesized to explore the relationship between ionic conductivity and assembled structures. Three block copolymers, comprising poly(N-vinylimidazolium bromide) (poly(NVI-Br)) as a hydrophilic poly(ionic liquid) segment and thermoresponsive poly(N-isopropylacrylamide) (poly(NIPAM)), having different compositions, were initially prepared by RAFT polymerization. The anion-exchange reaction of the poly(NVI-Br) in the block copolymers with lithium bis(trifluoromethanesulfonyl)imide (LiNTf2) proceeded selectively to afford amphiphilic block copolymers composed of hydrophobic poly(NVI-NTf2) and hydrophilic poly(NIPAM). Resulting poly(NVI-NTf2)-b-poly(NIPAM) exhibited ionic conductivities greater than 10-3 S/cm at 90 °C and 10-4 S/cm at 25 °C, which can be tuned by the comonomer composition and addition of a molten salt. Temperature-dependent ionic conductivity and assembled structures of these block copolymers were investigated, in terms of the comonomer composition, nature of counter anion and sample preparation procedure.

18.
Soft Matter ; 12(23): 5127-37, 2016 Jun 21.
Artículo en Inglés | MEDLINE | ID: mdl-27194585

RESUMEN

The spontaneous formation and thermo-responsiveness of a colloidally-stable interpolyelectrolyte complex (IPEC) based on a linear temperature-sensitive diblock copolymer poly(vinyl sulfonate)31-b-poly(N-isopropyl acrylamide)27 (PVS31-b-PNIPAM27) and a star-shaped quaternized miktoarm polymer poly(ethylene oxide)114-(poly(2-(dimethylamino)ethyl methacrylate)17)4 (PEO114-(qPDMAEMA17)4) was investigated in aqueous media at 0.3 M NaCl by means of dynamic light scattering (DLS), small angle X-ray scattering (SAXS), and cryogenic transmission electron microscopy (cryo-TEM). The micellar macromolecular co-assemblies show a temperature-dependent size and morphology, which result from the lower critical solution temperature (LCST) behavior of the PNIPAM-blocks. Hence, the micellar co-assemblies grow upon heating. At 60 °C, spherical core-shell-corona co-assemblies are proposed with a hydrophobic PNIPAM core, a water-insoluble IPEC shell, and a hydrophilic PEO corona. These constructs develop into a rod-like structure upon extended equilibration. In turn, PEO-arms and PNIPAM-blocks within a hydrophilic mixed two-component corona surround the water-insoluble IPEC domain at 20 °C, thereby forming spherical core-corona co-assemblies. Reversibility of the structural changes is suggested by the scattering data. This contribution addresses the use of a combination of oppositely charged thermo-responsive and bis-hydrophilic star-shaped polymeric components toward IPECs of diverse morphological types.

19.
Chem Commun (Camb) ; 52(45): 7269-72, 2016 Jun 07.
Artículo en Inglés | MEDLINE | ID: mdl-27180874

RESUMEN

Solution processable cross-linked core-shell poly[poly(ethylene glycol)methylether methacrylate]-block-poly(2,5-dibromo-3-vinylthiophene) (poly(PEGMA)m-b-poly(DB3VT)n) nanoparticles are firstly explored as charge storage materials for transistor-type memory devices owing to their efficient and controllable ability in electric charge transfer and trapping.

20.
Langmuir ; 31(42): 11399-408, 2015 Oct 27.
Artículo en Inglés | MEDLINE | ID: mdl-26421355

RESUMEN

As surfactants for preparation of nonaqueous microcapsule dispersions by the emulsion solvent evaporation method, three copolymers composed of stearyl methacrylate (SMA) and glycidyl methacrylate (GMA) with different monomer sequences (i.e., random, block, and block-random) were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Despite having the same comonomer composition, the copolymers exhibited different functionality as surfactants for creating emulsions with respective dispersed and continuous phases consisting of methanol and isoparaffin solvent. The optimal monomer sequence for the surfactant was determined based on the droplet sizes and the stabilities of the emulsions created using these copolymers. The block-random copolymer led to an emulsion with better stability than obtained using the random copolymer and a smaller droplet size than achieved with the block copolymer. Modification of the epoxy group of the GMA unit by diethanolamine (DEA) further decreased the droplet size, leading to higher stability of the emulsion. The DEA-modified block-random copolymer gave rise to nonaqueous microcapsule dispersions after evaporation of methanol from the emulsions containing colored dyes in their dispersed phases. These dispersions exhibited high stability, and the particle sizes were small enough for application to the inkjet printing process.

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