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We report a "grafting to" method for stably grafting high-molecular-weight polymer brushes on both active and inert surfaces using tadpole-like single-chain particles (TSCPs) with an interactive "head" as grafting units. The TSCPs can be efficiently synthesized through intrachain cross-linking one block of a diblock copolymer; the "head" is the intrachain cross-linked single-chain particle, and the "tail" is a linear polymer chain that has a contour length up to micrometers. When grafted to a surface, the "head", integrating numerous interacting groups, can synergize multiple weak interactions with the surface, thereby enabling stable grafting of the "tail" on both active and traditionally challenging inert surfaces. Because the structural parameters and composition of the "heads" and "tails" can be separately adjusted over a wide range, the interactivity of the "heads" with the surface and properties of the brushes can be controlled orthogonally, accomplishing surface brushes that cannot be achieved by existing methods.

Because intersystem crossing and phosphorescence decay are spin-forbidden in organic systems, it is challenging to obtain high-performance organic afterglow materials. Inspired by two-component design strategy from macromolecular self-assembly, here we report the utilization of synthetic polymers to control the excited state properties of difluoroboron β-diketonate (BF 2 bdk) and deuterated BF 2 bdk compounds for the fabrication of room-temperature organic afterglow materials. The polymer component can interact with BF 2 bdk excited states by dipole-dipole interactions, lower BF 2 bdk S 1 levels with insignificant effect on T 1 levels, reduce Δ E ST , and thus enhance intersystem crossing of BF 2 bdk excited states. The polymer component can also suppress intramolecular motion of BF 2 bdk triplets and protect BF 2 bdk triplets from oxygen quenching. The obtained BF 2 bdk-polymer afterglow materials exhibit emission lifetimes up to 2.2 s and high photoluminescence quantum yields under ambient conditions, display excellent processability and flexibility, and can function as efficient donors for excited state energy transfer to construct red afterglow materials.

Compartmentalized micelles (CMs) are promising tailor-made soft matters that mimic natural designed structures and functions. Despite the structure of complex CMs, manipulating CM structures accessibly and reversibly remains elusive. Here, we report the fabrication of CMs via a generally valid noncovalent postmodification process. Starting from precursor micelles (PMs) based on one diblock copolymer, aromatic modification leads to the compartmentalization of PMs into well-defined spherical CMs. Control over compartment number, size and distribution in CMs, and segment distribution in their linear hierarchical assemblies is attained by simply tuning the postmodification degree and solvent composition. We also demonstrate the reversible transformation between PM and CMs during several heating-cooling cycles, which endows the micelles with potential in reversible functional transitions in situ close to nature's capability. Moreover, both hierarchically assembled or ill-structured micelles can rearrange into homogeneous CMs after one heating-cooling cycle, featuring the postmodification guided compartmentalization strategy with unprecedented micelle reproducibility.

Background: To evaluate the effectiveness of varicella vaccine (VarV) as post-exposure prophylaxis (PEP) among children during varicella outbreaks., Material and Methods: A comprehensive literature search was performed in PubMed, Embase, Web of Science, SinoMed, Wanfang and CNKI. Relevant outcomes included the incidence of varicella. Pooled estimates were calculated using a fixed-effects or random-effects model according to the heterogeneity among studies., Results: A total of 15 studies with 7,474 children that received one or two dosages of VarV as PEP and 183,827 children who received no VarV were included in the meta-analysis. In total, one-dose and two-dose VarV as PEP had 43% (95% confidence interval (CI):27%, 55%) and 60% (95%CI: 35%, 75%) efficacy, respectively. When PEP was applied within 3 days, the pooled VarV as PEP for prevention of varicella was 80% (95%CI: 68%, 88%); when PEP was administered beyond 3 days, the pooled VarV as PEP for the prevention of varicella was 50% (95%CI: 11%, 72%). If the PEP was implemented with a coverage of more than 80%, the VarV could prevent 82% of varicella cases from occurring (95%CI: 15%, 96%); if the PEP covered a maximum of 80% of the susceptible cases, the VarV could prevent 65% of varicella cases from occurring (95%CI: 50%, 76%)., Conclusion: The two-dose VarV had better efficacy than one-dose VarV in the control of varicella outbreaks, especially if PEP was applied within 3 days of an outbreak and in conjunction with a high coverage rate ≥80%.

Constructing electrocatalysts with plentiful active sites, great mass transfer ability, and high electrical conductivity is critical to realize efficient hydrogen evolution reaction (HER). Hierarchically porous cobalt phosphide/N-doped nanotubular carbon networks (CoP/NCNs) that have all the features were fabricated in this work. For the fabrication, the polymeric worm-like micelles (PWs) with a large aspect ratio were coated by a uniform nanolayer of Zn-Co zeolitic imidazolate frameworks (Zn-Co-ZIFs) on their surface, resulting in the hybrid nanofibers PWs@Zn-Co-ZIFs (HPWs). Inheriting the randomly curved and entanglement properity of PWs, the rigid HPWs formed hybrid networks with the packing voids sized tens to 200 nm. Then, the hybrid networks were treated by pyrolysis-oxidation-phosphidation and ZnO-removal processes, leading to the hierarchically porous CoP/NCNs. In the CoP/NCNs, there are plentiful CoP nanoparticles embedded on the surface of conductive carbon network and fully exposed. When used for HER electrocatalyst, the CoP/NCNs only need small overpotentials (98 and 118 mV in acid and alkaline electrolyte) at 10 mA cm -2 . This novel strategy is instructive for tailoring hierarchically porous transition metal phosphide/carbon nanocomposites as promising electrocatalysts., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Herein, efficient fabrication of polymersomes that have unique and nonequilibrium morphologies is reported. Starting from preparing big polymeric vesicles sized around 2 µm with a flexible but crosslinkable structure, a controllable morphological transformation process from the vesicles via prolate vesicles and the pearl-chain-like structure, which are the two intermediate structures, to vesicle-end-capped tubes is conducted. Significantly, each of the intermediates is a regular polymersome and occupies a distinct phase space in the transformation process and thus can be separately processed and prepared. By crosslinking the structures, respectively, regular polymersomes with unique but stable morphologies are fabricated. Furthermore, the 1D polymersomes contain narrow necks. These narrow necks are sensitive to ultrasound vibration and broken by gentle ultrasound treatment to form regular open-ended tubes and open-ended vesicles, which are nonequilibrium but stable morphologies and difficult to prepare by existing methods., (© 2020 Wiley-VCH GmbH.)

Sparsely modified surfaces can be used as a general platform for precisely modifying small nanoparticles. However, strictly, rather than statistically, sparse surface modification remains a big challenge. Herein, we report a new and general method for strictly sparse modification of the surface of relatively large nanoparticles. The method is analogous to planting big trees and then removing the big crowns, leaving the stumps on the ground; due to the large exclusive size of the crowns, the stumps are strictly sparsely distributed. As a proof of concept, strictly sparse modification of surfaces was demonstrated by the successful preparation of "monovalent" and "divalent" golden nanoparticles (AuNPs) with different sizes. Starting from the "monovalent" and "divalent" AuNPs, AuNP dimers and chain-like AuNP assemblies were prepared, respectively.

Carbonized and activated wood scraps are appealing scaffolds upon which to host active materials for supercapacitors, realizing the transformation of waste into a valuable device. However, the active material when loaded on the inner walls of the wood tracheids can be easily peeled off, resulting in poor cycling stability of the capacitor and low energy density. Here, we designed a novel composite electrode material for high-performance supercapacitors based on a polyaniline/carbon nanotube composite material with a core-shell structure synthesized in situ in a carbonized wood scaffold. Carbon nanotubes with excellent conductivity were first synthesized in situ on the inner walls of the tracheids via chemical vapor deposition, which were stably embedded in the wood tracheids to increase the specific surface area and active material loading active sites. Then, a layer of polyaniline was deposited on the outer surface of each carbon nanotube via electrochemical deposition to form a core-shell nanostructure. The composite material as a single electrode has high specific capacitances of 240.0 F cm -3 and 1019.5 F g -1 at 10 mA cm -2 . Finally, the asymmetric supercapacitor based on the carbon nanotubes/carbonized wood scaffold as the anode and polyaniline/carbon nanotubes/carbonized wood scaffold as the cathode exhibited a high energy density of 40.5 W h kg -1 at 162.5 W kg -1 and a high capacity retention rate of 93.74% after 10 000 charge and discharge cycles at a current density of 20 mA cm -2 .

Herein, we report an example of self-driven morphological transition and the unique dissociation behavior of polymeric assemblies. Polymeric nanogels were introduced into the shell of polymeric assemblies and used as a powerful platform to endow the assemblies with unique properties and behaviors. It is exhibited that the nanogel can host an intrananogel cross-linking reaction and thus contracts automatically to change the geometrical packing parameters of the building blocks, driving morphological transitions of the assemblies; the transitions are self-driven without any external stimuli. Additionally, when the nanogels in the shell expand, the assemblies dissociate into small fragments even when the core is in a frozen state; in existing studies, polymeric assemblies with a frozen core cannot dissociate, except the core becomes dynamic under the stimuli. Both the self-driven morphological transition and the dissociation behavior are unique and have never been reported before.

Graphene-like g-C 3 N 4 nanosheets (NSs) have been successfully synthesized with a modified polymerization process of melamine by cocondensation with volatile salts. Volatile ammonium salts such as urea-NH 4 Cl/(NH 4 ) 2 SO 4 /(NH 4 ) 3 PO 4 were added with melamine to modulate the thermodynamic process during polymerization and optimize the structure formation in situ. The surface area, surface structure, and surface charge state of the obtained g-C 3 N 4 NSs could be controlled by simply adjusting the mass ratio of the melamine/volatile ammonium salt. As a consequence, the g-C 3 N 4 NSs exhibited much higher activity than bulk g-C 3 N 4 for the photocatalytic degradation of target pollutants (rhodamine B, methylene blue, and methyl orange), and it also exhibited greater hydrogen evolution under visible light irradiation with an optimal melamine/volatile ammonium salt ratio. The as-prepared g-C 3 N 4 NSs with melamine-urea-NH 4 Cl showed the highest visible light photocatalytic H 2 production activity of 1853.8 μmol·h -1 ·g -1 , which is 9.4 times higher than that of bulk g-C 3 N 4 from melamine. The present study reveals that the synergistic effect of the enhanced surface area, surface structure, and surface charge state is the key for the enhancement of photocatalytic degradation and hydrogen evolution, which could be controlled by the proposed strategy. The result is a good explanation for the hypothesis that adding properly selected monomers can truly regulate the polymerization process of melamine, which is beneficial for obtaining g-C 3 N 4 NSs without molecular self-assembly. Considering the inexpensive feedstocks used, a simple synthetic controlling method provides an opportunity for the rational design and synthesis, making it decidedly appealing for large-scale production of highly photocatalytic, visible-sensitizable, metal-free g-C 3 N 4 photocatalysts., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

In reported experimental studies, DNA/polymer self-assemblies are usually kinetically trapped, leading to the encapsulation and irregular collapse of DNA chains within the resultant assemblies. In striking contrast, eukaryotic cells use tetrasome-to-nucleosome pathways to escape possible kinetic trapping for the formation of well-defined 10 nm chromatin fibers. Here, we report a novel pathway for DNA and amphiphilic diblock copolymer self-assembly inspired by the tetrasome pathway with highly controllable kinetics. The polymer is an A- b-B diblock copolymer with a hydrophilic and noninteractive block A and a hydrophobic and interactive block B. Below the critical water content for the micellization, B blocks wrap the backbone of a DNA chain by weak electrostatic interactions to form a linear DNA/polymer complex. With a gradual increase in the water content, the diblock copolymer unimers in the bulk solution tend to aggregate on the linear DNA/polymer complex, which induces the originally wrapped DNA chain, to change its conformation to wrap around the polymer aggregate, guiding and tailoring the self-assembly. Highly controllable kinetics is achieved via the reduced DNA/polymer electrostatic interactions and the high dynamics of the polymer chains in the system. DNA/polymer self-assembly leads to tailorable and morphologically pure core-shell nanofibers. Compared to the DNA/micelle self-assembly pathway described in our previous study, the present self-assembly pathway exhibits advantages for the fabrication of flexible nanofibers with lengths in micrometers and the potential for unique applications in preparing not only 2D networks at extremely low percolation thresholds but also chemiresistors with large on/off current ratios.

We report the first example of the fabrication of pure, single-chain Janus particles (SCJPs). The SCJPs were prepared by double-cross-linking an A- b -B diblock copolymer in a common solvent. Inevitably, the double-cross-linking led to a mixture containing not only SCJPs but also multichain particles and irregular single-chain particles. Under well-controlled conditions, the SCJPs in the mixture self-assemble with high exclusivity to form regularly structured macroscopic assemblies (MAs) with a crystal-like appearance that precipitate from the suspension. Pure SCJPs that are uniform in size, shape and Janus structure were efficiently prepared by collection and dissociation of the MAs. Block copolymers with different structural parameters were successfully used for the exclusive self-assembly (ESA), and pure SCJPs with varied structural parameters were produced, confirming the reliability of the ESA method.

We report the first example of endowing the surface structure of a polymeric assembly with nearly atomic-level precision. The solenoidal wrapping of a DNA chain around the surface of a nanofibre transcribes the precise sequence structure of the DNA onto the nanofibre surface, resulting in a precise surface structure.

Objectives: To evaluate the effectiveness of post-exposure prophylaxis conducted during varicella outbreaks among students in Shanghai., Methods: Surveillance data were collected from September 1, 2013 to December 31, 2016 involving 3524 susceptible students in 109 primary and middle school classes where emergency vaccinations (EVs) had been administered. Students were divided into two groups according to their prior vaccination (PV) varicella vaccine status. A secondary attack rate was used to compare EV and non-EV groups using a chi-squared test. Stratification analyses were performed, adjusting for the EV administration date, the vaccination coverage rate, and the number of cases prior to the EV., Results: The effectiveness rate was 92.2% (95% confidence interval (CI): 37.1-99.0%) when EV was applied within 3 days following the outbreak onset date, and 95.2% (95% CI: 79.9-98.8%) when vaccination coverage was ≥80% among students with PV. When students with PV received an EV for varicella within 3 days, the effectiveness rate was 100%., Conclusions: EV showed high protective effectiveness for varicella during outbreaks, especially if administered within 3 days of an outbreak and in conjunction with a high coverage rate., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

We report a facile and versatile method for fabrication of multiheteroatom-doped hierarchically porous carbon with a large specific surface area, using the 3D network constructed by ZIF-8 coated wormlike micelles as template. The uniform and highly pure wormlike micelles developed in our laboratory is essential, because they not only are responsible for the formation of hierarchical porosity, but also play as a versatile platform for multiheteroatoms doping. In a primary experiment, S, N, B, and P heteroatoms were doped conveniently and the resultant porous carbons have the excellent oxygen reduction reaction performance comparable to the commercial 20% Pt/C.

Nanosized polymeric Janus particles (NPJPs) have important applications in a variety of theoretical and practical research fields. However, the methods that are versatile and can prepare NPJPs highly efficiently are very limited. Herein, we reported a two-step thermodynamically controlled preparation of NPJPs with a high yield using a diblock copolymer as the precursor. At the first step, A- b -B coassembled in the solution with a partner diblock copolymer C- b -B to form the mixed shell micelles (MSMs) with B core and A/C mixed shell. Then, intramicellarly covalently cross-linking the A block chains resulted in the complete phase separation of A and C chains in the mixed shell, leading to the direct conversion of the MSMs into NPJPs. The first step, diblock copolymer micellization, is known as a thermodynamically controlled process, and we also made the second step, conversion from MSMs to NPJPs, be thermodynamically controlled due to the application of covalent cross-linking. As the result, the conversion efficiency is close to 100%. Besides, it was further confirmed that the method can be applied to different systems and used to tune the Janus balance. Therefore, this conversion should be very significant for the fabrication and application of the NPJPs.

Herein, we report a facile but highly controllable method to induce core-core fusion for not only spherical but also worm-like polymeric micelles, leading to various complex but regular superstructures including "random worm-like co-micelles", "block worm-like co-micelles" and octopus-like superparticles.

Nanofibers are well-known nanomaterials that are promising for many important applications. Since sample preparation for the applications usually starts from a nanofiber solution, characterization of the original conformation of nanofibers in the solution is significant because the conformation affects remarkably the behavior of nanofibers in the samples. However, the characterization is very difficult by existing methods: light scattering can only roughly evaluate the conformation in solution; cryo-TEM is laborious, time-consuming, and challenging technically, and thus difficult to study a system statistically. Herein we report a novel and reliable method to recover the 3D original image of nanofibers in solution through theoretical analysis and Monte-Carlo simulations of TEM images of the nanofibers. Firstly, six kinds of monodisperse nanofibers with the same composition and inner structure but different contour lengths were prepared by the method developed in our laboratory. Then, each kind of nanofiber deposited on the substrate of the TEM sample was measured by TEM and meanwhile simulated by the Monte Carlo method. By matching the simulation results with the TEM results, we determined information about the nanofibers including their rigidity and the interaction between the nanofibers and the substrate. Furthermore, for each kind of nanofiber, based on the information, 3D images of the nanofibers in solution can be re-constructed, and then the average gyration radius and hydrodynamic radius can be calculated, which were compared with the corresponding values measured experimentally to demonstrate the reliability of this method.

Nanoparticles sized tens of nm with not only a highly complex but also a highly regular nanostructure, although ubiquitous in nature, are very difficult to prepare artificially. Herein, we report efficient solution-based preparation of narrow-disperse ABC three-segment hierarchical nanoparticles (HNPs) with a size of tens of nm through a three-level hierarchical self-assembly of A-b-B-b-C triblock copolymers in solution. An ABC HNP is composed of three nanoparticles, A, B, and C that are linearly connected; in the ABC HNP, the B nanoparticle is sandwiched between the A and C nanoparticles. The method for the preparation is highly efficient, because all of the A-b-B-b-C chains in the solution are converted into the ABC HNPs. Furthermore, the ABC HNPs self-assembled into Θ-shaped HNPs tens nm in size. Both the ABC and Θ-shaped HNPs, are highly complex but highly regular, and are novel HNPs, and they should be very promising for addressing various theoretical and practical problems., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nucleus-targeted drug delivery is a promising strategy for anticancer therapy, but in vivo nucleus-targeted drug delivery has been challenging. Limited by the channel size of the nucleopore, vehicles that enter the nucleus via the nucleopore actively should be small and decorated with nuclear localization signal (NLS). However, the small vehicle size may promote leakage of vehicles into normal tissues, and the positively-charged NLS can lead to strong non-specific interactions in vivo. In the present study, we demonstrate an in vivo nucleus-targeted drug delivery using large compound nanoparticles with detachable PEG shell. The nanoparticles are composed of PEG-benzoic imine-oligo-l-lysine/iridium(III) metallodrug complex and formed in a kinetically-controlled fashion. Under physiological conditions (pH 7.4), the nanoparticles are large (ca. 150 nm) and protected by an inert PEG shell. When internalized into intracellular acidic endo/lysosomes of cancer cells, the nanoparticles dissociate into smaller ones (ca. 40 nm) and the PEG chains detach due to the cleavage of the benzoic imine bond at low pH. The small nanoparticles, with exposure of the oligo-l-lysine after the detachment of the PEG shield, then translocate into the nucleus via the nucleopore due to the small size and nuclear localization ability of the oligo-l-lysine. Importantly, the small particles could significantly release the contained drug into the nucleus, leading to ca. 20-fold higher cytotoxicity compared to the native drug in vitro. Further in vivo application of the nucleus-targeting nano-system in a nude-mice model showed significant tumor inhibition and remarkable life-span elongation., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Mechanical responsiveness in many plants is produced by helical organizations of cellulose microfibrils. However, simple mimicry of these naturally occurring helical structures does not produce artificial materials with the desired tunable actuations. Here, we show that actuating fibres that respond to solvent and vapour stimuli can be created through the hierarchical and helical assembly of aligned carbon nanotubes. Primary fibres consisting of helical assemblies of multiwalled carbon nanotubes are twisted together to form the helical actuating fibres. The nanoscale gaps between the nanotubes and micrometre-scale gaps among the primary fibres contribute to the rapid response and large actuation stroke of the actuating fibres. The compact coils allow the actuating fibre to rotate reversibly. We show that these fibres, which are lightweight, flexible and strong, are suitable for a variety of applications such as energy-harvesting generators, deformable sensing springs and smart textiles.

Sum-frequency vibrational spectroscopy was employed to probe polymer contaminants on chemical vapor deposition (CVD) graphene and to study alkane and polyethylene (PE) adsorption on graphite. In comparing the spectra from the two surfaces, it was found that the contaminants on CVD graphene must be long-chain alkane or PE-like molecules. PE adsorption from solution on the honeycomb surface results in a self-assembled ordered monolayer with the C-C skeleton plane perpendicular to the surface and an adsorption free energy of ∼42 kJ/mol for PE(H(CH2CH2)nH) with n ≈ 60. Such large adsorption energy is responsible for the easy contamination of CVD graphene by impurity in the polymer during standard transfer processes. Contamination can be minimized with the use of purified polymers free of PE-like impurities.

A 3D network constructed from metal-organic framework composite nanowires with a uniform width and a loose (swollen) structure has been prepared. It contained micro-, meso- and macro-pores, which make the 3D network ideal for use as a catalyst, as evidenced by its high catalytic activity in the Knoevenagel reaction.

A hierarchically helical organization of carbon nanotubes into macroscopic fibers enables sophistication while controlling three-dimensional electromechanical actuations, e.g., an artificial swing and tail. The actuation generates a stress of more than 260 times that of a typical natural skeletal muscle and an accelerated velocity of more than 10 times that of a cheetah at low electric currents with high reversibility, good stability, and availability to various media., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Water-soluble monodisperse core-shell structured polymeric nanorings were robustly produced via precise self-assembly between a circular plasmid DNA (monodisperse) and monodisperse polymeric core-shell micelles; the structural parameters of the nanorings can be tailored by controlling the structural parameters of the DNA and the micelles. A study on the morphology-dependent properties of the obtained nanorings revealed that the nanorings exhibit a much higher binding affinity than their linear counterparts when interacting with oppositely charged spheres of a similar diameter. In addition, the formation of one-to-one nanoring/sphere complexes, in which the nanoring circles the equator of the sphere, was observed, which is manifested as a "host-guest" inclusion complex on the nanoscale.

Lysosomal imaging represents a potent tool for investigating the organization of related cellular events and their modulation via diagnostic and therapeutic approaches. However, specific labeling of the lysosome in live cells is a significant challenge. Taking advantage of the inherent lysosomal entry of nanoparticles and unique digestive inclusions in the lysosome, we developed a nanoparticle-based, enzyme-switchable fluorescence OFF-ON strategy for specific labeling of the lysosome and further imaging of extracellular acidification-induced lysosome trafficking in living cells. The nanoprobe comprised a 16 nm spherical gold nanoparticle as the core and an enzyme-responsive oligomer of fluorescein-conjugated oligo(4-vinyl-phenyl phosphate) as the shell. Due to quenching of the core gold nanoparticle, the nanoprobe was non-fluorescent. After incubation with cancer cells, the nanoprobe was rapidly internalized via scavenger receptor-mediated endocytosis and significantly shuffled into the lysosome. The nanoprobe specifically lighted up the lysosome owing to lysosome-induced fluorescence enhancement. Specifically, digestive inclusions in the lysosome hydrolyzed and released gold-quenched fluorescein molecules, leading to significant augmentation of fluorescence. On account of specific lysosomal labeling, the nanoprobe effectively facilitated imaging of a 4-6 μm anterograde trafficking event of the lysosome from the perinuclear region to the cell surface when an acidic extracellular environment developed. Our findings collectively highlight the use of nanoprobes for lysosomal imaging., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

In this study, tadpole-like single chain polymer nanoparticles (TSCPNs) were efficiently synthesized by intramolecularly cross-linking P4VP block of commercial block polymer of PMMA2250-b-P4VP286 in N,N-dimethylformamide using propargyl bromide as cross-linking agent. The intramolecular cross-linking reaction led to the production of TSCPNs with a linear tail and a cross-linked head. The as-prepared TSCPNs were then applied as emulsifier to stabilize water in chlorobenzene emulsion, and an extremely stabilized water in oil (W/O) emulsion was generated at a low TSCPNs concentration. The TSCPNs concentration was as low as 0.0075 wt % versus total weight of water and chlorobenzene for emulsion formation. The emulsifying performance of TSCPNs was better than that of low molecular surfactant, such as Span-80. The generated W/O emulsion provided an ideal medium for the reduction of oil-soluble p-nitroanisole by water-soluble sulfide to p-anisidine, an effective contact problem between the two reactants with different solubility was well solved through interfacial reaction.

Macromolecular self-assembly refers to the assembly of synthetic polymers, biomacromolecules and supra-molecular polymers. Through macromolecular self-assembly, the fabrication of ordered structures at different scales, the control of the dynamic assembly process and the integrations of advanced functions can be realized. Macromolecular self-assembly and nanotechnology research in China has developed rapidly, from the early periods of follow-up at low to high level and progress into a stage of innovation and creation. This review selects some representative progresses achieved recently, aiming to reflect the current status of macromolecular self-assembly and nanotechnology research in China.

We confirmed that the porous PVA dried gel with GNPs embedded in the network, which can be prepared very conveniently, is a stable and ultrasensitive 3D SERS substrate. The existence of the micropores within the gel is necessary for the ultrahigh sensitivity, and embedding of GNPs in the penetrable gel results in high stability.

Broader developments of nanoscience and nanotechnology require complexly but regularly structured nanoparticles whose fabrications in turn pose a great challenge to nanoscience and nanotechnology. In this communication, we report a new and robust method with a clear mechanism for fabricating narrowly size-distributed superparticles with a bicontinuous inner structure. The processes for the fabrication include: molecular self-assembly of a triblock copolymer in its selective solvent into the core-shell-corona micelles, the self-limited aggregation of the micelles (particles) into narrowly size-distributed superparticles constructed by the integrated micelles, and the final molecular self-assembly confined within the superparticles into cylinders that are crowded and interconnected to form the bicontinuous nanostructure; the molecular self-assembly into the micelles, the self-limited aggregation of the particles (i.e., the micelles), and the further molecular self-assembly within the superparticles occurred in a cascade manner.

Poly(propargyl pyridinium bromide), a kind of conjugated polyelectrolyte with polyacetylene as the backbone and pyridinium as side groups, was synthesized simply via reaction between pyridine and propargyl bromide under mild conditions. The resultant polymer was characterized by (1)H NMR, elemental analysis, FT-IR, and GPC-MALLS. An alkyne group was confirmed as the end group of the polymer chains by the alkyne/azide click chemistry, which reveals that the polymerization is terminated by the reaction between propargyl bromide and carbon anions. It is known that monosubstituted polyacetylenes reported have very weak fluorescence intensities, which limit their applications. As a monosubstituted polyacetylene, the freshly prepared poly(propargyl pyridinium bromide) also has a very weak fluorescence. However, we confirmed that addition of some anions to the polymer solution in DMF or DMSO leads to the fluorescence enhancements up to 25 times. Besides, heating the polymer solution at a temperature between 70 and 130 °C for longer than 0.5 h greatly enhanced the fluorescence intensity. The interaction with the anions or the heating enhances the effective exciton confinement within the conjugated backbone and thus results in the fluorescence enhancements. After the fluorescence enhancements, poly(propargyl pyridinium bromide) has relatively strong fluorescence emissions, which will make it promising in fluorescence-based applications.

Transporting drug-containing nanoparticles into the nucleus of cancer cells through nucleopores and then releasing the drug intranuclearly provide an efficient strategy to overcome the drug resistance mechanisms evolved by cancer cells. However, limited by the diameter of nucleopores, nanoparticles capable of going through nucleopores should be small enough, whereas the nanoparticles with the small size may have short circulation time in blood and low accumulation in solid tumors. We solved this dilemma successfully by preparing kinetically frozen large compound nanoparticles (sized 128 nm) of complex of oligolysine/iridium(III) compound (a potential anticancer drug) that can dissociate into small ones in lysosome environment. The small nanoparticles retain their small size in cytosol after escaping from the lysosomes, so that they can enter the nucleus actively through nucleaopores, with the help of oligolysine segments on the surfaces of nanoparticles acting as the nuclear targeting moieties. It is significant that the nanoparticles can release the contained Ir compound within the nucleus. Further study reveals that the release is triggered by DNA interaction with the nanoparticles, which is responsible for the observation that the release occurs only in the nucleus. We believe that the present study, representing the first example of DNA triggered intranuclear release from nanoparticles, will provide a promising pathway for chemotherapy., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

In this article, we demonstrate that by tethering carboxyl groups of poly(10,12-pentacosadiynoic acid) (PDA) to a poly(vinyl alcohol) (PVA) matrix, PDA, which is irreversible in its pure form, becomes reversible in the thermochromism. The tethering is realized by simple but deliberately designed processes: (1) Disperse the commercially available monomer 10,12-pentacosadiynoic acid (DA) nanocrystals in a PVA aqueous solution by the "NCCM" method invented in our laboratory. (2) Anneal and dry the mixture solution at a temperature higher than the melting point of pure DA crystal. (3) Polymerize the as-annealed DA/PVA blend films by UV irradiation. After the polymerization, PDA/PVA films with completely reversible thermochromism are obtained. The reversible PDA/PVA films can be easily dissolved in water, leading to water-dispersible nanoaggregates with the reversibility. Blends of PDA with other water-soluble polymers such as poly(ethylene oxide) (PEO), poly(acrylic acid) (PAA) and poly(allyamine) (PAM), were prepared respectively, by the same processes and under the same conditions. It is found that all these nanocomposites are irreversible or partially reversible in the thermochromism; either the relatively low glassy transition temperature of the polymer matrix (in the case of PEO) or the partial ionization nature of the polymer (in the cases of PAA and PAM) is responsible for the irreversibility or the partial reversibility.

The deliberately prepared one ssDNA/one micelle complex has an unstable toroidal DNA-bound region and stable upper and lower hemispheres, and thus can self-assemble along the plane of the unstable toroidal region into free-suspending films.

Small polymeric nanoparticles sized below 10 nm were effectively synthesized via free radical polymerization of a cross-linker in a glassy polymer matrix, owing to the successful prohibition of aggregation between the primary nanoparticles by the matrix.

Chromatic materials such as polydiacetylene change colour in response to a wide variety of environmental stimuli, including changes in temperature, pH and chemical or mechanical stress, and have been extensively explored as sensing devices. Here, we report the facile synthesis of carbon nanotube/polydiacetylene nanocomposite fibres that rapidly and reversibly respond to electrical current, with the resulting colour change being readily observable with the naked eye. These composite fibres also chromatically respond to a broad spectrum of other stimulations. For example, they exhibit rapid and reversible stress-induced chromatism with negligible elongation. These electrochromatic nanocomposite fibres could have various applications in sensing.

We report a novel strategy for the high-efficiency preparation of macrocyclic diblock copolymers at relatively high concentrations via the combination of supramolecular self-assembly and "selective" click reactions, relying on the fine control of spatial accessibility between terminal reactive groups. The linear precursor, alpha-alkynyl-omega-azido heterodifunctional poly(2-(2-methoxyethoxy)ethyl methacrylate)-b-poly(oligo(ethylene glycol) methyl ether methacrylate), linear-PMEO(2)MA-b-POEGMA-N(3), self-assembles into micelles with PMEO(2)MA cores and POEGMA coronas at elevated temperatures. The spatial separation between reactive alkynyl and azide groups precludes click reactions within micelle entities. On the other hand, due to the unimer-micelle exchange equilibrium and the fact that unimer concentration is typically low (critical micellization concentration, CMC), click reactions occur exclusively for unimers. This eventually led to complete intramolecular cyclization of all linear precursors.

We report a new type of carbon material-porous colossal carbon tubes. Compared with carbon nanotubes, colossal carbon tubes have a much bigger size, with a diameter of between 40 and 100 mum and a length in the range of centimeters. Significantly, the walls of the colossal tubes are composed of macroscopic rectangular columnar pores and exhibit an ultralow density comparable to that of carbon nanofoams. The porous walls of colossal tubes also show a highly ordered lamellar structure similar to that of graphite. Furthermore, colossal tubes possess excellent mechanical and electrical properties.

In this work, a novel cube-shaped cationic lipid based on the imidazolium salt of polyhedral oligomeric silsesquioxane (POSS) was complexed with double-stranded DNA. Because of the negative spontaneous curvature of the cationic POSS imidazolium lipid, an inverted hexagonal phase resulted above the melting point of POSS crystals. Depending on the competition between the crystallization of POSS molecules and the negative spontaneous curvature of cationic POSS imidazolium lipids, different self-assembled phase morphologies were obtained. A lamellar phase was obtained when the POSS crystallization was relatively slow. When the POSS crystallization was fast, an inverted hexagonal phase was obtained with POSS lamellar crystals grown in the interstitials of DNA cylinders. On the basis of a circular dichroism study, double-stranded DNA adopted the B-form helical conformation in the inverted hexagonal phase, whereas the helical conformation was largely destroyed in the lamellar phase.

We report here facile preparation of stabilized polymeric nanotubes with a hair-like shell using yttrium hydroxide nanotubes as the sacrificial template and block copolymer micelles as the precursor, and orientation of the polymeric nanotubes encapsulating magnetic particles under magnetic field.

Frechet-type benzyl ether dendrons of second and third generations with a carboxyl group (G2, G3) at the apex site could attach to poly(4-vinylpyridine) (PVP), forming hydrogen-bonded dendronized polymers (HB denpols) in their common solvent, chloroform. The HB denpols show unique self-assembly behavior, forming vesicles in the common solvent under ultrasonic treatment. The structure and morphology of the vesicles were characterized by dynamic light scattering (DLS), static light scattering (SLS), SEM, TEM, and AFM. The size of the vesicles decreases and the thickness of the vascular membrane increases as the molar ratio of Gx/PVP increases. The hydrogen bonding, pi-pi aromatic stacking of the dendrons, and the considerable difference in architecture between the dendron Gx and PVP are the main factors facilitating the assembly of the HB denpols in the common solvent.

The investigation on the formation mechanism of helical structures and the synthesis of helical materials is attractive for scientists in different fields. Here we report the synthesis of helical mesoporous materials with chiral channels in the presence of achiral surfactants. More importantly, we suggest a simple and purely interfacial interaction mechanism to explain the spontaneous formation of helical mesostructures. Unlike the proposed model for the formation of helical molecular chains or surpramolecular packing based on the geometrically motivated model or the entropically driven model, the origin of the helical mesostructured materials may be attributed to a morphological transformation accompanied by a reduction in surface free energy. After the helical morphology is formed, the increase in bending energy together with the derivation from a perfect hexagonal mesostructure may limit the curvature of helices. Our model may be general and important in the designed synthesis of helical mesoporous materials.

We report here the preparation of PEO-b-P2VPH+-S2O8(2-) micelles and their reversible multi-responsive behavior.

Conjugated polydiacetylene (PDA)/silica nanocomposites with tunable mesostructures and reversible thermochromatism were synthesized through self-directed assembly of diacetylenic silanes. In contrast to the previous studies, where the PDA side chains interacted weakly through noncovalent interactions, the side chains in the present nanocomposites are covalently connected to the inorganic silica frameworks, providing control over the molecular alignment, stability, and electronic properties. Furthermore, tuning the molecular architecture (e.g., the shape and side-chain length) allows control over the mesostructure (e.g., cubic and lamellar) and chromatic response of the nanocomposites (from irreversible to partially reversible and then to completely reversible). As a result of the covalent interactions, the nanocomposites also demonstrate higher reversible chromatic transition temperatures. This work not only provides responsive robust chromatic materials toward practically reusable PDA sensors but also is of great fundamental value for the design of supramolecular assembly and the understanding of the chromatic mechanism of PDA.

We succeeded recently in developing a series of new pathways to polymeric micelles and hollow spheres via intermolecular specific interactions. A new micellization mechanism of block copolymers was realized by using the specific interaction between a low molecular weight compound and one of the blocks in low-polarity solvents. Many more successes have been achieved by our "block copolymer-free" strategies. We are now able to use homopolymers, random copolymers, oligomers, etc. as building blocks to construct noncovalently connected micelles (NCCM), in which the core and shell are connected by hydrogen bonding. Some of such NCCMs are readily converted further into hollow spheres by cross-linking the shell and then switching the medium to one that dissolves the core. Rigid polymer chains and their complementary homopolymers can directly assemble into large hollow spheres thanks to the propensity to parallel packing of the rigid chains. In addition, some of the NCCMs show perfect stimuli-responsive properties. pH-dependent micellization and pH-dependent micelle-hollow-sphere transition are realized in water-soluble graft copolymers driven by complexation and decomplexation between the main chain and grafts.

According to our "block-copolymer-free" strategy for self-assembly of polymers, noncovalently connected micelles (NCCM) with poly(epsilon-caprolactone) (PCL) as the core and poly(acrylic acid) (PAA) as the shell in aqueous solutions were attained due to specific interactions between the component polymers. The micellar structure was then locked in by the reaction of PAA with diamine. Afterward, hollow spheres based on PAA network were obtained by either core degradation with lipase or core dissolution with dimethylformamide of the cross-linked micelles. The cavitation process was monitored by dynamic light scattering, which indicated a mass decrease and size expansion. The hollow structure is confirmed by transmission electron microscopy observations. The resultant hollow spheres are pH- and salt-responsive: there is a substantial volume increase when pH changes from acid to base, and vice versa. The volume change takes place dramatically over the pH-range from 5.8 to 7.5. Furthermore, this volume-pH-dependence is found to be completely reversible provided the effect of ionic strength is excluded. The volume change can be adjusted by changing the shell thickness and the cross-linking degree of the hollow spheres. The salt effect on the hollow sphere size depends on pH: with increasing salt concentration the size shows an increase, a decrease, and a little change in acidic, basic, and neutral media, respectively.

A simple mild solution method is developed to synthesize a novel nanoribbon multicomponent precursor. A new 1-D nanostructure, porous structured nanoribbons which are self-assembled by textured ZnO nanoparticles, was found upon removal of ligand molecules from the ribbonlike precursor. The structure combines 1-dimensional geometry with nanoparticle morphology and displays porous structure because there are gaps/pores between the particles. The orientation textured structure of the ZnO nanoparticles can be formed by controlling the annealing time. The ZnO nanoparticle nanoribbons exhibit a long geometrical shape, uniformity, a high aspect ratio, and different optical activities with different nanostuctures. These findings demonstrate a convenient, simple technique for production of the novel one-dimensional semiconductor nanostructure suitable for subsequent processing into nanostructures, materials, and devices.