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Anisotropic thermally conductive composites are very critical for precise thermal management of electronic devices. In this work, in order to prepare a composite with significant anisotropic thermal conductivity, polyamide 12/styrene–acrylic copolymer–boron nitride (PA12/SA–BN) composites with macro and micro double anisotropic structures were fabricated successfully using 3D printing and micro-shear methods. The morphologies and thermally conductive properties of composites were systematically characterized via SEM, XRD, and the laser flash method. Experimental results indicate that the through-plane thermal conductivity of the composite is 4.2 W/(m·K) with only 21.4 wt% BN, which is five times higher than that of the composite with randomly oriented BN. Simulation results show that the macro-anisotropic structure of the composite (caused by the selective distribution of BN) as well as the micro-anisotropic structure (caused by the orientation structure of BN) both play critical roles in spreading heat along the specified direction. Therefore, as-obtained composites with double anisotropic structures possess great potential for the application inefficient and controllable thermal management in various fields.

Approaches to achieve stable perovskite nanocrystals (PNCs) of interest, in particular those with large structural anisotropy, through protective coating of the inorganic shell at a single-nanocrystal (NC) level are comparatively few and limited in scope. Reported here is a robust amphiphilic-diblock-copolymer-enabled strategy for crafting highly-stable anisotropic CsPbBr3 nanosheets (NSs) by in situ formation of a uniform inorganic shell (1st shielding) that is intimately ligated with hydrophobic polymers (2nd shielding). The dual-protected NSs display an array of remarkable stabilities (i.e., thermal, photostability, moisture, polar solvent, aliphatic amine, etc.) and find application in white-light-emitting diodes. In principle, by anchoring other multidentate amphiphilic polymer ligands on the surface of PNCs, followed by templated-growth of shell materials of interest, a rich variety of dual-shelled, multifunctional PNCs with markedly improved stabilities can be created for use in optics, optoelectronics, and sensory devices.

Background Although pH and redox sensitiveness have been extensively investigated to improve therapeutic efficiency, the effect of disulfide bonds location and pH-triggered charge-reversal on cascade-targeting still need to be further evaluated in cancer treatment with multi-responsive nanoparticles. Purpose The aim of this study was to design multi-responsive DOX@MSNs-COS-NN-CMC, DOX@MSNs-COS-SS-CMC and DOX@MSNs-COS-CMC-SS and systematically investigate the effects of disulfide bonds location and charge-reversal on the cancer cell specificity, endocytosis mechanisms and antitumor efficiency. Results In vitro drug release rate of DOX@MSNs-COS-SS-CMC in tumor environments was 7-fold higher than that under normal physiological conditions after 200 h. Furthermore, the fluorescence intensity of DOX@MSNs-COS-SS-CMC and DOX@MSNs-COS-CMC-SS was 1.9-fold and 1.3-fold higher than free DOX at pH 6.5 and 10 mM GSH. In addition, vesicular transport might be a factor that affects the uptake efficiency of DOX@MSNs-COS-SS-CMC and DOX@MSNs-COS-CMC-SS. The clathrin-mediated endocytosis and endosomal escape of DOX@MSNs-COS-SS-CMC enhanced cellular internalization and preserved highly controllable drug release into the perinuclear of HeLa cells. DOX@MSNs-COS-SS-CMC exhibited a synergistic chemotherapy in preeminent tumor inhibition and less side effects of cardiotoxicity. Conclusion The cascade-targeting of charge-reversal and disulfide bonds shielding would be a highly personalized strategy for cervical cancer treatment.

A novel raspberry-like γ-Fe2O3@carbon dot (CD) nanocatalyst was prepared and applied for photoinduced electron transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization. The nanocatalyst was found to be an efficient photocatalyst in visible light-regulated PET-RAFT polymerization owing to the oxidative quenching mechanism between the photoexcited γ-Fe2O3@CDs and the RAFT agent in the PET process. Notably, polymerization can be reversibly ceased in the absence of light or under an external magnetic field. The superparamagnetic nature and high saturation magnetization value (∼30.4 emu g−1) of the nanocatalyst contribute to convenient recycling of the nanocatalyst after polymerization. The PET-RAFT polymerization with the nanocatalyst before and after recycling was investigated, which displayed all the characteristics of controlled/living polymerization systems.

An unconventional but facile approach to prepare size-tunable core/shell ferroelectric/polymeric nanoparticles with uniform distribution is achieved by metal-free atom transfer radical polymerization (ATRP) driven by visible light under ambient temperature based on novel hyperbranched aromatic polyamides (HBPA) as a functional matrix. Cubic BaTiO3/HBPA nanocomposites can be prepared by in-situ polycondensation process with precursors (barium hydroxide (Ba(OH)2) and titanium(IV) tetraisopropoxide (TTIP)) of ferroelectric BaTiO3 nanocrystals, because precursors can be selectively loaded into the domain containing the benzimidazole rings. At 1200 °C, the aromatic polyamide coating of cubic BaTiO3 nanoparticles are carbonized to form carbon layer in the inert environment, which prevents regular nanoparticles from gathering. In addition, cubic BaTiO3 nanoparticles are simultaneously transformed into tetragonal BaTiO3 nanocrystals after high temperature calcination (1200 °C). The outer carbon shell of tetragonal BaTiO3 nanoparticles is removed via 500 °C calcination in air. Bi-functional ligand can modify the surface of tetragonal BaTiO3 nanoparticles. PMMA polymeric chains are growing from the initiating sites of ferroelectric BaTiO3 nanocrystal surface via the metal-free ATRP technique to obtain core/shell ferroelectric BaTiO3/PMMA hybrid nanoparticles. Changing the molar ratio between benzimidazole ring units and precursors can tune the size of ferroelectric BaTiO3 nanoparticles in the process of polycondensation, and the thickness of polymeric shell can be tailored by changing the white LED irradiation time in the organocatalyzed ATRP process. The dielectric properties of core/shell BaTiO3/PMMA hybrid nanoparticles can be also tuned by adjusting the dimension of BaTiO3 core and the molecular weight of PMMA shell.

In this study, Nb2O5 nanorods/graphene composites (NbO NRs/GR) are prepared by one-pot alkaline hydrothermal process, utilizing the new roles of graphene oxide (GO) as the structure-directing and morphology-controlling agent for the growth of NbO NRs. Compared to blank NbO, NbO/GR composites exhibit significantly improved photocatalytic activity for 4-CP degradation under visible-light irradiation, although 4-CP and NbO do not absorb visible light themselves. The in-situ formation of surface complexes between 4-CP and NbO and the subsequent charge transfer based on LMCT mechanism can be responsible for the visible photocatalytic activity. And meanwhile, the photoelectrons transferred to GR surface from in-situ formed complex (NbO/4-CP) via NbO NRs can initiate the synergistic Cr(VI) reduction. The GR contents and NbO crystalline phase have great effects on the photocatalytic activity of NbO/GR composites toward simultaneous 4-CP degradation and Cr(VI) reduction. The amorphous NbO/GR composite with 4.0 wt% GR (NbO-400/GR-4.0%) shows the highest photocatalytic activity. The influences of various experimental conditions (including the surface fluorination of NbO/GR, the initial concentrations of 4-CP and Cr(VI), pH, reaction atmosphere, and adding radical scavengers) on the visible photocatalytic activities are investigated in detail. According to the catalytic activity, UV-vis DRS and FT-IR spectra of NbO/4-CP or NbO/GR/4-CP, and photocurrent response in aqueous 4-CP solution, the formation of the surface complex is evidenced and the visible-light catalytic mechanism based on LMCT process is proposed.

Multi-stimuli responsive fluorescence probe could pave the way for monitoring more complex environmental changes. Here we prepared multifunctional nanoparticle Fe3O4@SiO2@P(DMAEMA-co-TPEE), which displayed yolk-shell morphology with well-defined polymer brush. With superparamagnetic Fe3O4 component and pH/temperature dual sensitive PDMAEMA polymer brush, the as prepared nanoparticles (YS-NPs) exhibited as multi-stimuli responsive fluorescence probe for real-time visual monitoring of environmental changes such as magnetic field, temperature and pH. Such YS-NPs could also be applied as a sensitive detector for CO2 in aqueous solution. Notably, the solution of YS-NPs showed high colloidal stability during the environmental changes, and surface aggregation-induced emission (S-AIE) was proposed for the aggregation of TPE residue on the surface of YS-NPs.

Background Although pH and redox sensitiveness have been extensively investigated to improve therapeutic efficiency, the effect of disulfide bonds location and pH-triggered charge-reversal on cascade-targeting still need to be further evaluated in cancer treatment with multi-responsive nanoparticles. Purpose The aim of this study was to design multi-responsive DOX@MSNs-COS-NN-CMC, DOX@MSNs-COS-SS-CMC and DOX@MSNs-COS-CMC-SS and systematically investigate the effects of disulfide bonds location and charge-reversal on the cancer cell specificity, endocytosis mechanisms and antitumor efficiency. Results In vitro drug release rate of DOX@MSNs-COS-SS-CMC in tumor environments was 7-fold higher than that under normal physiological conditions after 200 h. Furthermore, the fluorescence intensity of DOX@MSNs-COS-SS-CMC and DOX@MSNs-COS-CMC-SS was 1.9-fold and 1.3-fold higher than free DOX at pH 6.5 and 10 mM GSH. In addition, vesicular transport might be a factor that affects the uptake efficiency of DOX@MSNs-COS-SS-CMC and DOX@MSNs-COS-CMC-SS. The clathrin-mediated endocytosis and endosomal escape of DOX@MSNs-COS-SS-CMC enhanced cellular internalization and preserved highly controllable drug release into the perinuclear of HeLa cells. DOX@MSNs-COS-SS-CMC exhibited a synergistic chemotherapy in preeminent tumor inhibition and less side effects of cardiotoxicity. Conclusion The cascade-targeting of charge-reversal and disulfide bonds shielding would be a highly personalized strategy for cervical cancer treatment.

The combination of piezoelectric material and ball milling leads to new frontiers in catalysis research. Here we used piezoelectric BaTiO3 nanoparticles as the additive for the degradation of dye pollutant in solid state in ball milling process. With the assistant of ppm level CuBr2 and H2O2, high degradation conversion (>99%) of dyes can be achieved in short time (10 min). BaTiO3 nanoparticles became temporarily highly polarized particles during BM process and generated electron-hole. These particles exhibited strong reducing properties and reduced Cu(II) into the active Cu(I) species which can catalyze H2O2 to generate highly active ·O2– to enhance the dye degradation. In addition to the general applicability for different dyes and larger scales, this BaTiO3 assist BM process was deduced to be a promising powerful platform for organic pollutant treatment in solid states.

A facile fabrication strategy of transparent and upconversion photoluminescent nylon 6 (PA6) nanofiber mats was developed based on PA6 nanofiber mats, carboxylic acid-functionalized upconversion nanoparticles (UCNP-COOH), and poly(methyl methacrylate) (PMMA) solution. UCNP-COOH were prepared by a solvothermal method, followed by the ligand exchange process. The electrospinning method and the spin-coating process were employed to combine PA6 nanofiber mats with UCNP-COOH and PMMA to introduce upconversion photoluminescent properties and transparency into the nanocomposite mats, respectively. The prepared UCNP-COOH/PA6/PMMA nanofiber mats are transparent and exhibit green emission, which are similar to UCNP-COOH when they were excited under 980 nm laser. The upconversion luminescent intensity of the functional nanofiber mats can be tailored by adjusting the weight fraction of UCNP-COOH as fillers. This facile strategy can be readily used to other types of intriguing nanocomposites for diverse applications.

In this work, we have explored a simple and facile approach to prepare optically active helical polyamides. The hydroxyl groups of l-TA and d-TA were protected by O-alkoyl ester, and the resulting enantiomers, l-2,3-di-O-acetyl-tartaric acid (l-ATA) and d-2,3-di-O-acetyl-tartaric acid (d-ATA) crystals, were obtained. A pair of aliphatic homochiral polyamides of PA-l and PA-d are prepared using l-ATA, d-ATA, and achiral 1,11-undecanediamine as building blocks via interfacial polycondensation. PA-l and PA-d display negative and positive mirror circular dichroism (CD) spectra images in both solution and solid state. Moreover, the polyamides in solid state display different CD signals and stronger optical activity compared to those in ethanol and even the related chiral monomers in solid state, which was due to the helical conformation of the polyamides in solid state. Scanning electron microscopy results indicated that the aggregations of PA-l express left-handed helical sense, whereas those of PA-d express right-handed helix. In addition, the induced CD signals from the chiral conformation of the backbone become weaker when increasing the temperature from 0 to 60 °C in dilute solution. Either of the polyamides displays relatively stable CD images in solid state when elevating the temperature from 0 to 90 °C.

Aiming at dissipating the undesired heat generated by the electronic devises during working process to the outside through a controllable way without affecting other adjacent components, novel polyamide 12 (PA12) based template composites with selectively distributed boron nitride (BN) have been explored successfully by simple and effective 3D printing technology coupled with roller-rolling method. The morphological structure, thermally conductive property as well as thermally conductive mechanism of the template composite were investigated systematically. The improved template composites showed significant localized and unidirectional thermally conductive property. And the through-plane thermal conductivity of the template composite can reach as high as 4.26 W/(m·K) with the BN content of 33.5 wt%, which is over 3 times that of the isotropic composite with the same BN content. Both of the experiment and simulated results revealed that the significantly enhanced thermally conductive property for the composites was attributed to the selectively distributed BN, which is beneficial to realize precise and controllable heat dissipation. This study sheds light on the rational design and fabrication of the high-efficiency composites with localized and unidirectional thermally conductive property for the application of thermal management system of the high-frequency and high-speed electronic devices.

A series of PA1111/BaTiO3 nanocomposites with different BaTiO3 contents are prepared by the in-situ salification-melt polymerization procedure. The morphological, spectroscopic studies and the property characterization are conducted. The results indicate that the proposed in-situ compositing method can effectively disperse BaTiO3 nanoparticles in PA1111 matrix, and the as-prepared nanocomposites exhibit improved dielectric and piezoelectric properties as BaTiO3 content up. For the nanocomposite with 10 wt% BaTiO3, compared with that of neat PA1111, d33 and g33 is increased by 1.6 and 1.4 times, respectively. The nanocomposites prepared by the in-situ procedure present high piezoelectricity enhancement efficiency, which is attributed to the uniform particle dispersion in the matrix endowed by the secondary interaction between the organic and inorganic components. This work not only helps broaden the application field of PA1111, but also provides a facile energy-saving and modifier-free compositing procedure for the preparation of the uniform polymer-based nanocomposites.

With the increasing demand for detection accuracy and sensitivity, dual‐band polarimetric image sensor has attracted considerable attention due to better object recognition by processing signals from diverse wavebands. However, the widespread use of polarimetric sensors is still limited by high noise, narrow photoresponse range, and low linearly dichroic ratio. Recently, the low‐dimensional materials with intrinsic in‐plane anisotropy structure exhibit the great potential to realize direct polarized photodetection. Here, strong anisotropy of 1D layered bismuth sulfide (Bi2S3) is demonstrated experimentally and theoretically. The Bi2S3 photodetector exhibits excellent device performance, which enables high photoresponsivity (32 A W−1), Ion/Ioff ratio (1.08 × 104), robust linearly dichroic ratio (1.9), and Hooge parameter (2.0 × 10−5 at 1 Hz) which refer to lower noise than most reported low‐dimensional materials‐based devices. Impressively, such Bi2S3 nanowire exhibits a good broadband photoresponse, ranging from ultraviolet (360 nm) to short‐wave infrared (1064 nm). Direct polarimetric imaging is implemented at the wavelengths of 532 and 808 nm. With these remarkable features, the 1D Bi2S3 nanowires show great potential for direct dual‐band polarimetric image sensors without using any external optical polarizer.

Cost-effective and green separation of aromatic pollutant from waste water is of great importance in sustainable chemistry and engineering but under challenges of high energy consumption and unsatisfactory separation efficiency. Herein, induced by the electrostatic interactions, lignosulfonate (LS) based superparamagnetic composite LS@γ-Fe2O3 was developed without any surface modification and activation process. The LS@γ-Fe2O3 magnetic composites exhibited meaningful amphiphilicity and then were applied as efficient material for the separation of toluene/water system through the combination of gravity filtration and magnetic demulsification methods. The results demonstrated that the composites exhibited an excellent separation rate (over 99.05 %) towards toluene/water with gravity filtration method. For the water with low toluene content (

Despite impressive recent advances in the synthesis of lead chalcogenide solid nanoparticles, there are no examples of lead chalcogenide hollow nanoparticles (HNPs) with controlled diameter and shell thickness as current synthetic approaches for HNPs have inherent limitations associated with their complexity, inability to precisely control the dimensions, and limited possibilities with regard to applicable materials. Herein, we report on an unconventional strategy for crafting uniform lead chalcogenide (PbS and PbTe) HNPs with tailorable size, surface chemistry, and near-IR absorption. Amphiphilic star-like triblock copolymers [polystyrene-block-poly(acrylic acid)-block-polystyrene and polystyrene-block-poly(acrylic acid)-block-poly(3,4-ethylenedioxythiophene)] were rationally synthesized and exploited as nanoreactors for the formation of uniform PbS and PbTe HNPs. Compared to their solid counterparts, the near-IR absorption of the HNPs is blue-shifted owing to the hollow interior. This strategy can be readily extended to other types of intriguing low-band-gap HNPs for diverse applications.

A facile route to fabricate size-tunable superparamagnetic/polymeric core/shell nanoparticles with uniform distribution was introduced based on metal-free atom transfer radical polymerization at ambient temperature.

An unconventional but robust strategy to fabricate uniform hybrid inorganic–organic core–shell superparamagnetic magnetite (Fe3O4) colloidal nanoclusters in situ was introduced based on water-soluble multi-arm star-shaped brush-like block copolymers as multifunctional polymeric nanoreactors, composed of poly(ethylene oxide) (PEO) as the main chain, poly(acrylic acid) (PAA) as functional graft chains, and the second PEO block as a shell (i.e., multi-arm star-shaped brush-like block copolymer [(PEO-g-PAA)-b-PEO]18) with different molecular weights and grafting densities. FeCl3 and FeCl2 as precursors of Fe3O4 were loaded into the graft chain PAA template domain of a multi-arm star-shaped brush-like block copolymer [(PEO-g-PAA)-b-PEO]18 polymeric nanoreactors, followed by an in situ reaction to form Fe3O4 nanoclusters. The dimensions of the clusters can be tuned precisely by changing the chain lengths of the PEO backbones of the PAA grafting region. In addition, the density of the subunits can also be tailored by adjusting grafting density of the PAA side chains, determined by the molar ratio of ethoxyethyl glycidyl ether (EEGE) to EO during the anionic copolymerization. The Fe3O4 colloidal nanocrystal clusters with superparamagnetic behavior at room temperature are highly water-dispersed because of the hydrophilic ligands of the surface-tethered PEO polymer shell.

An unconventional but robust route to fabricate highly pure α-Al2O3 colloidal nanocrystals with tunable surface chemistry and dimensions was introduced based on semi-aromatic polyamide (PA6Py) with pyridine rings as a functional matrix. The surface ligands of α-Al2O3 nanocrystals can be tuned by choosing different carboxyl-terminated polymers (e.g., PS and PEO).

Although polyamide-co-polyether, the most important co-polyamide species, has achieved big success, the inadequate biocompatibility still restricts it further application in biomedical area. In this paper, polydimethylsiloxane (PDMS) segment is introduced into copolymer to replace polyether segment, which is intended to fulfill the copolymer with improved surface performance. Two prepolymer condensation process was used to synthesis the novel PA1212-b-PDMS series, which is constructed by PDMS flexible segment (Mn = 1000 g/mol) and PA1212 rigid segment (Mn = 1000, 3000, 5000, 7000, 10,000 g/mol). FTIR and 1H NMR were carried out to evidence the success of the copolymerization and verify the chemical structure. Melting and crystallization behavior, thermal stability, and crystal structure of the series were characterized by DSC, TG and XRD, respectively. To explore the potential usage of the copolymers, mechanical properties were thoroughly investigated. The series possess tunable toughness and rigidity corresponding to different chain compositions. When Mn of PA1212 segment is above 5000 g/mol, the copolymer presents typical tough and stiff feature with an ultimate elongation rate of around 500% and a fair tensile strength around 35 MPa. More than that, the platelet adhesion and activation test was conducted to estimate the biocompatibility of the polymers. The contact angel goniometry and XPS were further utilized to understand their surface performance. The as-prepared copolymers give distinct-different performance from homo-polyamide and polyamide-co-polyether. Barely cell adhesion on the surface indicates the greatly improved biocompatibility achieved by the series, which promises the mechanical-property-adjustable novel co-polyamide a broad prospect in biomedical area.

Photo-induced metal free ATRP method was employed for the synthesis of star-shaped polymers. By using 21-Br-β-CD as the macroinitiator, 10-phenylphenothiazine as the photoredox catalyst, star-shaped PtBA homopolymers were synthesized. The photo-induced ATRP displayed all the characteristics of controlled/living polymerization systems and the good light control over the polymerization process. The successful chain extension with MMA demonstrated the high livingness of PtBA “arms” and good controllability of the Photo-induced metal free ATRP. Finally, the achieved PtBA-b-PMMA star-shaped copolymers were used as templates for the preparation of precisely size-tunable CdSe quantum dots after a simple hydrolyzing process.

Based on the electrostatic interaction, prepared γ-Fe2O3 nanoparticles with high positive charges (+ 45 mv) were modified by negative charged ligninsulfonate (LS, - 34 mv) to synthensize LS/γ-Fe2O3 composite. LS is low-price, environmentally friendly and renewable biomacromolecule. The LS/γ-Fe2O3 composite were applied in a Pickering miniemulsion polymerization as the only stabilizer, without any auxiliary comonomers and surfactants. The surface anchored γ-Fe2O3 induced the formation of strawberry-like hybrid latex particles who were endowed with superparamagnetic functional properties. Furthermore, the effect of the ratios of LS to γ-Fe2O3 on the stability of the LS/γ-Fe2O3 composites was investigated. The content of γ-Fe2O3 in the LS/γ-Fe2O3 composites should be lower than 66.7 wt%, or the stability of the Pickering miniemulsion polymerization would be destroyed, owing to the charge neutralization behavior of the LS and γ-Fe2O3. Within this range, the latex particle size increased with the increasing of γ-Fe2O3 content.

Organic-inorganic nanocomposites composed of polymers and nanoparticles offer a vast design space of potential material properties, depending heavily on the properties of these two constituents and their spatial arrangement. The ability to place polymers in direct contact with functional nanoparticles via strong bonding, that is, stable chemical interaction without the dissociation of surface capping polymers, provides a means of preventing nanoparticles from aggregation and increasing their dispersibility in nanocomposites, and promises opportunities to explore new properties and construction of miniaturized devices. However, this is still a challenging issue and has not yet been largely explored. Here, we report an unconventional strategy to create in situ organic-inorganic nanocomposites comprising monodisperse ferroelectric nanoparticles directly and permanently tethered with ferroelectric polymers by capitalizing on rationally designed amphiphilic star-like diblock copolymer as nanoreactors. The diameter of ferroelectric nanoparticles and the chain length of ferroelectric polymers can be precisely tuned. The dielectric and ferroelectric properties of nanocomposites containing different sizes of ferroelectric nanoparticles were scrutinized. Such bottom-up crafting of intimate organic-inorganic nanocomposites offers new levels of tailorability to nanostructured materials and promises new opportunities for achieving exquisite control over the surface chemistry and properties of nanocomposites with engineered functionality for diverse applications in energy conversion and storage, catalysis, electronics, nanotechnology, and biotechnology.

Atom transfer radical polymerization (ATRP) of 4-vinylpyridine, t-butyl acrylate, and styrene in sequential order from a β-cyclodextrin core yielded an amphiphilic star-like triblock copolymer, poly(4-vinylpyridine)-block-poly(t-butyl acrylate)-block-polystyrene (P4VP-b-PtBA-b-PS). Subsequently, star-like triblock copolymer composed of inner hydrophilic P4VP blocks, central hydrophobic PtBA blocks, and outer hydrophobic PS blocks with well-defined molecular architecture and molecular weight of each block was judiciously exploited as nanoreactor for synthesis of precisely shaped hairy plasmonic/semiconductor Au/TiO2 core/shell nanoparticles. The resulting Au/TiO2 nanoparticles were intimately and permanently tethered with outer PS chains that enabled the superior solubility of nanoparticles in nonpolar solvents. The PS chains on the surface of these bifunctional nanoparticles were carbonized by annealing in an inert atmosphere (i.e., yielding carbon-coated Au/TiO2 nanoparticles). In comparison to a widely ...

A series of novel water-soluble multi-arm star-shaped brush-like block copolymers, composed of poly(ethylene oxide) (PEO) as the main chain, poly(acrylic acid) (PAA) as functional graft chains, and a second PEO block as the shell (i.e., multi-arm star-shaped brush-like block copolymer (PEO-g-PAA)-b-PEO) with different molecular weights and grafting density, were rationally designed and synthesized by a combination of anionic copolymerization and atom transfer radical polymerization (ATRP). The anionic ring-opening copolymerization of ethylene oxide (EO) and ethoxyethyl glycidyl ether (EEGE) was conducted first by using α-cyclodextrin (α-CD) with 18 hydroxyl groups and diphenylmethyl sodium (DPMNa) as co-initiator system. The monomer reactivity ratios for EO and EEGE were also determined: r1(EO) = 1.18 ± 0.03 and r2(EEGE) = 0.79 ± 0.01, respectively. Then the resulting multi-arm star-shaped copolymers of poly(EO-co-EEGE) with hydroxyls as end functional groups were utilized as star-shaped macroinitiators to sequentially initiate the anionic ring-opening polymerization of monomer EO for the second block hydrophilic homopolymer PEO chain grown on the first block poly(EO-co-EEGE) arm end, and then the ethoxyethyl groups of the star-shaped block copolymers of poly(EO-co-EEGE)-b-PEO obtained were removed by hydrolysis. The formed multi-arm star-shaped block copolymers of EO and glycidol (Gly) with multi-pendant hydroxymethyls (star-shaped block copolymer poly(EO-co-Gly)-b-PEO) were then esterified by the reaction of the pendant hydroxyl groups of glycidol units of copolymers with 2-bromoisobutyryl bromide, and the resulting star-shaped brush-like macroinitiators were used to initiate the grafting polymerization of t-butyl acrylate (tBA) by ATRP technique. Finally, the tert-butyl ester groups of PtBA grafting side chains were selectively hydrolyzed in trifluoroacetic acid ​(TFA) to obtain the water-soluble multi-arm star-shaped brush-like block copolymer (PEO-g-PAA)-b-PEO. The water-soluble star-shaped brush-like (PEO-g-PAA)-b-PEO, which consisted of a functional PAA domain as the core and a hydrophilic PEO domain as the shell, were exploited as polymeric nanoreactors to structure-direct in situ fabrication of CdSe quantum dots (QDs) colloidal nanocrystal clusters composed of primary CdSe nanocrystals as subunits, with the secondary structures of CdSe nanocrystals. Spherical CdSe colloidal nanocrystal clusters were intimately and permanently capped with hydrophilic PEO chains on the surface to render the resulting clusters with high water dispersible property.

A series of optically active polyamides, PAnLATs (n = 9–12), were prepared by polycondensation of l-tartrate-derived diacid with achiral aliphatic diamines in which the number of the methylene is from 9 to 12. The monomers could be obtained easily, and the synthesis of the polyamides is facile. The number-average molecular weight (M̅n) of PA9LAT, PA10LAT, PA11LAT, and PA12LAT is 35 500, 24 400, 35 800, and 20 900 g/mol, respectively, and the related polydispersity index is 3.4, 3.3, 3.4, and 3.0. These polyamides display intense optical activity in solution. Particularly, the stronger ellipticities and different circular dichroism (CD) images were presented when the polymers were evaluated in the solid state. The crystalline properties of the polymers were studied to illuminate the enhanced aggregation-induced CD. Moreover, PA9LAT and PA11LAT have similar crystal parameters, and PA10LAT is similar to PA12LAT, which revealed why the chirality of the polyamides displays an odd–even effect. On the other hand, the solubility of the polymers in organic solvents was studied, and thermogravimetric-differential thermal analyzer was utilized to characterize the thermal properties.

A novel class of polymer, star-like poly(tert-butyl acrylate) (PtBA) capped with 4-isocyano-4′-(prop-2-yn-1-yloxy)biphenyl (CNBP), with a well-defined size was synthesized via atom transfer radical polymerization (ATRP) and click reaction (i.e., azide–alkyne cyclization). The star-like architecture was composed of 21 separate arms connected to a high-functionality β-cyclodextrin (β-CD) core. The inner star-like PtBA blocks were hydrolyzed into poly(acrylic acid) (PAA), yielding star-like CNBP-capped PAA (i.e., star-like PAA-CNBP). The starlike polymers were characterized by gel permeation chromatography (GPC) and dynamic light scattering (DLS) to confirm narrow size distribution, as well as being examined by proton nuclear magnetic resonance (1H-NMR), Fourier transform infrared spectroscopy (FTIR), Raman, and atomic force microscopy (AFM) to verify successful attachment of the click-functionalized capping agent (i.e., CNBP) with structural similarity to low molar mass liquid crystal, 4-cyano-4′-pentylbiphenyl (5CB). Structure and phase behavior were evaluated by AFM and optical imaging. Star-like PAA-CNBP was found to possess improved solubility in a liquid crystal host and interesting surface structures.

Extending the spectral absorption of organolead halide perovskite solar cells from visible into near-infrared (NIR) range renders the minimization of non-absorption loss of solar photons with improved energy alignment. Herein, we report on, for the first time, a viable strategy of capitalizing on judiciously synthesized monodisperse NaYF4 :Yb/Er upconversion nanoparticles (UCNPs) as the mesoporous electrode for CH3 NH3 PbI3 perovskite solar cells and more importantly confer perovskite solar cells to be operative under NIR light. Uniform NaYF4 :Yb/Er UCNPs are first crafted by employing rationally designed double hydrophilic star-like poly(acrylic acid)-block-poly(ethylene oxide) (PAA-b-PEO) diblock copolymer as nanoreactor, imparting the solubility of UCNPs and the tunability of film porosity during the manufacturing process. The subsequent incorporation of NaYF4 :Yb/Er UCNPs as the mesoporous electrode led to a high efficiency of 17.8 %, which was further increased to 18.1 % upon NIR irradiation. The in situ integration of upconversion materials as functional components of perovskite solar cells offers the expanded flexibility for engineering the device architecture and broadening the solar spectral use.