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Control over the assembly and morphology of nanoscale functional building blocks is of great importance to hybrid and porous nanomaterials. In this paper, by combining different types of spherical nanoparticles with different size ratios in a hierarchical assembly process which allows us to control the final structure of multi-component assemblies, we discuss self-assembly of an extensive range of supraparticles, labelled as AB particles, and an extension to novel ternary particles, labelled as ABC particles. For supraparticles, the organization of small nanoparticles is known to be inherently related to the size ratio of building blocks. Therefore, we studied the formation of supraparticles prepared by colloidal self-assembly using small silica nanoparticles (SiO 2 NPs) attached on the surface of large polystyrene latex nanoparticles (PSL NPs) with a wide size ratio range for complete and partial coverage, by controlling the electrostatic interactions between the organic and inorganic nanoparticles and their concentrations. In this way hierarchically ordered, stable supraparticles, either fully covered or partially covered, were realized. The partially covered, stable AB supraparticles offer the option to create ABC supraparticles of which the fully covered shell contains two different types of nanoparticles. This has been experimentally confirmed using iron oxide (Fe 3 O 4 ) nanoparticles together with silica nanoparticles as shell particles on polystyrene core particles. Cryo-electron tomography was used to visualize the AB binary and ABC ternary supraparticles and to determine the three-dimensional structural characteristics of supraparticles formed under different conditions.

Aggregation-induced emission (AIE) has, since its discovery, become a valuable tool in the field of nanoscience. AIEgenic molecules, which display highly stable fluorescence in an assembled state, have applications in various biomedical fields-including photodynamic therapy. Engineering structure-inherent, AIEgenic nanomaterials with motile properties is, however, still an unexplored frontier in the evolution of this potent technology. Here, we present phototactic/phototherapeutic nanomotors where biodegradable block copolymers decorated with AIE motifs can transduce radiant energy into motion and enhance thermophoretic motility driven by an asymmetric Au nanoshell. The hybrid nanomotors can harness two photon near-infrared radiation, triggering autonomous propulsion and simultaneous phototherapeutic generation of reactive oxygen species. The potential of these nanomotors to be applied in photodynamic therapy is demonstrated in vitro, where near-infrared light directed motion and reactive oxygen species induction synergistically enhance efficacy with a high level of spatial control.

Immunotherapies controlling the adaptive immune system are firmly established, but regulating the innate immune system remains much less explored. The intrinsic interactions between nanoparticles and phagocytic myeloid cells make these materials especially suited for engaging the innate immune system. However, developing nanotherapeutics is an elaborate process. Here, we demonstrate a modular approach that facilitates efficiently incorporating a broad variety of drugs in a nanobiologic platform. Using a microfluidic formulation strategy, we produced apolipoprotein A1-based nanobiologics with favorable innate immune system-engaging properties as evaluated by in vivo screening. Subsequently, rapamycin and three small-molecule inhibitors were derivatized with lipophilic promoieties, ensuring their seamless incorporation and efficient retention in nanobiologics. A short regimen of intravenously administered rapamycin-loaded nanobiologics (mTORi-NBs) significantly prolonged allograft survival in a heart transplantation mouse model. Last, we studied mTORi-NB biodistribution in nonhuman primates by PET/MR imaging and evaluated its safety, paving the way for clinical translation., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Designer particles that are embued with nanomachinery for autonomous motion have great potential for biomedical applications; however, their development is highly demanding with respect to biodegradability/compatibility. Previously, biodegradable propulsive machinery based on enzymes has been presented. However, enzymes are highly susceptible to proteolysis and deactivation in biological milieu. Biodegradable hybrid nanomotors powered by catalytic inorganic nanoparticles provide a proteolytically stable alternative to those based upon enzymes. Herein we describe the assembly of hybrid biodegradable nanomotors capable of transducing chemical energy into motion. Such nanomotors are constructed through a process of compartmentalized synthesis of inorganic MnO 2 nanoparticles (MnPs) within the cavity of organic stomatocytes. We show that the nanomotors remain active in cellular environments and do not compromise cell viability. Effective tumor penetration of hybrid nanomotors is also demonstrated in proof-of-principle experiments. Overall, this work represents a new prospect for engineering of nanomotors that can retain their functionality within biological contexts.

The formation of condensed (compacted) protein phases is associated with a wide range of human disorders, such as eye cataracts, amyotrophic lateral sclerosis, sickle cell anaemia and Alzheimer's disease. However, condensed protein phases have their uses: as crystals, they are harnessed by structural biologists to elucidate protein structures, or are used as delivery vehicles for pharmaceutical applications. The physiochemical properties of crystals can vary substantially between different forms or structures ('polymorphs') of the same macromolecule, and dictate their usability in a scientific or industrial context. To gain control over an emerging polymorph, one needs a molecular-level understanding of the pathways that lead to the various macroscopic states and of the mechanisms that govern pathway selection. However, it is still not clear how the embryonic seeds of a macromolecular phase are formed, or how these nuclei affect polymorph selection. Here we use time-resolved cryo-transmission electron microscopy to image the nucleation of crystals of the protein glucose isomerase, and to uncover at molecular resolution the nucleation pathways that lead to two crystalline states and one gelled state. We show that polymorph selection takes place at the earliest stages of structure formation and is based on specific building blocks for each space group. Moreover, we demonstrate control over the system by selectively forming desired polymorphs through site-directed mutagenesis, specifically tuning intermolecular bonding or gel seeding. Our results differ from the present picture of protein nucleation, in that we do not identify a metastable dense liquid as the precursor to the crystalline state. Rather, we observe nucleation events that are driven by oriented attachments between subcritical clusters that already exhibit a degree of crystallinity. These insights suggest ways of controlling macromolecular phase transitions, aiding the development of protein-based drug-delivery systems and macromolecular crystallography.

Mesoporous silica nanoparticles (MSNs) have been explored extensively as solid supports for proteins in biological and medical applications. Small (<200 nm) MSNs with ordered large pores (>5 nm), capable of encapsulating therapeutic small molecules suitable for delivery applications in vivo, are rare however. Here we present small, elongated, cuboidal, MSNs with average dimensions of 90 × 43 nm that possess disk-shaped cavities, stacked on top of each other, which run parallel to the short axis of the particle. Amine functionalization was achieved by modifying the MSN surface with 3-aminopropyltriethoxysilane or 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane (AP-MSNs and AEP-MSNs) and were shown to have similar dimensions to the nonfunctionalized MSNs. The dimensions of these particles, and their large surface areas as measured by nitrogen adsorption-desorption isotherms, make them ideal scaffolds for protein encapsulation and delivery. We therefore investigated the encapsulation and release behavior for seven model proteins (α-lactalbumin, ovalbumin, bovine serum albumin, catalase, hemoglobin, lysozyme, and cytochrome c). It was discovered that all types of MSNs used in this study allow rapid encapsulation, with a high loading capacity, for all proteins studied. Furthermore, the release profiles of the proteins were tunable. The variation in both rate and amount of protein uptake and release was found to be determined by the surface chemistry of the MSNs, together with the isoelectric point (pI), and molecular weight of the proteins, as well as by the ionic strength of the buffer. These MSNs with their large surface area and optimal dimensions provide a scaffold with a high encapsulation efficiency and controllable release profiles for a variety of proteins, enabling potential applications in fields such as drug delivery and protein therapy.

Binary nanocrystal superlattices, that is, ordered structures of two sorts of nanocolloids, hold promise for a series of functional materials with novel collective properties. Here we show that based on electron tomography a comprehensive, quantitative, three-dimensional characterization of these systems down to the single nanocrystal level can be achieved, which is key in understanding the emerging materials properties. On four binary lattices composed of PbSe, CdSe, and Au nanocrystals, we illustrate that ambiguous interpretations based on two-dimensional transmission electron microscopy can be prevented, nanocrystal sizes and superlattice parameters accurately determined, individual crystallographic point and plane defects studied, and the order/disorder at the top and bottom surfaces imaged. Furthermore, our results suggest that superlattice nucleation and growth occurred at the suspension/air interface and that the unit cells of some lattices are anisotropically deformed upon drying.

Innovations in liquid-phase electron microscopy (LP-EM) have made it possible to perform experiments at the optimized conditions needed to examine soft matter. The main obstacle is conducting experiments in such a way that electron beam radiation can be used to obtain answers for scientific questions without changing the structure and (bio)chemical processes in the sample due to the influence of the radiation. By overcoming these experimental difficulties at least partially, LP-EM has evolved into a new microscopy method with nanometer spatial resolution and sub-second temporal resolution for analysis of soft matter in materials science and biology. Both experimental design and applications of LP-EM for soft matter materials science and biological research are reviewed, and a perspective of possible future directions is given.

By using wet-chemical methods, cubic, tetrahedral, and randomly shaped Rh nanoparticles (NPs) with different surface terminations were synthesized and subsequently deposited on ZrO2 supports. To guide the NP shape, three capping agents were used during the synthesis: polyvinylpyrrolidone (PVP), trimethyl(tetradecyl)ammonium bromide (TTAB), and oleylamine (OAm). TTAB and PVP could not be completely removed from the final catalyst, leaving a capping residue as confirmed by X-ray photoelectron spectroscopy (XPS). In contrast, OAm could be fully removed. The influence of the NP shape and the influence of the capping agents were evaluated under CO hydrogenation conditions. Both the PVP and TTAB residues blocked parts of the Rh surface and dominated catalytic activity beyond the effects from NP shape and surface termination. OAm could be successfully removed. The extent of metal surface blocking by the capping residue, probed by chemisorption, is larger than the observed reduction in CO hydrogenation activity. This suggests that a majority of less-active sites are being blocked by the capping residue and that successful removal of the residue from the most active sites is possible. [ABSTRACT FROM AUTHOR]

Biological systems show impressive control over the shape, size and organization of mineral structures, which often leads to advanced physical properties that are tuned to the function of these materials. Such control is also found in magnetotactic bacteria, which produce-in aqueous medium and at room temperature-magnetite nanoparticles with precisely controlled morphologies and sizes that are generally only accessible in synthetic systems with the use of organic solvents and/or the use of high-temperature methods. The synthesis of magnetite under biomimetic conditions, that is, in water and at room temperature and using polymeric additives as control agents, is of interest as a green production method for magnetic nanoparticles. Inspired by the process of magnetite biomineralization, a rational approach is taken by the use of a solid precursor for the synthesis of magnetite nanoparticles. The conversion of a ferrous hydroxide precursor, which we demonstrate with cryo-TEM and low-dose electron diffraction, is used to achieve control over the solution supersaturation such that crystal growth can be regulated through the interaction with poly-(α,β)- dl-aspartic acid, a soluble, negatively charged polymer. In this way, stable suspensions of nanocrystals are achieved that show remanence and coercivity at the size limit of superparamagnetism, and which are able to align their magnetic moments forming strings in solution as is demonstrated by cryo-electron tomography. [ABSTRACT FROM AUTHOR]

Postsynthesis ammonium treatment induces a substantial increase in the catalytic activity of Au/Ti-SBA-15 catalysts for the direct vapor-phase epoxidation of propylene using hydrogen and oxygen. The PO formation rate of a calcined Au/Ti-SBA-15 catalyst prepared by this method increased from 4.3 mgPO h−1 g−1 cat to 37.2 mgPO h−1 g−1 cat at 200 °C compared with a catalyst prepared in an identical manner without this treatment. The catalysts were characterized by XRD, N2-sorption, UV–vis–NIR DRS, 29Si MAS NMR, FT-IR spectroscopy, and TEM to gain insight into the relationship between ammonia treatment and catalyst activity. 29Si MAS NMR measurements proved that the ammonium nitrate solution caused hydrolysis of ph name="sbnd" />Oph name="tbnd" /> or ph name="sbnd" />Oph name="tbnd" /> bonds, resulting in a Ti-SBA-15 surface with a greater amount of surface hydroxyl groups. FT-IR measurements indicated the presence of amine species that favor the homogeneous deposition of Au nanoparticles. This was confirmed by TEM measurements showing greater metal dispersion for NH4NO3-treated Au/Ti-SBA-15 materials. [Copyright &y& Elsevier]

Bicontinuousnanospheres have been observed (although rarely) froma variety of block copolymers with architectural and compositionalcomplexity, and often in the presence of additives. Unlocking keyfeatures involved in their formation presents possibilities for bicontinuousaggregates with varied functionality and application. An attractiveprospect is the ability to form them from much simpler polymeric structuresderived from facile syntheses. To that end, we herein report the formationof bicontinuous aggregates from simple amorphous amphiphilic diblockcopolymers of poly(ethylene oxide)-b-poly(n-butyl methacrylate), analogous to our previous reportof the same from a semicrystalline comb-like block copolymer. Moreover,we demonstrate that polymorphism can be achieved by altering the relativeblock proportions and the nonselective cosolvent. We find that thepolymeric structure is not the dominating factor in the formationof bicontinuous nanospheres but that the choice of cosolvent for thehydrophilic block appears to have greater influence on determiningthe end morphology. [ABSTRACT FROM AUTHOR]