Triblock Copolymers

The synthesis of high-molecular-weight ( M n up to 62,000 g/mol) polyesters has been achieved by acyclic diene metathesis (ADMET) polymerization of α,ω-dienes prepared from biobased bis(undec-10-enoate) and diols [ethylene glycol ( M1 ), propylene glycol ( M2 ), 1,9-nonanediol ( M3 ), 1,4-benzenedimethanol ( M4 ), and hydroquinone ( M5 )] using ruthenium-carbene catalysts. Replacement of the solvent during the ADMET polymerization was effective for obtainment of the high-molecular-weight polymers (expressed as P1 - P5 )...

Overexpression of epidermal growth factor receptor (EGFR) in cancer is a key cause of recurrence of cervical cancer (CC). Although the EGF-EGFR pathway has been studied for decades, preventing tumor growth and recurrence caused by peripheral EGF remains a great challenge. In this work, a strategy is proposed to reduce the stimulation of high concentration EGF on tumor growth by using a thermo-sensitive hydrogel. The hydrogel is a triblock copolymer composed of polyethylene glycol (PEG) and poly (lactide glycolide) (PLGA)...

A novel biodegradable amphiphilic triblock copolymer, PAEEP-PEG-PLLA(polyphosphate, polyethylene glycol, and polylactic acid), was synthesized by twice ring-opening polymerization and triphenylphosphine (TPP) was grafted onto the block copolymer to synthesize a carrier material (TPP-PAEEP-PEG-PLLA), which was identified by 1H-NMR spectroscopy. The TPP-PAEEP-PEG-PLLA nanoparticles encapsulated with ursolic acid were prepared by the emulsion-solvent evaporation method and characterized by dynamic light scattering...

The "von Neumann bottleneck" is a formidable challenge in conventional computing, driving exploration into artificial synapses. Organic semiconductor materials show promise but are hindered by issues such as poor adhesion and a high elastic modulus. Here, we combine polyisoindigo-bithiophene (PIID-2T) with grafted poly(dimethylsiloxane) (PDMS) to synthesize the triblock-conjugated polymer (PIID-2T-PDMS). The polymer exhibited substantial enhancements in adhesion (4.8-68.8 nN) and reductions in elastic modulus (1...

Polymer-drug conjugates (PDCs) provide possibilities for the development of multiresponsive drug delivery and release platforms utilized in cancer therapy. The delivery of Temozolomide (TMZ, a DNA methylation agent) by PDCs has been developed to improve TMZ stability under physiological conditions for the treatment of glioblastoma multiforme (GBM); however, with inefficient chemotherapeutic efficacy. In this work, we synthesized an amphiphilic triblock copolymer (P1-SNO) with four pendant functionalities, including (1) a TMZ intermediate (named MTIC) as a prodrug moiety, (2) a disulfide bond as a redox-responsive trigger to cage MTIC, (3) S-nitrosothiol as a light/heat-responsive donor of nitric oxide (NO), and (4) a poly(ethylene glycol) chain to enable self-assembly in aqueous media...

Biodegradable injectable polymer (IP) systems that form hydrogels in situ when injected into the body have considerable potential as medical materials. In this paper, we report a new two-solution mixed biodegradable IP system that utilizes the stereocomplex (SC) formation of poly(l-lactide) (PLLA) and poly(d-lactide) (PDLA). We synthesized triblock copolymers of PLLA and poly(ethylene glycol), PLLA- b -PEG- b -PLLA ( tri -L), and a graft copolymer of dextran (Dex) attached to a PDLA- b -PEG diblock copolymer, Dex-g-(PDLA- b -PEG) ( gb -D)...

It remains challenging to synthesize all-(meth)acrylic triblock thermoplastic elastomers (TPEs), due to the drastically different reactivities between the acrylates and methacrylates and inevitable occurrence of side reactions during polymerization of acrylates. By taking advantage of the easy structural modulation features of N-heterocyclic olefins (NHOs), we design and synthesize strong nucleophilic tetraphenylethylene-based NHOs varying in the number (i.e. mono-, dual- and tetra-) of initiating functional groups...

The multifaceted process of nerve regeneration following damage remains a significant clinical issue, due to the lack of a favorable regenerative microenvironment and insufficient endogenous biochemical signaling. However, the current nerve grafts have limitations in functionality, as they require a greater capacity to effectively regulate the intricate microenvironment associated with nerve regeneration. In this regard, we proposed the construction of a functional artificial scaffold based on a "two-pronged" approach...

The desalination performance of thin film nanocomposite (TFN) membranes is significantly influenced by the nature of nanofillers and the structure of the polyamide (PA) layer. Herein, a micelles regulated interfacial polymerization (MRIP) strategy is reported for the preparation of TFN membranes with enhanced nanofiltration (NF) performance. Specially, stable and ultrafine micelles, synthesized from the poly(ethylene oxide)-b-poly(4-vinyl pyridine)-b-polystyrene (PEO-PVP-PS) triblock copolymers, were utilized as regulators in the aqueous phase during the interfacial polymerization (IP) process...

We present an approximate analytical approach to the adsorption problem of ABA triblock copolymers confined between two parallel plates in a θ solvent and give the expression of the propagator q(x, t) as a piece-wise function by solving the modified diffusion equation. In this way, the role of separation between the two plates, adsorption energy and block lengths on segment concentration profile, chain conformations, and interaction potential is then investigated, which agrees well with the numerical results...

Drugs that form self-assembled supramolecular structures to be most-active is a promising way of creating new highly specific and active pharmaceuticals. Controlling the activity of bioactive supramolecular structures such as drug-loaded micelles is possible by both core/shell and inter-assembly cross-linking. However, if the flexibility of the assembly is mandatory for the activity cross-linking is not feasible. Thus, such structures cannot be manipulated in their activity. The present study demonstrates a novel concept to control the activity of not drug-releasing, non-cross-linked bioactive superstructures...

The degradation of (micro)gels and fractal aggregates based on self-assembled amphiphilic triblock copolymers has been investigated in water by confocal microscopy and light scattering respectively. The triblock copolymer consisted of a central hydrophilic poly(acrylic acid) (pAA) block and two hydrophobic end blocks that contained an equal amount of randomly distributed n -butyl acrylate ( n BA) and AA units. These latter units helped at tempering the hydrophobic end blocks resulting in the control and the fine tuning of the dynamics of the self-assembled triblock through the pH...

INTRODUCTION: Spatiotemporally controlled release of siRNA for anti-tumor therapy poses significant challenges. Near-infrared (NIR) light, known for its exceptional tissue penetration and minimal tissue invasiveness, holds promise as a viable exogenous stimulus for inducing controlled siRNA release in vivo. However, the majority of light-responsive chemical bonds exhibit absorption wavelengths in the ultraviolet (UV) or short-wavelength visible light range. METHODS: To achieve NIR-controlled siRNA release, the study synthesized a UV-sensitive triblock copolymer cRGD-poly(ethylene glycol)- b -poly(aspartic acid ester-5-(2'-(dimethylamino)ethoxy)-2-nitrobenzyl alcohol)- b -polyphenylalanine, abbreviated as cRGD-PEG-PAsp(EDONB)-PPHE...

HYPOTHESIS: There is a lack of understanding of the interplay between the copolymer composition profile and thermal transition observed in aqueous solutions of N-isopropyl acrylamide (NIPAM) copolymers, as well as the correlation between this transition and the formation and structure of copolymer self-assemblies. EXPERIMENTS: For this purpose, we investigated the response of five copolymers with the same molar mass and chemical composition, but with different composition profile in aqueous solution against temperature...

Fabrication of a biohybrid actuator requires muscle cells anisotropically aligned in a line, curve, or combination of lines and curves (similar to the microstructure of living muscle tissue) to replicate lifelike movements, in addition to considering the arrangement of skeletal structure or muscular structure with anisotropic straight patterns. Here, we report a UV laser-processed microstructure for freely directing cellular alignment to engineer a biohybrid actuator composed of poly(styrene- block -butadiene- block -styrene triblock copolymer) (SBS) thin film with tailor-made microgrooves (MGs) and skeletal myotubes aligned along these MGs...

It has been commonly believed that the ordered thermoplastic elastomers formed by the ABC triblock copolymer should have better mechanical performance than that by the ABA counterpart due to the higher bridging fraction. However, the thermoplastic elastomer of ABA was often observed to perform better than that of ABC. To compare the performance of two kinds of thermoplastic elastomers and unveil the underlying microscopic mechanism, we have calculated their stress-strain curves using coarse-grained molecular dynamics simulations in conjunction with self-consistent field theory...

Limb ischemia is a refractory disease characterized by persistent inflammation, insufficient angiogenesis, and tissue necrosis. Although mesenchymal stem cells (MSCs) have shown potential for treating limb ischemia, their therapeutic effects are limited by low engraftment rates. Therefore, developing an optimal MSC delivery system that enhances cell viability is imperative. Selenium, known for its cytoprotective properties in various cell types, offers a potential strategy to enhance therapeutic effect of MSCs...

Mesoporous honeycomb iron titanate using a sol-gel, evaporation-induced self-assembly method is synthesized. A triblock copolymer, F127, serves as a structure-directing agents, with iron chloride and titanium (IV) isopropoxide as inorganic precursors. The strong intermolecular force of attraction among urea, metal precursors, and polymer led to the formation of the mesoporous honeycomb structure. The study of physicochemical properties using different techniques reveals the formation of microstructures with a remarkable degree of porosity...

This study introduces a novel method that utilizes evolved gas analysis with time-of-flight mass spectrometry (EGA-TOFMS) coupled with principal component analysis (PCA) and Kendrick mass defect (KMD) analysis, called EGA-PCA-KMD, to analyze complex structural changes in polymer materials during thermo-oxidative degradation. While EGA-TOFMS captures exact mass data related to the degradation components in the temperature-dependent mass spectra of the evolved products, numerous high-resolution mass spectra with large amounts of ion signals and varying intensities provide challenges for interpretation...

pH-responsive micelles with positive charges are challenged by their significant effect on the cells/proteins and compromise their final fate due to electrostatic interactions. As one of the promising strategies, zwitterion incorporation in micelles has attracted considerable attention and displayed improved protein adsorption and blood circulation performances. However, previous reports in this field have been mostly limited in hemolysis for studying blood behaviour and lack a comprehensive understanding of their interactions with blood components...