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1.
Molecules ; 29(9)2024 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-38731481

RESUMEN

As the use of antibiotics increases, the increasing resistance of bacteria is the main reason for the reduced efficiency of antibacterial drugs, making the research of new antibacterial materials become new hot spot. In this article, two novel coordination polymers (CPs), namely, [Cd2(L)2(bibp)2]n (1) and [Ni(L)(bib)]n (2), where H2L = N,N'-bis(4-carbozvlbenzvl)-4-aminotoluene, bibp = 4,4'-bis(imidazol-1-yl)biphenyl, and bib = 1,3-bis(1-imidazoly)benzene, have been synthesized under solvothermal and hydrothermal condition. Structural clarification was performed through infrared spectrum and single-crystal X-ray diffraction analysis, while thermal analysis and XRD technology were used for the performance assessment of compounds 1 and 2. In addition, antibacterial performance experiments showed that compounds 1 and 2 have certain selectivity in their antibacterial properties and have good antibacterial properties against S. aureus. As the concentration of the compound increases, the inhibitory effect gradually strengthens, and when the concentration of the compound reaches 500 µg/mL and 400 µg/mL, the concentration of the S. aureus solution no longer increases and has been completely inhibited.


Asunto(s)
Antibacterianos , Pruebas de Sensibilidad Microbiana , Polímeros , Staphylococcus aureus , Antibacterianos/farmacología , Antibacterianos/química , Antibacterianos/síntesis química , Staphylococcus aureus/efectos de los fármacos , Polímeros/química , Polímeros/farmacología , Polímeros/síntesis química , Ligandos , Complejos de Coordinación/farmacología , Complejos de Coordinación/química , Complejos de Coordinación/síntesis química , Estructura Molecular , Compuestos Heterocíclicos/química , Compuestos Heterocíclicos/farmacología , Compuestos Heterocíclicos/síntesis química , Modelos Moleculares , Cristalografía por Rayos X
2.
Biomacromolecules ; 25(5): 3122-3130, 2024 May 13.
Artículo en Inglés | MEDLINE | ID: mdl-38696355

RESUMEN

Synthesis of polysaccharide-b-polypeptide block copolymers represents an attractive goal because of their promising potential in delivery applications. Inspired by recent breakthroughs in N-carboxyanhydride (NCA) ring-opening polymerization (ROP), we present an efficient approach for preparation of a dextran-based macroinitiator and the subsequent synthesis of dextran-b-polypeptides via NCA ROP. This is an original approach to creating and employing a native polysaccharide macroinitiator for block copolymer synthesis. In this strategy, regioselective (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) oxidation of the sole primary alcohol located at the C-6 position of the monosaccharide at the nonreducing end of linear dextran results in a carboxylic acid. This motif is then transformed into a tetraalkylammonium carboxylate, thereby generating the dextran macroinitiator. This macroinitiator initiates a wide range of NCA monomers and produces dextran-b-polypeptides with a degree of polymerization (DP) of the polypeptide up to 70 in a controlled manner (D < 1.3). This strategy offers several distinct advantages, including preservation of the original dextran backbone structure, relatively rapid polymerization, and moisture tolerance. The dextran-b-polypeptides exhibit interesting self-assembly behavior. Their nanostructures have been investigated by dynamic light scattering (DLS) and transmission electron microscopy (TEM), and adjustment of the structure of block copolymers allows self-assembly of spherical micelles and worm-like micelles with varied diameters and aspect ratios, revealing a range of diameters from 60 to 160 nm. Moreover, these nanostructures exhibit diverse morphologies, including spherical micelles and worm-like micelles, enabling delivery applications.


Asunto(s)
Dextranos , Péptidos , Polimerizacion , Dextranos/química , Péptidos/química , Péptidos/síntesis química , Polímeros/química , Polímeros/síntesis química , Óxidos N-Cíclicos/química , Anhídridos/química , Polisacáridos/química , Micelas
3.
ACS Appl Mater Interfaces ; 16(17): 22493-22503, 2024 May 01.
Artículo en Inglés | MEDLINE | ID: mdl-38647220

RESUMEN

Poly(levodopa) nanoparticles (P(l-DOPA) NPs) are another kind of melanin mimetic besides well-established polydopamine nanoparticles (PDA NPs). Due to the presence of carboxyl groups, the oxidative polymerization of l-DOPA to obtain particles was not as efficient as that of dopamine. Several established methods toward P(l-DOPA) NP fabrication do not combine convenience, morphological regularity, size controllability, low cost, and adaptability to metal-free application scenarios. In this work, P(l-DOPA) NPs were successfully prepared in hot water with the assistant of organic quaternary ammonium, due to the extra physical cross-linking mediated by cations. The employed physical interactions could also be affected by quaternary ammonium structure (i.e., number of cation heads, length of alkyl chain) to achieve different polymerization acceleration effects. The obtained P(l-DOPA) NPs retained superior photothermal properties and outperformed PDA-based melanin materials. Furthermore, P(l-DOPA) NPs were used in photothermal tumor therapy and showed better efficacy. This study offers new insights into the synthesis of melanin-like materials, as well as new understanding of the interaction between quaternary ammonium and bioinspired polyphenolic materials.


Asunto(s)
Dihidroxifenilalanina/análogos & derivados , Indoles , Levodopa , Melaninas , Nanopartículas , Compuestos de Amonio Cuaternario , Compuestos de Amonio Cuaternario/química , Compuestos de Amonio Cuaternario/farmacología , Nanopartículas/química , Melaninas/química , Animales , Ratones , Levodopa/química , Terapia Fototérmica , Humanos , Línea Celular Tumoral , Polímeros/química , Polímeros/síntesis química , Polímeros/farmacología
4.
Int J Mol Sci ; 25(8)2024 Apr 20.
Artículo en Inglés | MEDLINE | ID: mdl-38674103

RESUMEN

pH-sensitive amphiphilic diblock polyphosphoesters containing lactic acid units were synthesized by multistep one-pot polycondensation reactions. They comprise acid-labile P(O)-O-C and C(O)-O-C bonds, the cleavage of which depends on the pH of the medium. The structure of these copolymers was characterized by 1H, 13C {H}, 31P NMR, and size exclusion chromatography (SEC). The newly synthesized polymers self-assembled into the micellar structure in an aqueous solution. The effects of the molecular weight of the copolymer and the length of the hydrophobic chain on micelle formation and stabilityand micelle size were studied via dynamic light scattering (DLS). Drug loading and encapsulation efficiency tests using doxorubicin revealed that hydrophobic drugs can be delivered by copolymers. It was established that the molecular weight of the copolymer, length of the hydrophobic chain and content of lactate units affects the size of the micelles, drug loading, and efficiency of encapsulation. A copolymer with 10.7% lactate content has drug loading (3.2 ± 0.3) and efficiency of encapsulation (57.4 ± 3.2), compared to the same copolymer with 41.8% lactate content (1.63%) and (45.8%), respectively. It was demonstrated that the poly[alkylpoly(ethylene glycol) phosphate-b-alkylpoly(ethylene glycol)lactate phosphate] DOX system has a pH-sensitive response capability in the result in which DOX was selectively accumulated into the tumor, where pH is acidic. The results obtained indicate that amphiphilic diblock polyphosphoesters have potential as drug carriers.


Asunto(s)
Doxorrubicina , Portadores de Fármacos , Ácido Láctico , Micelas , Polímeros , Concentración de Iones de Hidrógeno , Portadores de Fármacos/química , Portadores de Fármacos/síntesis química , Doxorrubicina/química , Doxorrubicina/farmacología , Ácido Láctico/química , Polímeros/química , Polímeros/síntesis química , Humanos , Ésteres/química , Interacciones Hidrofóbicas e Hidrofílicas , Peso Molecular
5.
J Am Chem Soc ; 146(18): 12577-12586, 2024 May 08.
Artículo en Inglés | MEDLINE | ID: mdl-38683934

RESUMEN

Dynamic supramolecular assemblies, driven by noncovalent interactions, pervade the biological realm. In the synthetic domain, their counterparts, supramolecular polymers, endowed with remarkable self-repair and adaptive traits, are often realized through bioinspired designs. Recently, controlled supramolecular polymerization strategies have emerged, drawing inspiration from protein self-assembly. A burgeoning area of research involves mimicking the liquid-liquid phase separation (LLPS) observed in proteins to create coacervate droplets and recognizing their significance in cellular organization and diverse functions. Herein, we introduce a novel perspective on synthetic coacervates, extending beyond their established role in synthetic biology as dynamic, membraneless phases to enable structural control in synthetic supramolecular polymers. Drawing parallels with the cooperative growth of amyloid fibrils through LLPS, we present metastable coacervate droplets as dormant monomer phases for controlled supramolecular polymerization. This is achieved via a π-conjugated monomer design that combines structural characteristics for both coacervation through its terminal ionic groups and one-dimensional growth via a π-conjugated core. This design leads to a unique temporal LLPS, resulting in a metastable coacervate phase, which subsequently undergoes one-dimensional growth via nucleation within the droplets. In-depth spectroscopic and microscopic characterization provides insights into the temporal evolution of disordered and ordered phases. Furthermore, to modulate the kinetics of liquid-to-solid transformation and to achieve precise control over the structural characteristics of the resulting supramolecular polymers, we invoke seeding in the droplets, showcasing living growth characteristics. Our work thus opens up new avenues in the exciting field of supramolecular polymerization, offering general design principles and controlled synthesis of precision self-assembled structures in confined environments.


Asunto(s)
Polimerizacion , Sustancias Macromoleculares/química , Sustancias Macromoleculares/síntesis química , Polímeros/química , Polímeros/síntesis química , Extracción Líquido-Líquido/métodos , Estructura Molecular , Separación de Fases
6.
Int J Biol Macromol ; 266(Pt 2): 131230, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38574909

RESUMEN

Due to the biodegradable and biocompatible nature of chitin and chitosan, they are extensively used in the synthesis of hydrogels for various applications. In this work, deacetylation of chitin is carried out with alkaline poly(dimethyldiallylammonium-hydroxide) that gave a higher amount of water-soluble chitin (with 84 % of the degree of deacetylation = chitosan0.84) compared to deacetylation using NaOH. The water-soluble chitosan0.84 is used as intercalating chains for the preparation of acrylic acid and vinylimidazole-based hydrogels. The quaternization of imidazole groups is done with 1,ω-dibromoalkanes, which sets off the crosslinking in the above polymer network. A set of three chitosan0.84 intercalated hydrogels, namely Cs-C4-hydrogel, Cs-C5-hydrogel, and Cs-C10-hydrogel are prepared bearing butyl, pentyl, and decyl chains as respective crosslinkers. The swell ratios of these intercalated hydrogels are compared with those of non-intercalated hydrogels (C4-hydrogel, C5-hydrogel, and C10-hydrogel). Chitosan0.84 intercalated Cs-C10-hydrogel has excellent swelling properties (2330 % swelling ratio) among six synthesized hydrogels. SEM analysis reveals that decyl crosslinker-bearing hydrogels are highly porous. The multi-functionality of Cs-C10-hydrogel and C10-hydrogel is explored towards -the controlled release of paracetamol/urea, and methyleneblue dye absorption. These studies disclose that chitosan0.84 intercalated hydrogels are showing superior-swelling behavior, high paracetamol/urea loading capacities and better dye entrapment than their non-intercalated counterparts.


Asunto(s)
Acetaminofén , Quitina , Preparaciones de Acción Retardada , Hidrogeles , Líquidos Iónicos , Urea , Hidrogeles/química , Hidrogeles/síntesis química , Líquidos Iónicos/química , Quitina/química , Acetaminofén/química , Urea/química , Liberación de Fármacos , Acetilación , Quitosano/química , Portadores de Fármacos/química , Portadores de Fármacos/síntesis química , Polímeros/química , Polímeros/síntesis química
7.
Macromol Rapid Commun ; 45(9): e2300685, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38339795

RESUMEN

The air filtration materials with high efficiency, low resistance, and extra antibacterial property are crucial for personal health protection. Herein, a tree-like polyvinylidene fluoride (PVDF) nanofibrous membrane with hierarchical structure (trunk fiber of 447 nm, branched fiber of 24.7 nm) and high filtration capacity is demonstrated. Specifically, 2-hydroxypropyl trimethyl ammonium chloride terminated hyperbranched polymer (HBP-HTC) with near-spherical three-dimensional molecular structure and adjustable terminal positive groups is synthesized as an additive for PVDF electrospinning to enhance the jet splitting and promote the formation of branched ultrafine nanofibers, achieving a coverage rate of branched nanofibers over 90% that is superior than small molecular quaternary ammonium salts. The branched nanofibers network enhances mechanical properties and filtration efficiency (99.995% for 0.26 µm sodium chloride particles) of the PVDF/HBP-HTC membrane, which demonstrates reduced pressure drop (122.4 Pa) and a quality factor up to 0.083 Pa-1 on a 40 µm-thick sample. More importantly, the numerous quaternary ammonium salt groups of HBP-HTC deliver excellent antibacterial properties to the PVDF membranes. Bacterial inhibitive rate of 99.9% against both S. aureus and E. coli is demonstrated in a membrane with 3.0 wt% HBP-HTC. This work provides a new strategy for development of high-efficiency and antibacterial protection products.


Asunto(s)
Antibacterianos , Escherichia coli , Nanofibras , Polímeros , Polivinilos , Staphylococcus aureus , Nanofibras/química , Antibacterianos/farmacología , Antibacterianos/química , Antibacterianos/síntesis química , Escherichia coli/efectos de los fármacos , Staphylococcus aureus/efectos de los fármacos , Polivinilos/química , Polímeros/química , Polímeros/farmacología , Polímeros/síntesis química , Membranas Artificiales , Pruebas de Sensibilidad Microbiana , Filtros de Aire , Compuestos de Amonio Cuaternario/química , Compuestos de Amonio Cuaternario/farmacología , Filtración/métodos , Tamaño de la Partícula , Polímeros de Fluorocarbono
8.
Macromol Rapid Commun ; 45(9): e2300644, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38350089

RESUMEN

A tetra(ethylene glycol)-based 1,3,4,5-tetrasubstituted poly(1,2,3-triazolium) is synthesized in two steps including: i) the catalyst-free polyaddition of a diazide and an activated internal dialkyne and ii) the N-alkylation of the resulting 1,2,3-triazole groups. In order to provide detailed structure/properties correlations different analogs are also synthesized. First, parent poly(1,2,3-triazole)s are obtained via AA+BB polyaddition using copper(I)-catalyzed alkyne-azide cycloaddition or metal-free thermal alkyne-azide cycloaddition (TAAC). Poly(1,2,3-triazole)s with higher molar masses are obtained in higher yields by TAAC polyaddition. A 1,3,4-trisubstituted poly(1,2,3-triazolium) structural analog obtained by TAAC polyaddition using a terminal activated dialkyne and subsequent N-alkylation of the 1,2,3-triazole groups enables discussing the influence of the methyl group in the C-4 or C-5 position on thermal and ion conducting properties. Obtained polymers are characterized by 1H, 13C, and 19F NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, size exclusion chromatography, and broadband dielectric spectroscopy. The targeted 1,3,4,5-tetrasubstituted poly(1,2,3-triazolium) exhibits a glass transition temperature of -23 °C and a direct current ionic conductivity of 2.0 × 10-6 S cm-1 at 30 °C under anhydrous conditions. The developed strategy offers opportunities to further tune the electron delocalization of the 1,2,3-triazolium cation and the properties of poly(1,2,3-triazolium)s using this additional substituent as structural handle.


Asunto(s)
Alquinos , Reacción de Cicloadición , Polímeros , Triazoles , Triazoles/química , Polímeros/química , Polímeros/síntesis química , Alquinos/química , Estructura Molecular , Catálisis , Cobre/química
9.
Macromol Rapid Commun ; 45(9): e2300652, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38407457

RESUMEN

Pyrrole-based polymers (PBPs), a type of fascinating functional polymers, play a crucial role in materials science. However, efficient synthetic strategies of PBPs with diverse structures are mainly focused on conjugated polypyrroles and still remain challenging. Herein, an atom and step economy protocol is described to access various 2,4-disubstituted PBPs by in situ formation of pyrrole core structure via copper-catalyzed [3+2] polycycloaddition of dialkynones and diisocyanoacetates. A series of PBPs is prepared with high molecular weight (Mw up to 18 200 Da) and moderate to good yield (up to 87%), which possesses a fluorescent emission located in the green to yellow light region. Blending the PBPs with polyvinyl alcohol, the stretchable composite films exhibit a significant strengthening of the mechanical properties (tensile stress up to 59 MPa, elongation at break >400%) and an unprecedented stress-responsive luminescence enhancement that over fourfold fluorescent emission intensity is maintained upon stretching up to 100%. On the basis of computational studies, the unique photophysical and mechanical properties are attributed to the substitution of carbonyl chromophores on the pyrrole unit.


Asunto(s)
Cobre , Polímeros , Pirroles , Pirroles/química , Cobre/química , Catálisis , Polímeros/química , Polímeros/síntesis química , Estructura Molecular , Reacción de Cicloadición
10.
Chempluschem ; 89(5): e202300734, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38216541

RESUMEN

Four alkaline earth metal complexes of ketoprofen (Hket) and indomethacin (Hind) were synthesized and characterized: [Ca(ket)2(H2O)2]n (1), [Mg(ket)2(H2O)2] (2), [Ca(ind)2(EtOH)2]n (3), and [Mg(ind)2(EtOH)2] (4). All compounds were studied by elemental analysis (EA), flame atomic absorption spectrometry (FAAS), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). Crystal structures of 1 and 3 were determined by single crystal X-ray diffraction technique T=100 K. The structure of 1 is dominated by a one-dimensional coordination polymer, while 3 is formed by a two-dimensional layer stabilized by the calcium zig-zag chains and π⋅⋅⋅π stacking interactions. Crystal packing arrangements were characterized by fingerprint plots (FPs) that were derived from the Hirshfeld surfaces (HSs). The antioxidant and antimicrobial activities of complexes were evaluated against Gram-positive and Gram-negative bacteria as well as yeasts.


Asunto(s)
Antiinflamatorios no Esteroideos , Antioxidantes , Complejos de Coordinación , Pruebas de Sensibilidad Microbiana , Polímeros , Antioxidantes/química , Antioxidantes/farmacología , Antioxidantes/síntesis química , Antiinflamatorios no Esteroideos/química , Antiinflamatorios no Esteroideos/farmacología , Antiinflamatorios no Esteroideos/síntesis química , Cristalografía por Rayos X , Complejos de Coordinación/química , Complejos de Coordinación/síntesis química , Complejos de Coordinación/farmacología , Polímeros/química , Polímeros/síntesis química , Polímeros/farmacología , Calcio/química , Antibacterianos/farmacología , Antibacterianos/química , Antibacterianos/síntesis química , Modelos Moleculares , Bacterias Gramnegativas/efectos de los fármacos , Bacterias Grampositivas/efectos de los fármacos , Antiinfecciosos/farmacología , Antiinfecciosos/química , Antiinfecciosos/síntesis química , Indometacina/farmacología , Indometacina/química
11.
Macromol Rapid Commun ; 45(8): e2300675, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38163327

RESUMEN

Despite their industrial ubiquity, polyolefin-polyacrylate block copolymers are challenging to synthesize due to the distinct polymerization pathways necessary for respective blocks. This study utilizes MILRad, metal-organic insertion light-initiated radical polymerization, to synthesize polyolefin-b-poly(methyl acrylate) copolymer by combining palladium-catalyzed insertion-coordination polymerization and atom transfer radical polymerization (ATRP). Brookhart-type Pd complexes used for the living polymerization of olefins are homolytically cleaved by blue-light irradiation, generating polyolefin-based macroradicals, which are trapped with functional nitroxide derivatives forming ATRP macroinitiators. ATRP in the presence of Cu(0), that is, supplemental activators and reducing agents , is used to polymerize methyl acrylate. An increase in the functionalization efficiency of up to 71% is demonstrated in this study by modifying the light source and optimizing the radical trapping condition. Regardless of the radical trapping efficiency, essentially quantitative chain extension of polyolefin-Br macroinitiator with acrylates is consistently demonstrated, indicating successful second block formation.


Asunto(s)
Resinas Acrílicas , Polienos , Polimerizacion , Polienos/química , Polienos/síntesis química , Resinas Acrílicas/química , Resinas Acrílicas/síntesis química , Catálisis , Polímeros/química , Polímeros/síntesis química , Paladio/química , Estructura Molecular , Acrilatos/química , Luz
12.
Macromol Rapid Commun ; 45(8): e2300678, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38183637

RESUMEN

Covalent organic frameworks (COFs) represent a new type of crystalline porous polymers that possess pre-designed skeletons, uniform nanopores, and ordered π structure. These attributes make them well-suited for the design of light-emitting materials. However, the majority of COFs exhibits poor luminescence due to aggregation-caused quenching (ACQ), resulting from the strong interaction between adjacent layers. To break the limitation, the building units with three methoxy groups on the walls are used to construct TM-OMe-EBTHz-COF, which suppresses the ACQ effects to improve light-emitting activity of COF. The TM-OMe-EBTHz-COF exhibits a notable emission of yellow-green luminescence in the solid state, with a remarkably high absolute quantum yield of 21.1%. The methoxy groups and hydrazine linkage form three coordination sites, contributing to excellent performance in metal ions sensing. The TM-OMe-EBTHz-COF demonstrates high sensitivity and selectivity to Fe3+ ion. Importantly, the low detection limit is below 150 nanomolar, ranking it among the best-performing Fe3+ sensor systems.


Asunto(s)
Hierro , Estructuras Metalorgánicas , Estructuras Metalorgánicas/química , Estructuras Metalorgánicas/síntesis química , Hierro/química , Hierro/análisis , Iones/química , Iones/análisis , Polímeros/química , Polímeros/síntesis química , Porosidad , Estructura Molecular , Luminiscencia , Límite de Detección , Tamaño de la Partícula , Propiedades de Superficie
13.
Macromol Rapid Commun ; 45(8): e2300690, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38207336

RESUMEN

The compositional scope of polymer zwitterions has grown significantly in recent years and now offers designer synthetic materials that are broadly applicable across numerous areas, including supracolloidal structures, electronic materials interfaces, and macromolecular therapeutics. Among recent developments in polymer zwitterion syntheses are those that allow insertion of reactive functionality directly into the zwitterionic moiety, yielding new monomer and polymer structures that hold potential for maximizing the impact of zwitterions on the macromolecular materials chemistry field. This manuscript describes the preparation of zwitterionic choline phosphate (CP) methacrylates containing either aromatic or aliphatic thiols embedded directly into the zwitterionic moiety. The polymerization of these functional CP methacrylates by reversible addition-fragmentation chain-transfer methodology yields polymeric zwitterionic thiols containing protected thiol functionality in the zwitterionic units. After polymerization, the protected thiols are liberated to yield thiol-rich polymer zwitterions which serve as precursors to subsequent reactions that produce polymer networks as well as polymer-protein bioconjugates.


Asunto(s)
Polimerizacion , Polímeros , Compuestos de Sulfhidrilo , Compuestos de Sulfhidrilo/química , Polímeros/química , Polímeros/síntesis química , Fosforilcolina/química , Fosforilcolina/análogos & derivados , Estructura Molecular , Metacrilatos/química
14.
Macromol Rapid Commun ; 45(8): e2300674, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38234077

RESUMEN

Defined, branched polymer architectures with low dispersity and architectural purity are of great interest to polymer science but are challenging to synthesize. Besides star and comb, especially the pom-pom topology is of interest as it is the simplest topology with exactly two branching points. Most synthetic approaches to a pom-pom topology reported a lack of full control and variability over one of the three topological parameters, the backbone or arm molecular weight and arm number. A new, elegant, fast, and scalable synthetic route without the need for post-polymerization modification (PPM) or purification steps during the synthesis to a pom-pom and a broad variety of topologies made from styrene and dienes is reported, with potential application to barbwire, bottlebrush, miktoarm star, Janus type polymers, or multi-graft copolymers. The key is to inset short poly(2-vinyl-pyridine) blocks (<2 mol% in the branched product) into the backbone as branching points. Carb anions can react at the C6 carbon of the pyridine ring, grafting the arms onto the backbone. Since the synthetic route to polystyrene pom-poms has only two steps and is free of PPM or purification, large amounts of up to 300 g of defined pom-pom structures can be synthesized in one batch.


Asunto(s)
Aniones , Polimerizacion , Poliestirenos , Poliestirenos/química , Aniones/química , Estructura Molecular , Polímeros/química , Polímeros/síntesis química , Polivinilos/química , Polivinilos/síntesis química
15.
Nature ; 615(7951): 251-258, 2023 03.
Artículo en Inglés | MEDLINE | ID: mdl-36890370

RESUMEN

Biological fluids, the most complex blends, have compositions that constantly vary and cannot be molecularly defined1. Despite these uncertainties, proteins fluctuate, fold, function and evolve as programmed2-4. We propose that in addition to the known monomeric sequence requirements, protein sequences encode multi-pair interactions at the segmental level to navigate random encounters5,6; synthetic heteropolymers capable of emulating such interactions can replicate how proteins behave in biological fluids individually and collectively. Here, we extracted the chemical characteristics and sequential arrangement along a protein chain at the segmental level from natural protein libraries and used the information to design heteropolymer ensembles as mixtures of disordered, partially folded and folded proteins. For each heteropolymer ensemble, the level of segmental similarity to that of natural proteins determines its ability to replicate many functions of biological fluids including assisting protein folding during translation, preserving the viability of fetal bovine serum without refrigeration, enhancing the thermal stability of proteins and behaving like synthetic cytosol under biologically relevant conditions. Molecular studies further translated protein sequence information at the segmental level into intermolecular interactions with a defined range, degree of diversity and temporal and spatial availability. This framework provides valuable guiding principles to synthetically realize protein properties, engineer bio/abiotic hybrid materials and, ultimately, realize matter-to-life transformations.


Asunto(s)
Materiales Biomiméticos , Biomimética , Polímeros , Conformación Proteica , Pliegue de Proteína , Proteínas , Secuencia de Aminoácidos , Polímeros/síntesis química , Polímeros/química , Proteínas/química , Materiales Biomiméticos/síntesis química , Materiales Biomiméticos/química , Líquidos Corporales/química , Citosol/química , Albúmina Sérica Bovina/química , Biología Sintética
16.
Nature ; 610(7932): 502-506, 2022 10.
Artículo en Inglés | MEDLINE | ID: mdl-36171292

RESUMEN

In the realm of particle self-assembly, it is possible to reliably construct nearly arbitrary structures if all the pieces are distinct1-3, but systems with fewer flavours of building blocks have so far been limited to the assembly of exotic crystals4-6. Here we introduce a minimal model system of colloidal droplet chains7, with programmable DNA interactions that guide their downhill folding into specific geometries. Droplets are observed in real space and time, unravelling the rules of folding. Combining experiments, simulations and theory, we show that controlling the order in which interactions are switched on directs folding into unique structures, which we call colloidal foldamers8. The simplest alternating sequences (ABAB...) of up to 13 droplets yield 11 foldamers in two dimensions and one in three dimensions. Optimizing the droplet sequence and adding an extra flavour uniquely encodes more than half of the 619 possible two-dimensional geometries. Foldamers consisting of at least 13 droplets exhibit open structures with holes, offering porous design. Numerical simulations show that foldamers can further interact to make complex supracolloidal architectures, such as dimers, ribbons and mosaics. Our results are independent of the dynamics and therefore apply to polymeric materials with hierarchical interactions on all length scales, from organic molecules all the way to Rubik's Snakes. This toolbox enables the encoding of large-scale design into sequences of short polymers, placing folding at the forefront of materials self-assembly.


Asunto(s)
Ciencia de los Materiales , Polímeros , ADN/química , Emulsiones/síntesis química , Emulsiones/química , Polímeros/síntesis química , Polímeros/química , Ciencia de los Materiales/métodos , Coloides/síntesis química , Coloides/química
17.
J Phys Chem Lett ; 13(6): 1617-1627, 2022 Feb 17.
Artículo en Inglés | MEDLINE | ID: mdl-35142518

RESUMEN

Revealing interfacial shear-induced structural responsiveness has long been an important topic in that most fluids in nature and human life are in motion and cause interesting boundary phenomena. It is amazing how the polymer chain conformation or local structural features at a boundary change under the effective shear condition. In this study, microfluidic-assisted sum frequency generation (SFG) vibrational spectroscopy and all-atom molecular dynamics (MD) simulation are combined to reveal that the shear flow can effectively block the so-called thermal coil-to-globule transition of the poly(N-isopropylacrylamide) (PNIPAM) brushes on the solid substrate, and the normal coil-to-globule transition transfers to a coil-to-stretch one under shear flow with increasing ambient temperature. Such findings are attributed to the balance between the shear flow and the molecular interaction with respect to the polymer chains and adjacent water molecules, thus demonstrating the significant effect of the shear flow on the structural and dynamic behaviors of the polymer chains at the boundaries from the molecular level.


Asunto(s)
Acrilamidas/química , Resinas Acrílicas/química , Simulación de Dinámica Molecular , Polímeros/síntesis química , Modelos Moleculares , Estructura Molecular , Polímeros/química , Propiedades de Superficie , Temperatura , Agua
18.
ACS Appl Mater Interfaces ; 14(4): 5090-5100, 2022 Feb 02.
Artículo en Inglés | MEDLINE | ID: mdl-35060376

RESUMEN

Pulmonary delivery of anti-inflammatory siRNA presents a promising approach for localized therapy of acute lung injury (ALI), while polycationic vectors can be easily trapped by the negatively charged airway mucin glycoproteins and arbitrarily internalized by epithelial cells with nontargetability for immunological clearance. Herein, we report a material, the dopamine (DA)-grafted hyaluronic acid (HA-DA), coating on an anti-TNF-α vector to address these limitations. HA-DA was simply synthesized and facilely coated on poly(ß-amino ester) (BP)-based siRNA vectors via electrostatic attraction. The resulting HA-DA/BP/siRNA displayed significantly enhanced mucus penetration, attributable to the charge screen effect of HA-DA and the bioadhesive nature of the grafting DA. After transmucosal delivery, the nanosystem could target diseased macrophages via CD44-mediated internalization and rapidly escape from endo/lysosomes through the proton sponge effect, resulting in effective TNF-α regulation. Meanwhile, DA modification endowed the coating material with robust antioxidative capability to scavenge a broad spectrum of reactive oxygen/nitrogen species (RONS), which protected the lung tissue from oxidative damage and synergized with anti-TNF-α to inhibit a cytokine storm. As a result, a remarkable amelioration of ALI was achieved in a lipopolysaccharide (LPS)-stimulated mice model. This study provides a multifunctional coating material to facilitate pulmonary drug delivery for the treatment of lung diseases.


Asunto(s)
Lesión Pulmonar Aguda/tratamiento farmacológico , Dopamina/uso terapéutico , Portadores de Fármacos/uso terapéutico , Depuradores de Radicales Libres/uso terapéutico , Ácido Hialurónico/uso terapéutico , ARN Interferente Pequeño/uso terapéutico , Animales , Dopamina/análogos & derivados , Dopamina/síntesis química , Portadores de Fármacos/síntesis química , Portadores de Fármacos/química , Liberación de Fármacos , Depuradores de Radicales Libres/síntesis química , Depuradores de Radicales Libres/química , Humanos , Ácido Hialurónico/análogos & derivados , Ácido Hialurónico/síntesis química , Activación de Macrófagos/efectos de los fármacos , Macrófagos/efectos de los fármacos , Masculino , Ratones , Ratones Endogámicos C57BL , Moco/metabolismo , Células 3T3 NIH , Nanopartículas/química , Nanopartículas/uso terapéutico , Polímeros/síntesis química , Polímeros/química , Células RAW 264.7 , ARN Interferente Pequeño/química , Factor de Necrosis Tumoral alfa/antagonistas & inhibidores
19.
Carbohydr Polym ; 280: 119009, 2022 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-35027122

RESUMEN

In this study, a kind of polymeric ionic liquid (PIL) called PIL-Cl was synthesized and modified to obtain conductive graphene coated carboxymethyl cellulose hybrid fibers. Carboxymethyl cellulose (CMC) was formed into fibers by wet spinning assisted with PILCl. Co-precipitation test of CMC and PIL-Cl demonstrated that PIL-Cl could precipitate with CMC through strong electrostatic interaction and molar ratio of CMC and PIL-Cl (calculated in repeating units) would affect the formation of precipitation. Secondly, modified PIL-Cl named PIL-Ac was used as an intermediate connecting CMC fiber and graphene to fabricate conductive CMC/PIL/graphene fibers. A series of tests were performed on CMC/PIL/graphene fibers, including Raman spectroscopy, scanning electron microscopy and conductivity test. The results showed that PIL-Cl could help form CMC fiber, and PIL-Ac could functionalize it and make it conductive.


Asunto(s)
Carboximetilcelulosa de Sodio/química , Grafito/química , Líquidos Iónicos/química , Polímeros/química , Conductividad Eléctrica , Enlace de Hidrógeno , Polímeros/síntesis química , Electricidad Estática
20.
ACS Appl Mater Interfaces ; 14(4): 5815-5824, 2022 Feb 02.
Artículo en Inglés | MEDLINE | ID: mdl-35044158

RESUMEN

The residue of pesticides in crops, soil, and water continues to be a widespread concern due to the threat to human health and food safety. With the aim to develop highly sensitive sensing materials and portable detection devices, two dicarbazole-based fluorescent micro-/mesoporous polymers (JYs) with a larger specific surface area and pore sizes ranging from 1.1 to 34.2 nm are synthesized. The Stern-Volmer constants of JY fluorescence quenching for imidacloprid (50,063 M-1) exceed 23-51 times those of the reported porous organic polymers (980-2173 M-1). Of particular interest is the observation that JYs show rapid fluorescence response (2 s) and ultralow detection limit (30 ppb) for imidacloprid in water medium. The pronounced chemsensing property is attributed to the synergistic role of the hierarchical pore structure, large π-conjugation of chromophore groups, and strong inner filter effect between the polymer and imidacloprid molecule. Moreover, the pesticide detection of JYs exhibits good interference resistance in complicated service environments such as the extract liquids of the apple peel and field soil as well as aqueous solutions of various cations and anions. Because of the portability, excellent reusability, and sensitive fluorescence response, the prepared JYs and detection devices have promising applications in the on-site monitoring and early warning of the pesticide residues.


Asunto(s)
Carbazoles/química , Colorantes Fluorescentes/química , Residuos de Plaguicidas/análisis , Polímeros/química , Carbazoles/síntesis química , Colorantes Fluorescentes/síntesis química , Contaminación de Alimentos/análisis , Malus/química , Polímeros/síntesis química , Porosidad , Suelo/química , Contaminantes del Suelo/análisis , Espectrometría de Fluorescencia
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