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Current interest in nanoparticle ensembles is motivated by their collective synergetic properties that are distinct from or better than those of individual nanoparticles and their bulk counterparts. These new advanced optical, electronic, magnetic, and catalytic properties can find applications in advanced nanomaterials and functional devices, if control is achieved over nanoparticle organization. Self-assembly offers a cost-efficient approach to produce ensembles of nanoparticles with well-defined and predictable structures. Nanoparticles functionalized with polymer molecules are promising building blocks for self-assembled nanostructures, due to the comparable dimensions of macromolecules and nanoparticles, the ability to synthesize polymers with various compositions, degrees of polymerization, and structures, and the ability of polymers to self-assemble in their own right. Moreover, polymer ligands can endow additional functionalities to nanoparticle assemblies, thus broadening the range of their applications.In this Account, we describe recent progress of our research groups in the development of new strategies for the self-assembly of nanoparticles tethered to macromolecules. At the beginning of our journey, we developed a new approach to patchy nanoparticles and their self-assembly. In a thermodynamically driven strategy, we used poor solvency conditions to induce homopolymer surface segregation in pinned micelles (patches). Patchy nanoparticles underwent self-assembly in a well-defined and controlled manner. Following this work, we overcame the limitation of low yield of the generation of patchy nanoparticles, by using block copolymer ligands. For block copolymer-capped nanoparticles, patch formation and self-assembly were "staged" by using distinct stimuli for each process. We expanded this work to the generation of patchy nanoparticles via dynamic exchange of block copolymer molecules between the nanoparticle surface and micelles in the solution. The scope of our work was further extended to a series of strategies that utilized the change in the configuration of block copolymer ligands during nanoparticle interactions. To this end, we explored the amphiphilicity of block copolymer-tethered nanoparticles and complementary interactions between reactive block copolymer ligands. Both approaches enabled exquisite control over directional and self-limiting self-assembly of complex hierarchical nanostructures. Next, we focused on the self-assembly of chiral nanostructures. To enable this goal, we attached chiral molecules to the surface of nanoparticles and organized these hybrid building blocks in ensembles with excellent chiroptical properties. In summary, our work enables surface engineering of polymer-capped nanoparticles and their controllable and predictable self-assembly. Future research in the field of nanoparticle self-assembly will include the development of effective characterization techniques, the synthesis of new functional polymers, and the development of environmentally responsive self-assembly of polymer-capped nanoparticles for the fabrication of nanomaterials with tailored functionalities.

Nanomedicines have the potential to provide advanced therapeutic strategies in combating tumors. Polymer-prodrug-based nanomedicines are particularly attractive in cancer therapies owing to the maximum drug loading, prolonged blood circulation, reduced premature leakage and side effects in comparison with conventional nanomaterials. However, the difficulty in precisely tuning the composition and drug loading of polymer-drug conjugates leads to batch-to-batch variations of the prodrugs, thus significantly restricting their clinical translation. Polyprodrug nanomedicines inherit the numerous intrinsic advantages of polymer-drug conjugates and exhibit well-controlled composition and drug loading via direct polymerization of therapeutic monomers, representing a promising nanomedicine for clinical tumor therapies. In this review we summarize recent advances in the development of polyprodrug nanomedicines for tumor elimination. Various types of polyprodrug nanomedicines and the corresponding properties are first summarized. The unique advantages of polyprodrug nanomedicines and their key roles in various tumor therapies are further highlighted. Finally, current challenges and our perspectives on future research of polyprodrug nanomedicines are discussed. This article is protected by copyright. All rights reserved.

The intellectualization and complication of existing self-shaping materials are limited by the inseparable monotonic relationship between their deformation rate and deformation degree (i.e., a higher deformation rate is accompanied by a high deformation degree). This causes that they can only deform from 2D to 3D states. Here, a simple yet versatile strategy to decouple the monotonic correlation between the deformation rate and deformation degree of self-shaping hydrogels is presented for achieving complex deformations from 2D to temporary 3D to 3D (2D-to-4D). It is demonstrated that when the gradient hydrogels prepared by photopolymerization possess dense polymer networks, the local regions with a high deformation rate can exhibit a low deformation degree. The resulting hydrogels can thus deform in a novel 2D-to-4D mode under external stimuli. During the deformation, they first transform into the temporary shapes induced by the local deformation rate difference, and then transform into the final shapes determined by the local deformation degree difference. Through controlling the ultraviolet irradiation direction and time to precisely program the local gradients of self-shaping hydrogels, they can be designed to produce various unprecedented yet controllable 2D-to-4D shape evolutions on demand, such as transformable origami, sequential gesture actions in finger-guessing games, mobile octopuses, time switch, etc.

Polymer-grafted hairy nanoparticles (HNPs) that combine the unique properties of inorganic nanoparticles (NPs) and polymers are attractive building blocks for the layer-by-layer assembly of functional hybrid materials, but the adsorption behaviors of HNPs on substrates remain unclear. This article describes a systematic study on the adsorption behaviors of charged polymer-grafted HNPs on oppositely charged substrates in different solvent media via a combination of experiments and simulations. It is shown in simulations that the adsorption process of HNPs is associated with the release of counterions around charged polymers on HNPs, thus resulting in a higher energy barrier of NP adsorption than bare NPs without charged polymer tethers. This energy barrier decreases with decreasing the dielectricity of solvents or ionization degree of grafted polymers or increasing ionic strength of the solution. Furthermore, the theoretical prediction is confirmed in experiments by using a model system of poly(acrylic acid)-grafted silica NPs and poly(diallyldimethylammonium chloride)-modified wafers. The work provides guidance for the electrostatic assembly of HNPs into functional hybrid composites with applications in membranes, optical devices, and biomedicines.

The technique of anterior cervical corpectomy and fusion (ACCF) for strut grafting has become a widespread and actively applied for many cervical complaints including cervical degeneration of the intervertebral disks, cervical trauma, cancer, rheumatoid arthritis and multilevel cervical spondylotic diseases. To avoid the complications of the old techniques, the construct stability and long anterior screw-plate designs of the bone strut have been improved by using effective biomaterials. The nanostructured hydroxyapatite (HAp) incorporated with biocompatible polymer matrixes is an effective biomedical material and creating a functional properties applied for different tissue replacements such as dental, hips, knees, tendon and ligaments and tissue repair for maxillofacial reconstruction, stabilization of the jaw bone and spinal fusion. In the present investigation, we have successfully designed cylindrical nano titanium dioxide (n-TiO

Hydrodynamic flow in a microfluidic (MF) device offers a high-throughput platform for the continuous and controllable self-assembly of amphiphiles. However, the role of hydrodynamics on the assembly of colloidal amphiphiles (CAMs) is still not well understood. This Article reports a systematic study of the assembly of CAMs, which consist of Au nanoparticles (AuNPs) grafted with amphiphilic block copolymers, into vesicles with a monolayer of CAMs in the membranes using laminar flows in MF flow-focusing devices. Our experimental and simulation studies indicate that the transverse diffusion of solvents and colloids across the boundary of neighboring lamellar flows plays a critical role in the assembly of CAMs into vesicles. The dimension of the vesicles can be controlled in the range of 100-600 nm by tuning the hydrodynamic conditions of the flows. In addition, the diffusion coefficient of CAMs was also critical for their assembly. Under the same flow conditions, larger CAMs generated larger assemblies as a result of the reduced diffusion rate of large amphiphiles. This work could provide fundamental guidance for the preparation of nanoparticle vesicles with applications in bioimaging, drug delivery, and nano- and microreactors.

Self-assembly of gold nanorods (NRs) in linear, polymer-like chains offers the ability to test and validate theoretical models of molecular polymerization. Practically, NR chains show multiple promising applications in sensing of chemical and biological species. Both areas of research can strongly benefit from the development of a quantitative tool for characterization of the structure of NR chains in the course of self-assembly, based on the change in ensemble-averaged optical properties of plasmonic polymers; however, quantitative correlation between the extinction spectra and the structural characteristics of NR chains has not been reported. Here, we report such a tool by a quantitatively correlating the red shift of the longitudinal surface plasmon band of gold NRs and the average aggregation number of NR chains. The generality of the method is demonstrated for NRs with different aspect ratios, for varying inter-rod distances in the chains, and for varying initial concentrations of NRs in solution. We modeled the extinction spectra of the NR chains by combining the theory of step-growth polymerization with finite-difference time-domain simulations and a resistor-inductor-capacitor model, and obtained agreement between the theoretical and experimental results. In addition to capturing quantitatively the ensemble physics of the polymerization, the proposed 'plasmonic counter' approach provides a real-time cost- and labor-efficient method for the characterization of self-assembly of plasmonic polymers.

The hydrodynamics of laminar flow in a microfluidic device has been used to control the continuous self-assembly of gold nanoparticles (NPs) tethered with amphiphilic block copolymers. Spherical micelles, giant vesicles (500 nm-2.0 μm), or disk-like micelles could be formed by varying the flow rates of fluids. Such vesicles can release encapsulated hydrophilic species by using near-IR light.

Nanorod Polymers Nanoparticles and colloids have been used to model crystallization and melting phenomena. Liu et al. (p. 197 ) studied the polymerization kinetics of nanoparticles. Functionalized arrowhead nanorods acted as linkable units that joined together in solvent-tuned assembly. The results resembled common processes of chemical polymerization: Growth was controlled kinetically and could be interpreted by formulas for step-growth polymerization and branching. Furthermore, some isomerization phenomena were observed, as was the formation of cyclic “macromolecules.”

Organized arrays of anisotropic nanoparticles show electronic and optical properties that originate from the coupling of shape-dependent properties of the individual nanorods. The organization of nanorods in a controllable and predictable way provides a route to the fabrication of new materials and functional devices. So far, significant progress has been achieved in the self-assembly of nanorod arrays, yet the realization of a range of different structures requires changing the surface chemistry of the nanoparticles. We organized metal nanorods in structures with varying geometries by using a striking analogy between amphiphilic ABA triblock copolymers and the hydrophilic nanorods tethered with hydrophobic polymer chains at both ends. The self-assembly was tuneable and reversible and it was achieved solely by changing the solvent quality for the constituent blocks. This approach provides a new route to the organization of anisotropic nanoparticles by using the strategies that are established for the self-assembly of block copolymers.

This communication reports the amphiphilic block copolymer driven self-assembly of Au nanoflowers into nanoparticle vesicles and the near-infrared light triggered release of hydrophilic molecules encapsulated in vesicles.

Asymmetric multicomponent nanoparticles (AMNPs) offer new opportunities for new-generation materials with improved or new synergetic properties not found in their individual components. There is, however, an urgent need for a synthetic strategy capable of preparing hybrid AMNPs with fine-tuned structural and compositional complexities. Herein, we report a new paradigm for the controllable synthesis of polymer/metal AMNPs with well-controlled size, shape, composition, and morphology by utilizing interfacial polymerization. The hybrid AMNPs display a new level of structural–architectural sophistication, such as controlled domain size and the number of each component of AMNPs. The approach is simple, versatile, cost-effective, and scalable for synthesizing large quantities of AMNPs. Our method may pave a new route to the design and synthesis of advanced breeds of building blocks for functional materials and devices.