The past several decades have witnessed substantial advances in synthesis and self-assembly of inorganic nanocrystals (NCs) due largely to their size- and shape-dependent properties for use in optics, optoelectronics, catalysis, energy conversion and storage, nanotechnology, and biomedical applications. Among various routes to NCs, the nonlinear block copolymer (BCP) nanoreactor technique has recently emerged as a general yet robust strategy for crafting a rich diversity of NCs of interest with precisely controlled dimensions, compositions, architectures, and surface chemistry. It is notable that nonlinear BCPs are unimolecular micelles, where each block copolymer arm of nonlinear BCP is covalently connected to a central core or polymer backbone. As such, their structures are static and stable, representing a class of functional polymers with complex architecture for directing the synthesis of NCs. In this review, recent progress in synthesizing NCs by capitalizing on two sets of nonlinear BCPs as nanoreactors are discussed. They are star-shaped BCPs for producing 0D spherical nanoparticles, including plain, hollow, and core-shell nanoparticles, and bottlebrush-like BCPs for creating 1D plain and core/shell nanorods (and nanowires) as well as nanotubes. As the surface of these NCs is intimately tethered with the outer blocks of nonlinear BCPs used, they can thus be regarded as polymer-ligated NCs (i.e., hairy NCs). First, the rational design and synthesis of nonlinear BCPs via controlled/living radical polymerizations is introduced. Subsequently, their use as the NC-directing nanoreactors to yield monodisperse nanoparticles and nanorods with judiciously engineered dimensions, compositions, and surface chemistry is examined. Afterward, the intriguing properties of such polymer-ligated NCs, which are found to depend sensitively on their sizes, architectures, and functionalities of surface polymer hairs, are highlighted. Some practical applications of these polymer-ligated NCs for energy conversion and storage and drug delivery are then discussed. Finally, challenges and opportunities in this rapidly evolving field are presented.
In stark contrast to conventional organic ligand-capped counterparts, the ability to create stable metal halide perovskite nanocrystals strongly tethered with conjugated polymers (CPs) represents an important endeavor toward tailoring charge carrier dynamics at their interface that critically underpins applications of this unique class of all semiconducting, organic-inorganic nanomaterials for optoelectronics. This, however, has yet to be largely explored. Herein, we report, for the first time, the unraveling of efficient charge separation at judiciously designed CP/perovskite quantum dot (QD) interface for photoinduced atom transfer radical polymerization (p-ATRP). Such scrutiny is rendered by in situ crafting an array of monodisperse, highly stable, CP-ligated perovskite QDs with precisely controlled dimensions of each constituent via capitalizing on unimolecular, amphiphilic starlike block copolymers as nanoreactors. The intimate and permanent surface tethering of CPs imparts remarkable thermal, photo, and polar solvent stabilities of CP-ligated perovskite QDs. More importantly, they manifest efficient interfacial charge separation with a profound dependence on the length of ligated CPs and the size of perovskite QDs. The outstanding structural stabilities and charge separation characteristic enable CP-ligated perovskite QDs as robust photocatalysts for p-ATRP of a wide selection of monomers with stable and controllable reaction kinetics, also depending crucially on the length of CPs and the size of perovskite QDs. In principle, an exciting variety of CP-ligated, uniform perovskite QDs with virtually unlimited material choice of both markedly improved stabilities and tunable electronic band alignments can be readily accessed by exploiting the amphiphilic starlike block copolymer nanoreactor strategy for use in photodetectors, sensors, and LEDs, among other areas.
Surface-enhanced Raman scattering (SERS) is widely used to provide chemical and physical information, causing widespread attention in many fields, such as biochemical and bioscience fields.To get high SERS signals, noble nanoparticles are applied in SERS detection.Hollow urchin-like gold nanoparticles (HU-GNPs) are a novel nanostructure, which contains rough surfaces and sharp branches.Owing to "Hot spots" effect, it can enhance the surrounding electromagnetic field, generating good SERS effects.In this paper, using seed-mediated growth method, hollow urchin-like gold nanoparticles were prepared.Besides, controllable synthesis was achieved to get the optimal HU-GNPs with good morphology, uniformity and SERS enhancement.And then, SERS substrates were built with HU-GNPs by electrostatic self-assembly method.The SERS signals of NBA can be detected at different concentrations from 10-5 M to 10-9 M. At the same time, field emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), and surface enhanced Raman scattering (SERS) were used for the characterization of the nanoparticles.
Colour substances in dyeing effluents normally cause certain difficulties in traditional biological treatment processes due to their nonbiodegradable nature. It is necessary to remove colour from dyeing effluents with the help of some physical or chemical treatment processes. This study aims to investigate the colour removal from dyeing wastewater using a TiO 2 -sensitized photo-oxidation process and the biodegradability of the products formed in the wastewater. Synthetic dyeing wastewater samples were exposed to near UV radiation at a wavelength of 350 nm in the presence of TiO 2 and aeration. The results show that most dyes used in the experiment can be degraded by the sensitized photo-oxidation successfully. Colour removal from the wastewater was above 95% after 4-6 hours treatment. It was found that there was a relationship between the chemical oxygen demand (COD), total organic carbon (TOC) and biochemical oxygen demand (BOD). While COD and TOC in the wastewater were decreased during the reaction, BOD was found to be increased, which implies that the TiO 2 -sensitized photo-oxidation can enhance the biodegradability of the dyeing wastewater. As a process, it might be an effective method to remove colour and to further remove COD after treating dyeing effluent by a conventional biological treatment process.
<p><a></a><a>The development of Earth-abundant reusable and no-toxic heterogeneous catalyst applied in the pharmaceutically, bio-active relevant compounds synthesis as well as other organic syntheses still remains as the most important goal of the general chemical research. N-methylated compounds, as one of the most essential bioactive compounds,</a> have been widely used in the fine and bulk industries for the production of high-value chemicals including pharmaceuticals, agrochemicals, and dyes. As their reports, activated toxic methyl iodide and dimethyl sulfoxide were usually employed in the traditional N-methylation, which easily suffer from narrow scopes of amines, generation of by-products, and a large amount of waste. <a>Very recently, </a>transition metal-catalyzed methylation of amines has become an efficient, practical, and cost-effective method for the one-pot selective synthesis of N-methylamines with C<sub>1</sub> sources. Herein, we first developed a simple and <a>environmentally friendly</a> method for the preparation of efficient, reusable, and low-cost graphene spheres encapsulated Ni/NiO nanoalloy catalysts (Ni/NiO@C) for highly selective synthesis of the N-methylated compounds by using various functional amines and aldehydes under easily handle-able and industrially <a></a><a>applicable </a>conditions.<b> </b>A large number of primary, secondary amines (more than 70 examples) could be converted smoothly to the corresponding N, N-dimethylamines with the participation of different functional aldehydes. The gram-scale synthesis was also demonstrated in an excellent yield; not only that, the catalyst was further proved that it could be easily recycled by its intrinsic magnetism and reused up to ten times without losing activity and selectivity. Both of them are the great advantages in contrast to other catalysts reported previously. And also, for the first time, we have developed the highly efficient, cost-effective tandem synthesis of N, N-dimethylamines products in a one-pot process by means of aldehydes and NH<sub>3</sub>. As far as we know, this is the first example of the synthesis of tertiary amines with the combined reaction process of reductive amination of aldehydes and N-methylation of primary amines only with the single one earth-abundant metal catalyst. Overall, the advantages of this newly developed method including operational simplicity, high stability, easily recyclable, cost-effective of the catalyst, and good functional group compatibility for the synthesis of N-methylation products, as well as the highly efficient and industrial applicable tandem synthesis process.</p>
China is a significant producer and consumer of various brominated flame retardants (BFRs), raising environmental concerns due to their widespread presence and potential threats to ecosystems and organisms. This study adopts a life cycle perspective, combining material flow analysis, multimedia environmental modeling, and ecological risk assessment to systematically analyze the substance metabolism and ecological risks of six BFR types in China from 1970 to 2021. The findings reveal that China's cumulative BFR consumption reached 3.3 Mt, with the electronics sector being the predominant contributor at 52.1%. Consequently, 1.5 kt of BFRs were released into the environment, with 24.9%, 31.5%, and 43.6% being discharged into the air, water, and soil, respectively. Notably, the proportion of novel BFRs in emissions has steadily increased over the years, exemplified by the increase in decabromodiphenyl ethane (DBDPE) from 21.3% in 2010 to 30.1% in 2021. Geographically, BFR concentrations are higher in the eastern and southwestern regions compared to those in the northwest. Presently, certain BFRs like tetrabromobisphenol A (TBBPA) and DBDPE exhibit moderate to high ecological risks, primarily concentrated in the Shandong and Sichuan provinces. A combination of efficient recycling, emission control, and substitution with novel flame-retardant can minimize the exposure of BFRs to the environment and organisms.
Environmentally friendly crosslinked polymer networks feature degradable covalent or non-covalent bonds, with many of them manifesting dynamic characteristics. These attributes enable convenient degradation, facile reprocessibility, and self-healing capabilities. However, the inherent instability of these crosslinking bonds often compromises the mechanical properties of polymer networks, limiting their practical applications. In this context, environmentally friendly dual-crosslinking polymer networks (denoted EF-DCPNs) have emerged as promising alternatives to address this challenge. These materials effectively balance the need for high mechanical properties with the ability to degrade, recycle, and/or self-heal. Despite their promising potential, investigations into EF-DCPNs remain in their nascent stages, and several gaps and limitations persist. This Review provides a comprehensive overview of the synthesis, properties, and applications of recent progress in EF-DCPNs. Firstly, synthetic routes to a rich variety of EF-DCPNs possessing two distinct types of dynamic bonds (i.e., imine, disulfide, ester, hydrogen bond, coordination bond, and other bonds) are introduced. Subsequently, complex structure- and dynamic nature-dependent mechanical, thermal, and electrical properties of EF-DCPNs are discussed, followed by their exemplary applications in electronics and biotechnology. Finally, future research directions in this rapidly evolving field are outlined.
The key to exploiting perovskite nanocrystals (NCs) for long-term practical use in optoelectronic materials and devices lies in the ability to access stable NCs. Herein, we report the crafting of hairy perovskite NCs with a set of markedly improved stabilities by capitalizing on rationally designed star-like molecular bottlebrush trilobes as nanoreactors. An intriguing star-like molecular bottlebrush trilobe, poly(2-hydroxyethyl methacrylate)-graft-(poly(acrylic acid)-block-partially cross-linked polystyrene (denoted PHEMA-g-(PAA-b-cPS)) is synthesized. Subsequently, it is employed as a polymeric nanoreactor to direct the growth of green-emitting all-inorganic perovskite CsPbBr3 NCs intimately and stably tethered by partially cross-linked PS "hairs" (i.e., cPS-capped CsPbBr3 NCs). The resulting CsPbBr3 NCs exhibit an array of impressive stabilities against UV irradiation, moisture, heat, and water, due to permanently ligated hydrophobic cPS "hairs" on the surface of CsPbBr3 NCs as a result of the original covalent bonding between PAA and cPS blocks. More importantly, cPS-capped CsPbBr3 NCs manifest outstanding stability in various polar organic solvents. Such greatly improved stability can be attributed to the reduced surface defects enabled by the favorable interaction (i.e., coordination interaction and hydrogen bonding) between CsPbBr3 NCs and polar solvents, which dominates over their dissolution by polar solvents. Such exceptional stabilities impart the use of cPS-capped CsPbBr3 NCs as a selective probe for tracing the presence of Cl–/I– in polar organic solvents. The amphiphilic nonlinear block copolymer nanoreactor strategy can afford easy access to stable perovskite NCs of interest with controlled compositions and surface chemistry. They may find applications in solar cells, LEDs, photodetectors, lasers, bioimaging, biosensors, etc.
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