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1.
Mater Horiz ; 10(10): 4398-4406, 2023 Oct 02.
Artigo em Inglês | MEDLINE | ID: mdl-37466338

RESUMO

Simultaneously gluing hydrophobic and hydrophilic materials is a highly desired but intractable task. Herein, we developed a facile strategy using reversibly interlocked macromolecular networks (ILNs) as an adhesive. As shown by the proof-of-concept assembly of glass/ILNs/fluoropolymer (i.e., a simplified version of a photovoltaic module), the sandwiched ILNs were stratified after hot-pressing owing to temporary decrosslinking enabled by the built-in reversible covalent bonds. The fragmented component networks were enriched near their respective thermodynamically favored substrates to form a Janus-like structure. Strong elaborate interfacial bespoke chemical bonds and mechanical interlocking were thus established accompanied by the reconstruction of ILNs after cooling, which cooperated with the robust cohesion of the core part of the ILNs resulting from topological entanglements and led to a record-high peeling strength of 64.86 N cm-1. Also, the ILN-based Janus-like adhesive possessed reversible recyclability, adhesivity and on-demand de-bondability. The molecular design detailed in this study serves as a guide for developing a high-performance smart adhesive that firmly bonds non-sticking materials. Compared with existing Janus adhesives, our ILNs-based adhesive not only shows extremely useful reversibility but also greatly simplifies the adhesion process with no surface treatment required.

2.
Adv Mater ; 35(14): e2211009, 2023 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-36660910

RESUMO

The development of photochemical self-healing polymers faces the the following bottlenecks: i) only the surface cracks can be restored and ii) materials' mechanical properties are lower. To break these bottlenecks, cross-linked poly(urethane-dithiocarbamate)s carrying photo-reversible dithiocarbamate bonds covalently linked to indole chromophores and benzyl groups are designed. The conjugated structure of the chromophore and benzyl enhances the addition reactivity of thiocarbonyl moiety and facilitates photo-cleavage of CS bond, so that transfer of the created radicals among dithiocarbamate linkages is promoted. Accordingly, reshuffling of the reversibly cross-linked networks via dynamic exchange between the activated dithiocarbamates is enabled in both surface layer and the interior upon exposure to the low-intensity ultraviolet (UV) light from the sun. It is found that the damages up to a centimeter below the surface can be effectively recovered in the sunshine, which greatly exceeds the maximum penetration distance of UV light (hundreds of microns). Besides, tensile strength and failure strain of the poly(urethane-dithiocarbamate) are superior to the reported photo-reversible polymers, achieving the record-high 33.8 MPa and 782.0% owing to the wide selectivity of soft/hard blocks, multiple interactions, and appropriate cross-linking architecture. The present work provides a novel paradigm of photo self-healing polymers capable of re-bonding cracks even out of the reach of the illumination.

3.
Nat Commun ; 13(1): 2633, 2022 May 12.
Artigo em Inglês | MEDLINE | ID: mdl-35551199

RESUMO

To impart self-healing polymers largely adjustable dynamicity and mechanical performance, here we develop libraries of catalyst-free reversible polythioureas directly from commodity 1,4-phenylene diisothiocyanate and amines via facile click chemistry based modular assembly. By using the amine modules with various steric hindrances and flexibilities, the reversible thiourea units acquire triggering temperatures from room temperature to 120 °C. Accordingly, the derived self-healable, recyclable and controlled degradable dynamically crosslinked polythioureas can take effect within wide temperature range. Moreover, mechanical properties of the materials can be tuned covering plastics, elastomers and fibers using (i) different assemble modules or (ii) solid-state stretching. Particularly, unidirectional stretching leads to the record-high tensile strength of 266 MPa, while bidirectional stretching provides the materials with biaxial strengths up to over 120 MPa. The molecular mechanism and technological innovations discussed in this work may benefit promotion and application of self-healing polymers towards greatly diverse demands and scenarios.

4.
J Biomed Mater Res A ; 109(12): 2506-2515, 2021 12.
Artigo em Inglês | MEDLINE | ID: mdl-34110080

RESUMO

ß-1,3-D-glucan has been reported to have a series of bioactivities including antitumor, antimicrobial, anti-inflammatory and antioxidative effects; however, its insolubility in neutral aqueous solution significantly restricts the potential application in biological and medicine fields. Herein, a water-soluble aminated ß-1,3-D-glucan (AG) was synthesized and the anti-inflammatory effect, cytotoxicity and plasmid DNA (pDNA) binding capacity of AG, serum stability, the particle sizes and zeta potentials of AG/pDNA nanocomposites, and the transfection efficiency and mechanism of action were studied. AG shows no obvious cytotoxicity within the range of working concentration (1-64 µg/ml) and it exerts potent anti-inflammatory effect independent on Dectin-1 and TLR2. AG/pDNA nanocomposites prepared by electrostatic interaction possess an appropriate particle size ranged from 192.8 to 118.4 nm and zeta potentials ranged from 20.880 to 27.16 mV with the N/P ratios from 5 to 100. AG/pDNA nanocomposites at the N/P ratios of 10 and 20 were able to show superior transfection efficiencies in RAW 264.7 cells as a result of their suitable particle size, zeta potential, anti-inflammatory effect, and the specific interaction with pattern recognition receptors (Dectin-1 and TLR2). These results indicate that AG is a potential candidate for DNA delivery system due to its potent anti-inflammatory effect and high transfection efficiency.


Assuntos
Anti-Inflamatórios/farmacologia , Portadores de Fármacos , Terapia Genética/métodos , Proteoglicanas/química , Proteoglicanas/farmacologia , Transfecção/métodos , Animais , Sobrevivência Celular/efeitos dos fármacos , DNA/metabolismo , Técnicas de Transferência de Genes , Lectinas Tipo C/metabolismo , Camundongos , Nanocompostos , Tamanho da Partícula , Plasmídeos/genética , Proteoglicanas/toxicidade , Células RAW 264.7 , Receptor 2 Toll-Like/metabolismo
5.
ACS Appl Mater Interfaces ; 13(24): 28737-28748, 2021 Jun 23.
Artigo em Inglês | MEDLINE | ID: mdl-34106701

RESUMO

The colossal volumetric expansion (up to 300%) of the silicon (Si) anode during repeated charge-discharge cycles destabilizes the electrode structure and causes a drastic drop in capacity. Here in this work, commercial poly(acrylic acid) (PAA) is cross-linked by hydroxypropyl polyrotaxane (HPR) via reversible boronic ester bonds to achieve a water-soluble polymeric binder (PAA-B-HPR) for making the Si anode of the Li-ion battery. Slidable α-cyclodextrins of modified polyrotaxane are allowed to move around when the unwanted volume variation occurs in the course of lithiation and delithiation so that the accumulated internal stress can be equalized throughout the system, while the reversible boronic ester bonds are capable of healing the damages created during manufacturing and service to maintain the electrode integrity. As a result, the Li-ion battery assembled with the Si anode comprised of the PAA-B-HPR binder possesses outstanding specific capacity and cycle stability within a wide temperature range from 25 to 55 °C. Especially, the Si@PAA-B-HPR anode exhibits a discharge specific capacity of 1056 mA h/g at 1.4 A/g after 500 cycles under a higher temperature of 55 °C, and the corresponding capacity fading rate per cycle is only 0.10%. The present work opens an avenue toward the practical application of the Si anode for Li-ion batteries.

6.
Macromol Rapid Commun ; 41(22): e2000371, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32959451

RESUMO

The fascinating pulley effect from moveable α-cyclodextrin (α-CD) based polyrotaxane favors toughening of hydrogels, but the strategy is rarely applied in bulk polymers because of the severe aggregation trend of α-CDs. Herein, the authors propose a simple approach to moderately modify the α-CDs of polyrotaxane by introducing large steric side groups and reactive CC so as to minimize the unwanted hydrogen bonds-induced aggregation of α-CDs and hydrophilicity of polyrotaxane. Accordingly, the proof-of-concept material, poly(methyl acrylate) crosslinked by the modified polyrotaxane, turns out to be rather homogeneous with optical transparency. The polyrotaxane crosslinks are movable under external force as disclosed by in situ small-angle X-ray scattering and other techniques, which is correlated to the relative amount of α-CDs. A few polyrotaxane crosslinkers prove to be sufficient to simultaneously improve strength and toughness of poly(methyl acrylate) owing to the stress equalization. The present work provides an expandable toolbox for enhancing polymers.


Assuntos
Ciclodextrinas , Rotaxanos , Hidrogéis , Interações Hidrofóbicas e Hidrofílicas , Polietilenoglicóis , Polímeros
7.
ACS Appl Mater Interfaces ; 12(24): 27614-27624, 2020 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-32468811

RESUMO

A novel strategy for developing homogeneous reversibly interlocking polymer networks (RILNs) with enhanced mechanical properties and underwater self-healing ability is proposed. The RILNs are prepared by the topological reorganization of two preformed cross-linked polymers containing reversible catechol-Fe3+ coordinate bonds and imine bonds and exhibit enhanced mechanical properties, superior underwater self-healing effect within a wide pH range, and water-assisted recycling ability through synergetic action between the reversible catechol-Fe3+ and imine bonds. At higher pH values, the catechol-Fe3+ coordinate bonds are responsible for self-healing, while the imine bonds maintain the stability of the materials. In neutral water, the imine bonds mainly account for self-healing, and hydrogen bonds and entanglements between the two networks prevent the material from collapsing. Under a lower pH value, intermolecular hydrogen bonds and entanglements contribute to self-healing. The outcomes of this work provide a new idea for developing robust multifunctional underwater self-healing materials.

8.
Nanotechnology ; 31(33): 335717, 2020 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-32375129

RESUMO

N-doped carbon-based materials are crucial electrically conductive additives and non-metal electrocatalysts for the oxygen reduction reaction. At present, many pieces of research are focused on the effects of micropore, mesopore and hierarchical pore structure on the catalytic activity, however, there are few works concerning the role of large-dimension through-hole structure. Hence, in this work, we prepare two kinds of carbon materials with large through-hole structure, i.e. N-doped carbon hollow-spheres and hollow-tubes, as the oxygen reduction catalysts. The synthesis follows template-free morphology-controlled pyrolysis, which is more convenient than the preparation of conventional N-doped nanotubes and graphene. The resultant N-doped carbon hollow-spheres and hollow-tubes evidently enhanced their ORR catalytic activity, remarkable long-term stability and methanol resistance. The large-dimension through-hole structure is found to account for the increase in mass transfer.

9.
ACS Appl Mater Interfaces ; 12(20): 22534-22542, 2020 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-32338869

RESUMO

Implantable and wearable materials, which are usually used in/on a biological body, are mostly needed with biomimetic self-healing function. To enable repeatable large-wound self-healing and volume/structure recovery, we verified a proof-of-concept approach in this work. We design a polymer hydrogel that combines temperature responsiveness with an intrinsic self-healing ability through host-guest orthogonal self-assembly between two types of poly(N-isopropylacrylamide) (PNIPAM) oligomers. The result is thermosensitive, capable of fast self-repair of microcracks based on reversible host-guest assembly. More importantly, when a large open wound appears, the hydrogel can first close the wound via volume swelling and then completely self-repair the damage in terms of intrinsic self-healing. Meanwhile, its original volume can be easily recovered by subsequent contraction. As demonstrated by the experimental data, such millimeter-level wound self-healing and volume recovery can be repeatedly carried out in response to the short-term cooling stimulus. With low cytotoxicity and good biocompatibility, moreover, this highly intelligent hydrogel is greatly promising for practical large-wound self-healing in wound dressing, electronic skins, wearable biosensors, and humanoid robotics, which can tolerate large-scale human motions.


Assuntos
Resinas Acrílicas/química , Adamantano/análogos & derivados , Materiais Biocompatíveis/química , Hidrogéis/química , beta-Ciclodextrinas/química , Estudo de Prova de Conceito , Temperatura de Transição
10.
ACS Appl Mater Interfaces ; 11(34): 31346-31355, 2019 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-31381290

RESUMO

The present work is focused on developing external stress-free two-way triple shape memory polymers (SMPs). Accordingly, a series of innovative approaches are proposed for the material design and preparation. Polyurethane prepolymers carrying crystalline polytetrahydrofuran (PTMEG) and poly(ε-caprolactone) (PCL) as the switching phases are respectively synthesized in advance and then cross-linked to produce the target material. The stepwise method is believed to be conducive to manipulation of the relative contribution of PCL and PTMEG. Moreover, the chain extender, 2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol (UPy), is incorporated to establish hydrogen bonds among the macromolecules. By straightforward stretching treatment at different temperatures, the hydrogen bond networks are successfully converted into an internal stress provider, which overcomes the challenge of stress relaxation of the melted low melting temperature polymer (i.e., PTMEG) and increases the efficiency of stress transfer. Meanwhile, the contraction force of the switching phases is tuned to match the internal tensile stress. As a result, the internal stress provider can closely collaborate with melting/recrystallization of the crystalline domains, leading to the repeated multiple shape memory effects. The cross-linked polyurethane is thus able to reversibly morph among three shapes and displays its potentials as soft robot and actuator. The strategy reported here has the advantages of easily accessible raw materials, simple reaction, and facile programing/deprograming/reprograming, so that it possesses wide applicability.

11.
RSC Adv ; 9(8): 4157-4161, 2019 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-35520197

RESUMO

Solid-state electrolytes have emerged as a promising alternative to existing liquid electrolytes for next-generation flexible Li metal batteries with enhanced safety and stability. Nevertheless, the brittleness and inferior room temperature conductivity are major obstacles for practical applications. Herein, for the first time, we have fabricated a flexible lithium ion conductive glass-ceramic fiber by using a melt-spun homogeneous NASICON-type structured Li1.5Al0.5Ge1.5(PO4)3 (LAGP) glass melt and annealed at 825 °C. The annealed samples exhibited a higher lithium ion conductivity than the air-quenched sample due to the presence of a well-crystallized crystal grain in the annealed sample. Meanwhile, the ionic conductivity has shown an inverse relationship with the diameter of annealed LAGP glass-ceramic fibers. The results revealed that the annealed glass-ceramic fiber, with a diameter of 10 µm, resulted in lithium ion conductivity of 8.8 × 103 S cm-1 at room temperature.

12.
ACS Macro Lett ; 8(9): 1141-1146, 2019 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-35619451

RESUMO

Two simple methods are proposed to respectively impart external force-free reversible shape memory effect to commercial polyolefins: ultrahigh molecular weight polyethylene (UHMWPE) and polypropylene (PP). The key issues lie in the utilization of the partially entangled molecular chains of UHMWPE and the medium crystalline phases of PP as the reversible internal stress providers. The acquired reversible shape memory effect further proves to be applicable for assisting repeatedly self-healing of wider cracks. Compared to the conventional approaches, which used to introduce cross-linkages into the target materials, the present ones only need physical treatment, so that the valuable thermoplasticity of polyolefins is retained. This work can be regarded as an example of the concept "physically converting instead of chemically modifying" for the preparation of functional polymeric materials based on market available plastics.

13.
ACS Appl Mater Interfaces ; 10(44): 38538-38546, 2018 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-30284805

RESUMO

To enable repeated intrinsic self-healing of wider cracks in polymers, a proof-of-concept approach is verified in the present work. It operates through two-way shape memory effect (SME)-aided intrinsic self-healing. Accordingly, a reversible C-ON bond is introduced into the main chain of crosslinked polyurethane (PU) containing an elastomeric dispersed phase (styrene-butadiene-styrene block copolymer, SBS). The PU/SBS blend was developed by the authors recently, and proved to possess an external stress-free two-way SME after programming. As a result, the thermal retractility offered by the SME coupled with the reversible C-ON bonds can be used for successive crack closure and remending based on synchronous fission/radical recombination of C-ON bonds. Moreover, multiwalled carbon nanotubes are incorporated to impart electrical conductivity to the insulating polymer. Repeated autonomic healing of wider cracks is thus achieved through narrowing of cracks followed by chemical rebonding under self-regulating Joule heating. No additional programming is needed after each healing event, which is superior to one-way SME-assisted self-healing. The outcomes set an example of integrating different stimuli-responsivities into single materials.

14.
Acta Biomater ; 78: 211-223, 2018 09 15.
Artigo em Inglês | MEDLINE | ID: mdl-30098441

RESUMO

Presently, clinically approved adjuvants (such as aluminum salts) fail to induce cellular immune responses, which is crucial to defend against intracellular pathogens (including HIV, malaria, tuberculosis and Ebola) and cancer. However, Freund's complete adjuvant potently stimulates both humoral and cellular immune responses, accompanying by high toxicity and severe side reactions. Here in this work, a CpG-oligodeoxynucleotides (CpG-OND) crosslinked aminated ß-glucan-Ovalbumin dual targeting nanoparticle (CpG-OND-AG-OVA) is prepared through a simple and mild ionic complexation method. The aminated ß-glucan plays dual roles as antigen presenting cells (APCs) targeted carrier and immunopotentiator (targeting and activating dectin-1 on APCs). Meanwhile, CpG-OND also plays dual roles as ionic crosslinker and immunopotentiator (targeting and activating Toll-like receptor 9 in APCs). The adjuvant activity of the particles is evaluated through in vitro and in vivo experiments. The particles significantly enhance uptake and sustained proteolytic processing of antigens, and result in APCs maturation, inducing robust Th1 and Th2-type immune responses comparable to Freund's adjuvant without obvious toxicity. The potent adjuvant activity of the nanoparticles may originate from dual targeting synergistic effects between aminated ß-glucan and CpG-OND. Accordingly, the dual targeting nanoparticles may be a promising vaccine adjuvant for inducing robust humoral and cellular immune responses against infectious diseases and cancers. STATEMENT OF SIGNIFICANCE: An ideal adjuvant for subunit vaccine should act as both a carrier to enhance the uptake, sustained processing and cytosolic delivery of antigens, and an immunopotentiator to stimulate antigen presenting cells (APCs) for activation of naive T cells. Additionally, it should be easy to obtain and safe with negligible toxicity. Unfortunately, both synthetic and natural polymers that have been developed into antigen delivery system cannot completely fulfill the requirements. In the present study, the authors design nanoparticles with aminated ß-glucan and CpG-oligodeoxynucleotides (CpG-OND) through a simple and mild method. ß-Glucan (a dectin-1 and TLR2 targeted PAMP) and CpG-OND (a TLR9 targeted PAMP) are readily accessible. Aminated ß-glucan plays dual roles in the nanoparticle as APCs targeted carrier and immunopotentiator. Meanwhile, CpG-OND also plays dual roles as crosslinker and APCs targeted immunopotentiator. By making use of synergistic effect of the dual targeting vaccine adjuvant with aminated ß-glucan and CpG-OND, the nanoparticles induce robust antigen specific immune responses comparable to Freund's adjuvant without obvious toxicity.


Assuntos
Adjuvantes Imunológicos/farmacologia , Aminas/química , Imunidade Celular/efeitos dos fármacos , Imunidade Humoral/efeitos dos fármacos , Oligodesoxirribonucleotídeos/farmacologia , Vacinas/imunologia , beta-Glucanas/farmacologia , Animais , Anticorpos/sangue , Apresentação de Antígeno/efeitos dos fármacos , Diferenciação Celular/efeitos dos fármacos , Citocinas/metabolismo , Sinergismo Farmacológico , Feminino , Imunização , Ativação de Macrófagos/efeitos dos fármacos , Macrófagos/efeitos dos fármacos , Macrófagos/metabolismo , Camundongos , Camundongos Endogâmicos BALB C , Nanopartículas/química , Nanopartículas/ultraestrutura , Especificidade de Órgãos , Ovalbumina/imunologia , Células RAW 264.7 , Baço/citologia
15.
Nanotechnology ; 29(46): 465402, 2018 Nov 16.
Artigo em Inglês | MEDLINE | ID: mdl-30156562

RESUMO

Development of bifunctional non-metal electrocatalyst for oxygen reduction reactions (ORRs) and oxygen evolution reactions (OERs) with high efficiency, durable stability and low cost is a crucial and challenging issue. However, the heteroatom-doped carbon material including a carbon-based conductive additive would be easily oxidized under the high potential needed for driving the OER. Besides, the interaction between the heteroatom-doped carbon material that possesses electrocatalyst activity and a carbon-based conductive additive is weak, affecting the performance of the electrocatalyst. In this context, we introduce CoS nanoparticles into a three-dimensional N-doped carbon framework (CoS/NCF) by a morphology-retaining pyrolysis of polyaniline/CoS framework precursor, in which the polyaniline framework provides abundant functional groups to nucleate and grow CoS nanoparticles while retaining its interconnected three-dimensional porous structure. Benefiting from (i) the lower OER potential of CoS nanoparticles than the electro-oxidation decomposition potential of a carbon material and (ii) the strong affinity of CoS nanoparticles for a N-doped carbon framework, higher stability than commercial Pt/C system and greater catalytic activity towards ORR with an onset potential of about 0.921 V versus reversible hydrogen electrode (RHE) are observed. Furthermore, only a potential of 1.515 V versus RHE is required for achieving a current density of 10 mA cm-2.

16.
Macromol Rapid Commun ; 39(12): e1700714, 2018 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-29749065

RESUMO

Development of two-way shape memory polymers that operate free of external force remains a great challenge. Here, the design criteria for this type of material are proposed, deriving a novel fabrication strategy accordingly, which employs conventional crosslinked polyurethane (PU) containing crystalline poly(ε-caprolactone) (PCL) as the proof-of-concept material. Having been simply trained by stretching and thermal treatment without additional ingredients and chemicals, the PU is coupled with a two-way shape memory effect. The core advancement of this study lies in the successful conversion of the inherent hydrogen bond network, which is often the easiest to overlook, into an internal stress provider. The temperature-dependent reversible melting/recrystallization of the crystalline phases elaborately works with the tensed hydrogen bond network, leading to implementation of the two-way shape memory effect. An average reversible strain of as high as ≈20% along the stretch direction is obtained through cooperation adjustment of chemical crosslinking density, crystallinity, and concentration of hydrogen bonds. Meanwhile, the highest internal tension offered by the hydrogen bond network is determined to be 0.10 MPa. Owing to the great convenience characterized by material selection, preparation, programming, and application, the current work may open up an avenue for production and usage of the smart material.


Assuntos
Materiais Biocompatíveis/química , Poliésteres/química , Polímeros/química , Poliuretanos/química , Materiais Biocompatíveis/síntese química , Cristalização , Ligação de Hidrogênio , Estrutura Molecular , Polímeros/síntese química , Espectroscopia de Infravermelho com Transformada de Fourier , Temperatura
17.
Nanotechnology ; 29(12): 12LT01, 2018 03 23.
Artigo em Inglês | MEDLINE | ID: mdl-29424366

RESUMO

A quadrupole electric field-mediated exfoliation method is proposed to convert micron-sized hexagonal boron nitride (h-BN) powder into few-layer hexagonal boron nitride nanosheets (h-BNNS). Under optimum conditions (400 Hz, 40 V, 32 µg ml-1, sodium deoxycholate, TAE medium), the h-BN powders (thickness >200 nm, horizontal scale ∼10 µm) are successfully exfoliated into 0.5-4 nm (1-10 layers) thick h-BNNS with the same horizontal scale. Dynamic laser scattering and atomic force microscope data show that the yield is 47.6% (for the portion with the thickness of 0.5-6 nm), and all of the vertical sizes are reduced to smaller than 18 nm (45 layers).

18.
J Mater Chem B ; 6(39): 6288-6301, 2018 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-32254619

RESUMO

The aim of vaccines is to imitate the immune responses induced by pathogen infection without causing disease. Therefore, strategies of designing vaccine delivery systems by mimicking key features of pathogens are often used. For this purpose, the present study prepares pathogen-mimicking ß-glucan-conjugated hollow silica particles by using polystyrene or bacteria particles as templates. The particles perfectly duplicate the structure and morphology of pathogens and possess excellent properties of hollow silica particles, including large opening pore channels, large interior cavities, high loading of OVA (ovalbumin) and controlled release capability, biocompatibility, tunability of surface functionality and immunopotentiating activity. In addition, the particles are antigen presenting cells (APCs) targeted by specific interaction with ß-glucan specific receptors on the surface of APCs, which can enhance the uptake and sustained proteolytic processing of antigens and induce APC maturation. Eventually, potent Th1 and Th2-type immune responses are aroused. The size and shape of the particles have a significant impact on the antigen uptake and immunoadjuvant activity. The degree of antigen uptake enhancement is ranked in the following order: PS HSP@glucan (nanoscale spherical) > E. coli HSP@glucan (micron-sized rod-like) > S. aureus HSP@glucan (micron-sized spherical). The PS HSP@glucan is more apt to induce a Th1-type immune response, while the E. coli HSP@glucan is more apt to induce a Th2-type immune response. The particles may thus provide a promising strategy for development of novel vaccine delivery systems for inducing robust humoral and cellular immune responses against infectious diseases and cancers.

19.
ACS Appl Mater Interfaces ; 9(42): 37300-37309, 2017 Oct 25.
Artigo em Inglês | MEDLINE | ID: mdl-28984125

RESUMO

To improve reliability, durability, and reworkability of bulk polymers utilized in ubiquitous acidic water, the authors develop a novel hyperbranched polymer capable of self-healing and recycling in a low-pH aqueous environment. The hyperbranched polymer has many hydrophilic and hydrophobic terminal groups. When it is damaged in acidic water, the hydrophilic groups are protonated, forming hydrogen bonds, and closing the crack. Meanwhile, hydrophobic interactions of hydrophobic groups are gradually established across the interface because of the intimate contact of the cracked surface, further reinforcing the rebonded portion. The amphiphilic structure proves to meet both the thermodynamic and kinetic requirements for autonomous rehabilitation. As a result, the unfavored water, which used to impede adhesion between hydrophobic polymeric materials, turns into a positive aid to crack healing. The mechanism involved is carefully analyzed and verified in terms of micro- and macroscopic techniques. The proposed operating environment-oriented design of the stimulus-responsive macromolecule may help to broaden the family of underwater self-healing polymers and their application scope.

20.
Macromol Rapid Commun ; 38(16)2017 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-28627040

RESUMO

The present communication reports a novel strategy to fabricate reversible shape-memory polymer that operates without the aid of external force on the basis of a two-phase structure design. The proof-of-concept material, crosslinked styrene-butadiene-styrene block copolymer (SBS, dispersed phase)/polycaprolactone-based polyurethane (PU, continuous phase) blend, possesses a closely connected microphase separation structure. That is, SBS phases are chemically bonded to crosslinked PU by means of a single crosslinking agent and two-step crosslinking process for increasing integrity of the system. Miscibility between components in the blend is no longer critical by taking advantage of the reactive blending technique. It is found that a suitable programming leads to compressed SBS, which serves as internal expansion stress provider as a result. The desired two-way shape-memory effect is realized by the joint action of the temperature-induced reversible opposite directional deformabilities of the crystalline phase of PU and compressed SBS, accompanying melting and orientated recrystallization of the former. Owing to the broadness of material selection and manufacturing convenience, the proposed approach opens an avenue toward mass production and application of the smart polymer.


Assuntos
Técnicas de Química Analítica , Polímeros/síntese química , Elastômeros , Fenômenos Mecânicos , Poliuretanos/química , Estirenos/química , Temperatura
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