Hui Zhao

Sichuan University | SCU · Department of Chemical Engineering

As gene therapy continues to evolve, the development of safe and effective cationic polymer carriers is critical. In this work, three polymers have been prepared by ring-opening polymerization on the basis of peptide-lipoic acid monomers. By adjusting the sequence of the peptides, redox-responsive cationic polymers with different positive charge nu...

Mimicking the non-equilibrium assemblies found in living systems driven by bioenergy, we presented a novel chemical fuel-driven transient 2D SOFs, formed via the redox reaction-driven transient self-assembly of tetraphenylene-based structural...

Chemical fuel-driven supramolecular systems have been developed showing out-of-equilibrium functions such as transient gelation and oscillations. However, these systems suffer from undesired waste accumulation and they function only in open systems. Herein, we report non-equilibrium supramolecular polymerizations in a closed system, which is built...

Post-polymerization modification of pendant-activated ester groups on polymer backbones is a versatile tool to obtain multifunctional water-soluble polymers that cannot be synthesized by typical methods of polymerization. For the first time, short-chain PEG functionalized hydroxybenzoic acid esters (PHBE) were employed to synthesize novel monomers...

Due to low activity and poor wettability of carbon fiber (CF), the interaction between CF and polyphenylene sulfide (PPS) matrix is weak, which decreases the mechanical properties of CF reinforced PPS （CF/PPS） composites. In this article, the interfacial adhesion of CF/PPS composites was strengthened by using a water-soluble poly (amic acid) ammoni...

Inspired by biofuel-driven dissipative self-assembly in nature, chemical fuel-driven supramolecular systems have been developed showing out-of-equilibrium functions such as transient gelation and oscillations. However, these systems suffer from undesired waste accumulation and they function only in open systems. Herein, we report non-equilibrium su...

Elastic materials based on biomass fiber reinforced natural rubber (NR) composites featured by renewability, environmental friendliness, and outstanding toughness have attracted intensive attention. However, the improvement in tensile strength via natural fiber reinforcement is always accompanied by the compromise in toughness, which is rooted in t...

Directional sensors endowed by inherent anisotropic structure have drawn great attention in intelligent sensing systems. Unidirectional lyophilization is the mainstream technique to architect anisotropic structure particularly for water dispersible systems as the ice template can be readily removed at the melting point of water (0 °C). However, it...

RAFT polymerization of 4-(dimethylamino)phenyl acrylate (MAPA) using 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl] pentanoic acid (CDTPA) as the chain transfer agent and AIBN as initiator yielded well-defined and narrowly distributed poly(4-(dimethylamino)phenyl acrylate) (PMAPA). As confirmed...

Metal halide perovskite quantum dots (QDs) hold great promise as building blocks for next-generation light emitting devices (LEDs). The preparation of perovskite QD films with high photoluminescence quantum yield (PLQY) is the key to realizing efficient LEDs. However, the conventional deposition method of spin-coating of pre-synthesized QD ink solu...

Pesticides have been always restricted by poor efficacy and inacceptable toxicity. In this work, a pH-sensitive controlled-release nano-capsule of fungicide, [email protected] (ZIF is a subclass of MOF), was prepared based on metal-organic framework (MOF) for higher antifungal effect and low bio-toxicity. The [email protected] was formed by physica...

The use of UV irradiation as a reaction stimulus provides a facile mean to obtain spatial and temporal control over polymer conjugation reactions. In this work, UV irradiation was used to induce an activated ester-amine conjugation of polymeric building blocks via photo-induced deprotection of an amine and subsequent reaction with an activated este...

In most synthetic nanoreactor systems, catalysed products do not promptly diffuse away from the nanoreactor, which leads to lower than expected catalytic efficiencies. To address the diffusion problem, transient polymer micelle nanoreactor systems were achieved using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) as the fuel and activated este...

The last decade has witnessed the exploration of exceptional optoelectronic and photovoltaic properties of perovskite solar cells (PSCs) at the laboratory scale. Unfortunately, their sensitivity to moisture causes bulk degradation, hindering the commercialization of PSC devices. Despite the numerous strategies that have been developed to date in th...

Organization of gold nanoobjects by oligonucleotides has resulted in many three‐dimensional colloidal assemblies with diverse size, shape, and complexity; nonetheless, autonomous and temporal control during formation remains challenging. In contrast, living systems temporally and spatially self‐regulate formation of functional structures by interna...

Golden ratio: Four‐dimensional gold (Au) nanostructures were fabricated by a dissipative assembly strategy. The dissipative character of the system was realized by utilizing deoxyribonucleic acid (DNA) as the fuel and exonuclease III (Exo III) as the energy‐dissipating unit, to generate AuNPs functionalized with short single‐stranded DNA oligonucle...

On the basis of the major application for block copolymers to use them as separation membranes, lithographic mask, and as templates, the preparation of highly oriented nanoporous thin films requires the selective removal of the minor phase from the pores. In the scope of this study, thin film of polystyrene-block-poly(ethylene oxide) block copolyme...

Four pyrene-functionalized polyacetylenes were designed and prepared through a typical post-polymerization modification route, which is the highly efficient reaction between activated ester and primary anime groups. The chemical structures of the resultant polymers were characterized with multiple spectroscopic techniques and the data indicated the...

Nickel-catalyzed cycloaddition of alkynes and 2-sulfobenzoic anhydrides gives highly functionalized thiochromenones. The reaction undergoes a deoxygenative rather than decarbonylative pathway and shows advantages of an excellent isolated yield (up to 95%), high reaction efficiency, and high regioselectivity. As one of the resulted products, 2,3-di(...

Transport at the molecular scale is a prerequisite for the development of future molecular factories. Here, we have designed oligoanionic molecular sliders on polycationic tracks that exploit Brownian motion and diffusive binding to transport cargo without using a chemical fuel. The presence of the polymer tracks increases the rate of bimolecular r...

Funktionelle Polymere lassen sich mithilfe der Willgerodt‐Kindler‐Reaktion direkt aus elementarem Schwefel bei Raumtemperatur herstellen. Dies eröffnet einen neuen Zugang zur Synthese und Anwendung von Polythioamiden und Polythioharnstoffen eröffnet.

Follow the yellow brick road: Functional polymers can be prepared directly at room temperature from elemental sulfur by the Willgerodt–Kindler reaction. This method opens a new synthetic door for the synthesis and application of polythioamides and polythioureas.

The compartmentalization of cell-free gene expression systems in liposomes provides an attractive route to the formation of protocells, but these models do not capture the physical (crowded) environment found in living systems. Here, we present a microfluidics-based route to produce monodisperse liposomes which can shrink almost three orders of mag...

Photocaged poly(N‐isopropyl acrylamide) (PNIPAM)s, copolymers consisting of N‐isopropyl acrylamide (NIPAM) and N‐isopropyl‐N‐(2‐nitrobenzyl) acrylamide, are prepared by free radical polymerization. Upon UV irradiation, the hydrophobic o‐nitrobenzyl group is cleaved, which subsequently releases the caged NH group and generates more hydrogen bonds wi...

Thermo-responsive and active functional fiber mats were prepared from random copolymer of poly(pentafluorophenyl acrylate-co-N-isopropylacrylamide) (P(PFPA-co-NIPAM)), which was synthesized by a controlled radical polymerization process based on reversible addition-fragmentation chain transfer (RAFT). As reactive sites, pentafluorophenyl ester (PFP...

Chitosan (CS) has been widely used as temporary mechanical supporter for the regeneration of bone, owing to its biocompatibility, biodegradability and versatility in orthopedic treatment. CS rod material is a promising candidate for internal fixation devices. However, the mechanical strength of existing CS rod materials is still unsatisfactory. In...

The chemical behaviour of molecules can be significantly modified by confinement to volumes comparable to the dimensions of the molecules. Although such confined spaces can be found in various nanostructured materials, such as zeolites, nanoporous organic frameworks and colloidal nanocrystal assemblies, the slow diffusion of molecules in and out of...

The ability to guide the assembly of nanosized objects reversibly with external stimuli, in particular light, is of fundamental importance, and it contributes to the development of applications as diverse as nanofabrication and controlled drug delivery. However, all the systems described to date are based on nanoparticles (NPs) that are inherently...

Highly ordered block copolymer thin films have been studied extensively during the last years because they afford versatile self assembled morphologies via a bottom-up approach. They promise to be used in applications such as polymeric membranes or templates for nanostructured materials. Among the block copolymer structures, perpendicular cylinders...

Precise control of the self-assembly of selected components within complex mixtures is a challenging goal whose realization is important for fabricating novel nanomaterials. Herein we show that by decorating the surfaces of metallic nanoparticles with differently substituted azobenzenes, it is possible to modulate the wavelength of light at which t...

Precise control of the self-assembly of selected components within complex mixtures is a challenging goal whose realization is important for fabricating novel nanomaterials. Herein we show that by decorating the surfaces of metallic nanoparticles with differently substituted azobenzenes, it is possible to modulate the wavelength of light at which t...

Poly(pentafluorophenyl acrylate)-block-poly(N-isopropylacrylamide) (PPFPA-b-PNIPAM) is synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Light-responsive moieties of ortho-nitrobenzyl (ONB)-protected diamine are partially introduced to the PFPA moieties via postpolymerization modification. The amphiphilic block...

Activated ester polymers, pioneered by Ferruti and Ringsdorf in the 1970s, are attractive polymeric materials because they can easily be converted into functional polymers by reacting with amine nucleophiles. In the present study, methyl salicylate acrylate, salicyl acrylate and tert.-butyl salicylate acrylate monomers were polymerized yielding thr...

Monosaccharide-functionalized poly(phenylacetylenes) (PPAs) are synthesized with high yield and molecular weight, but it shows no solvating power to multiwalled carbon nanotubes (MWCNTs) by simply blending them together. Polymerization of monosaccharide-functionalized monomers in the presence of MWCNTs (in situ polymerization) leads to the hybrids...

Hydroxyl-functionalized poly(propylene carbonate) (PPC) was synthesized by a zinc glutarate catalyst mediated terpolymerization of carbon dioxide (CO2), propylene oxide (PO), and 2-[[(2-nitrophenyl)methoxy]methyl]oxirane (monomer A). PPC with varying monomer A contents (0–10.6 mol %) were obtained and could be transformed into hydroxyl-functionaliz...

Polystyrene-block-poly(maleimide pentafluorophenyl ester-co-styrene)-block-poly(ethylene oxide) with an o-nitrobenzyl ester junction was synthesized by “one-step” RAFT polymerization. Highly ordered and locally reactive nanoporous thin films were obtained from the photocleavable triblock copolymer after spin coating, solvent annealing, UV exposure,...

The synthesis and characterization of a photocleavable block copolymer containing an ortho-nitrobenzyl (ONB) linker between poly(methyl methacrylate) and poly(d-lactide) blocks is presented here. The block copolymers were synthesized via atom transfer radical polymerization (ATRP) of MMA followed by ring-opening polymerization (ROP) of d-Lactide an...

A robust route for the preparation of nanoscopic line patterns from polystyrene-block-poly(ethylene oxide) featuring a photocleavable o-nitrobenzyl ester junction is demonstrated. After mild UV (λ = 365 nm) exposure and selective removal of the PEO microdomains, the polymer trench patterns are used as scaffold to fabricate highly ordered arrays of...

A series of poly(pentafluorophenyl (methyl)acrylates)-block-poly(ethylene oxide) with o-nitrobenzyl ester photocleavable junctions (PPFP(M)A-hv-PEO) were synthesized by RAFT polymerization. The block copolymers were used to fabricate thin films and fibers by spin-coating and electrospinning, respectively. After solvent annealing, UV exposure, and w...

A robust route for the preparation of nanoscopic dot/line patterns with long range lateral order from poly(styrene-block-ethylene oxide) (PS-b-PEO) with an o-nitrobenzyl ester junction (PS-hν-PEO) is demonstrated. Solvent annealing condition is optimized to achieve the highly ordered cylindrical block copolymer (BCP) microdomains oriented normal or...

Novel fluorescent organic soft porous crystals have been designed and prepared based on a multi-substituted silole bearing 1-phenyl-2,2-dicyanoethene moieties (molecule 8). 8 exhibited a series of emission colors, ranging from yellow to dark red with an over 70 nm shift of emission maximum. Molecule 8 also showed the ability to reversibly switch be...

Polymers featuring photolabile groups are the subject of intense research because they allow the alteration of polymer properties simply by irradiation. In particular, the o-nitrobenzyl group (o-NB) is utilized frequently in polymer and materials science. This Perspective pays particular attention to the increasing utilization of this chemical grou...

Three dimethyltetraphenylsiloles (DMTPSs) symmetrically substituted on their 2,5-positions with electron-accepting (A), i.e. aldehyde (ALD) and dicyanovinyl (DCV) or donating (D), i.e. diphenylamine (DPA) moieties were designed and synthesized via facile reaction procedures. The propeller-shaped luminogens exhibit aggregation-induced/enhanced emiss...

Copolymers featuring pentafuorophenyl ester and o-nitrobenzyl (ONB) protected amine moieties have been prepared. Upon UV irradiation, the ONB protected amine group was released, which subsequently induced a crosslinking by a spontaneous reaction with pentafluorophenyl esters, resulting in stable, reactive patterned thin films. Remaining esters were...

We demonstrate a facile synthetic route to functional disubstituted polyacetylenes bearing highly polar groups based on polymer reactions. A pentafluorophenyl (PFP) ester-containing diphenylacetylene was designed and polymerized to obtain PFP activated ester-functionalized disubstituted polyacetylene (P1). P1 was used as a parent polymer to further...

Functional poly(phenylacetylene)s (PPAs) bearing different azobenzene pendants were synthesized in desirable yields and molecular weight by using organorhodium complexes [Rh(diene)Cl]2 as catalysts. The structure of the derived azobenzene-functionalized PPAs was characterized by NMR, IR, and UV spectroscopic techniques. Their photoinduced isomeriza...

Suspensions containing quaternized poly(pyridylacetylene) (PPyA) and AgX (X = Br and I) were obtained by simply mixingPPyA with water soluble silver salts. The suspensions were stable in the dark at room temperature, and could be cast into uniform films. After exposure to UV-light for sufficient time, Agnanoparticles were in situ generated in the p...

Pentafluorophenyl (PFP) ester-functionalized poly(phenylacetylene)s (PPAs, P1, P2, and P3) were designed and synthesized in desirable yields and molecular weight by using organorhodium complexes as catalysts. Furthermore, these PFP-containing PPAs were used as precursors to prepare a series of mono- and dual-functionalized PPAs by the substitution...

Poly(styrene-block-ethylene oxide) with an o-nitrobenzyl ester photocleavable junction (PS-hν-PEO) was synthesized by a combined RAFT polymerization and “click chemistry“ approach and represents the first report utilizing this method for the synthesis of photocleavable block copolymers. After solvent annealing, highly ordered thin films were prepar...

Chitosan (CS) rods are a good candidate as temporary mechanical supports in bone regeneration, however the bending strength and bending modulus should be improved to match commercially available devices used for bone fracture internal fixation. Poly(p-amino-phenylacetylene)/multi-walled carbon nanotubes (PaPA/MWCNTs) hybrids with superparamagnetic...

Functional polyacetylenes containing pyridinium side groups (PPyA-MX, X = Br and I) were successfully synthesized. Spectroscopic techniques such as 1H-NMR, 13C-NMR, and FTIR spectroscopy were used to characterize the structure of the obtained polymers. The characterization data were well consistent with the expected macromolecular structures. PPyA-...

Phosphorescence has rarely been observed in pure organic chromophore systems at room temperature. We herein report efficient phosphorescence from the crystals of benzophenone and its derivatives with a general formula of (X-C6H4)2C═O (X = F, Cl, Br) as well as methyl 4-bromobenzoate and 4,4′-dibromobiphenyl under ambient conditions. These luminogen...

Phenylacetylene and 1-pentyne derivatives containing aminated tetraphenylethene (TPE) units 1 and 2 are synthesized. The TPE-functionalized luminogens are nonemissive in dilute solutions but luminescent as solid aggregates, showing a novel behavior of aggregation-induced emission (AIE). The monomers are polymerized to their corresponding polymers P...

Disubstituted polyacetylenes are fluorescent polymers, and they are more stable than their monosubstituted counterparts. In comparison with the reports about those monosubstituted polyacetylenes, there is only one example showing the dispersing effects of disubstituted polycetylenes on carbon nanotubes. In this letter we demonstrated the fabricatio...

Phenylacetylene derivatives containing carbazole (1) and fluorene (2) moieties were polymerized by [Rh(nbd)Cl]2 into corresponding polymers P1 and P2 of high molecular weights (Mw ∼ 150 × 103–465 × 103) in high yields (up to 98%). The polymers were characterized by NMR, IR, UV, PL, and CV techniques. Hybrids of the polymers with multiwalled carbon...

Polymerization of a phenylacetylene monomer bearing a dendron moiety was carried out by using a rhodium complex Rh[(nbd)Cl2]2 as catalyst. The structure of the resultant was characterized with infrared (IR), nuclear magnetic resonance ( NMR ) , and UV-Visible absorption spectroscopic techniques ; the experimental data confirmed the generation of th...

Regioselective 1,3-dipolar polycycloadditions of tetraphenylethene (TPE)-containing diazides 1–3 and bis(aroylacetylene) 4 are initiated by simple heating, affording poly(aroyltriazole)s (PATAs) PI–PIII with high molecular weights in high yields. The PATAs are completely soluble in common organic solvents and stable at temperatures up to 358 °C. Th...

We report a fluorescence “turn-on” method to detect the critical micelle concentration (CMC) of surfactants. This method works well for both cationic and anionic surfactants. It employs an unprecedented mechanism (aggregation-induced emission, or AIE) to determine the CMC values, and the results are consistent with the data obtained by the classica...

Tetraphenylethene (TPE)-containing polytriazoles (P3) with high molecular weights in high yields was synthesized by the Cu(I)-catalyzed click polymerization of diyne with diazides. The diyne and diazide monomers, namely 1,4-bis(propargyloxy) benzene (1), 1,2-bis[4-(azidohexyloxy)phenyl]-1,2- diphenylethene (2a), and 1,2-bis[(4-azidomethyl)phenyl]-1...

Acetylenic monomers containing highly polar functional groups, especially those with active hydrogen atoms, have been difficult to polymerize because their toxic interactions with transition metal complexes deactivate catalyst systems. In this work, we succeeded in direct polymerizations of a series of highly polar phenylacetylene derivatives. The...

A group of triphenylamine-functionalized polyacetylenes (TPA-PAs) were synthesized using [Rh(nbd)Cl]2 as catalyst in high yields (up to 93%). The polymers were characterized by NMR, IR, UV, PL, and CV analyses. The TPA pendants endowed the polymers with desirable redox activity and high photoconductivity. When an electron-withdrawing formyl group w...

4-[3-(1-Pyrenyl)propylcarbonyloxy]-1-butyne (PyB) and 4-ferrocenylcarbonyloxy-1-butyne (FcB) were effectively polymerized by zwitterionic rhodium complex Rh+(nbd)[C6H5B-(C6H5)3], giving corresponding polymers PPyB and PFcB with high molecular weights (Mw up to 33300) in high yields (up to 83%). The polymers are excellent solvating agents in making...