SupraCells: Living Mammalian Cells Protected within Functional Modular Nanoparticle-Based Exoskeletons.

Creating a synthetic exoskeleton from abiotic materials to protect delicate mammalian cells and impart them with new functionalities could revolutionize fields like cell-based sensing and create diverse new cellular phenotypes. Herein, the concept of "SupraCells," which are living mammalian cells encapsulated and protected within functional modular nanoparticle-based exoskeletons, is introduced. Exoskeletons are generated within seconds through immediate interparticle and cell/particle complexation that abolishes the macropinocytotic and endocytotic nanoparticle internalization pathways that occur without complexation.

Metal-Organic Framework Nanoparticle-Assisted Cryopreservation of Red Blood Cells.

The development of hybrid nanomaterials mimicking antifreeze proteins that can modulate/inhibit the growth of ice crystals for cell/tissue cryopreservation has attracted increasing interests. Herein, we describe the first utilization of zirconium (Zr)-based metal-organic framework (MOF) nanoparticles (NPs) with well-defined surface chemistries for the cryopreservation of red blood cells (RBCs) without the need of any (toxic) organic solvents. Distinguishing features of this cryoprotective approach include the exceptional water stability, low hemolytic activity, and the long periodic arrangement of organic linkers on the surface of MOF NPs, which provide a precise spacing of hydrogen donors to recognize and match the ice crystal planes.

Modular Metal-Organic Polyhedra Superassembly: From Molecular-Level Design to Targeted Drug Delivery.

Targeted drug delivery remains at the forefront of biomedical research but remains a challenge to date. Herein, the first superassembly of nanosized metal-organic polyhedra (MOP) and their biomimetic coatings of lipid bilayers are described to synergistically combine the advantages of micelles and supramolecular coordination cages for targeted drug delivery. The superassembly technique affords unique hydrophobic features that endow individual MOP to act as nanobuilding blocks and enable their superassembly into larger and well-defined nanocarriers with homogeneous sizes over a broad range of diameters.

Establishing the effects of mesoporous silica nanoparticle properties on in vivo disposition using imaging-based pharmacokinetics.

The progress of nanoparticle (NP)-based drug delivery has been hindered by an inability to establish structure-activity relationships in vivo. Here, using stable, monosized, radiolabeled, mesoporous silica nanoparticles (MSNs), we apply an integrated SPECT/CT imaging and mathematical modeling approach to understand the combined effects of MSN size, surface chemistry and routes of administration on biodistribution and clearance kinetics in healthy rats. We show that increased particle size from ~32- to ~142-nm results in a monotonic decrease in systemic bioavailability, irrespective of route of administration, with corresponding accumulation in liver and spleen.

Mesoporous Silica-Based Nanoparticles for Light-Actuated Biomedical Applications via Near-Infrared Two-Photon Absorption.

In this review, we highlight the design of nanomaterials for two-photon excitation, in order to treat tumors with a high accuracy. Indeed two-photon excitation allows remote control of the nanoparticles with a spatio-temporal resolution. The nanomaterials are based on mesoporous silica-organosilica nanoparticles including core-shell systems.

Biodegradable Silica-Based Nanoparticles: Dissolution Kinetics and Selective Bond Cleavage.

Silica-based nanomaterials are extensively used in industrial applications and academic biomedical research, thus properly assessing their toxicity and biodegradability is essential for their safe and effective formulation and use. Unfortunately, there is often a lot of confusion in the literature with respect to the toxicity and biodegradability of silica since various studies have yielded contradictory results. In this contribution, we first endeavor to underscore that the simplistic model of silica should be discarded in favor of a more realistic model recognizing that all silicas are not created equal and should thus be considered in the plural as silicas and silica hybrids, which indeed hold various biocompatibility and biodegradability profiles.

Author Correction: Ultra-thin enzymatic liquid membrane for CO separation and capture.

The original version of this Article contained an error in the spelling of the author Stanley S. Chou, which was incorrectly given as Stan Chou. This has now been corrected in both the PDF and HTML versions of the Article.

Ultra-thin enzymatic liquid membrane for CO separation and capture.

The limited flux and selectivities of current carbon dioxide membranes and the high costs associated with conventional absorption-based CO sequestration call for alternative CO separation approaches. Here we describe an enzymatically active, ultra-thin, biomimetic membrane enabling CO capture and separation under ambient pressure and temperature conditions. The membrane comprises a ~18-nm-thick close-packed array of 8 nm diameter hydrophilic pores that stabilize water by capillary condensation and precisely accommodate the metalloenzyme carbonic anhydrase (CA).

Two-Photon-Excited Silica and Organosilica Nanoparticles for Spatiotemporal Cancer Treatment.

Coherent two-photon-excited (TPE) therapy in the near-infrared (NIR) provides safer cancer treatments than current therapies lacking spatial and temporal selectivities because it is characterized by a 3D spatial resolution of 1 µm and very low scattering. In this review, the principle of TPE and its significance in combination with organosilica nanoparticles (NPs) are introduced and then studies involving the design of pioneering TPE-NIR organosilica nanomaterials are discussed for bioimaging, drug delivery, and photodynamic therapy. Organosilica nanoparticles and their rich and well-established chemistry, tunable composition, porosity, size, and morphology provide ideal platforms for minimal side-effect therapies via TPE-NIR.

Mesoporous Silica and Organosilica Nanoparticles: Physical Chemistry, Biosafety, Delivery Strategies, and Biomedical Applications.

Predetermining the physico-chemical properties, biosafety, and stimuli-responsiveness of nanomaterials in biological environments is essential for safe and effective biomedical applications. At the forefront of biomedical research, mesoporous silica nanoparticles and mesoporous organosilica nanoparticles are increasingly investigated to predict their biological outcome by materials design. In this review, it is first chronicled that how the nanomaterial design of pure silica, partially hybridized organosilica, and fully hybridized organosilica (periodic mesoporous organosilicas) governs not only the physico-chemical properties but also the biosafety of the nanoparticles.

Thermoresponsive pegylated bubble liposome nanovectors for efficient siRNA delivery via endosomal escape.

Aim: Improving the delivery of siRNA into cancer cells via bubble liposomes. Designing a thermoresponsive pegylated liposome through the introduction of ammonium bicarbonate salt into liposomes so as to control their endosomal escape for gene therapy.

Methods: A sub-200 nm nanovector was fully characterized and examined for cellular uptake, cytotoxicity, endosomal escape and gene silencing.

Cellular Internalization and Biocompatibility of Periodic Mesoporous Organosilica Nanoparticles with Tunable Morphologies: From Nanospheres to Nanowires.

This work describes the sol-gel syntheses of para-substituted phenylene-bridged periodic mesoporous organosilica (PMO) nanoparticles (NPs) with tunable morphologies ranging from nanowires to nanospheres. The findings show the key role of the addition of organic co-solvents in the aqueous templates on the final morphologies of PMO NPs. Other factors such as the temperature, the stirring speed, and the amount of organic solvents also influence the shape of PMO NPs.

Colloidal Gold Nanoclusters Spiked Silica Fillers in Mixed Matrix Coatings: Simultaneous Detection and Inhibition of Healthcare-Associated Infections.

Healthcare-associated infections (HAIs) are the infections that patients get while receiving medical treatment in a medical facility with bacterial HAIs being the most common. Silver and gold nanoparticles (NPs) have been successfully employed as antibacterial motifs; however, NPs leaching in addition to poor dispersion and overall reproducibility are major hurdles to further product development. In this study, the authors design and fabricate a smart antibacterial mixed-matrix membrane coating comprising colloidal lysozyme-templated gold nanoclusters as nanofillers in poly(ethylene oxide)/poly(butylene terephthalate) amphiphilic polymer matrix.

Degradability and Clearance of Silicon, Organosilica, Silsesquioxane, Silica Mixed Oxide, and Mesoporous Silica Nanoparticles.

The biorelated degradability and clearance of siliceous nanomaterials have been questioned worldwide, since they are crucial prerequisites for the successful translation in clinics. Typically, the degradability and biocompatibility of mesoporous silica nanoparticles (MSNs) have been an ongoing discussion in research circles. The reason for such a concern is that approved pharmaceutical products must not accumulate in the human body, to prevent severe and unpredictable side-effects.

Engineering Hydrophobic Organosilica Nanoparticle-Doped Nanofibers for Enhanced and Fouling Resistant Membrane Distillation.

Engineering and scaling-up new materials for better water desalination are imperative to find alternative fresh water sources to meet future demands. Herein, the fabrication of hydrophobic poly(ether imide) composite nanofiber membranes doped with novel ethylene-pentafluorophenylene-based periodic mesoporous organosilica nanoparticles is reported for enhanced and fouling resistant membrane distillation. Novel organosilica nanoparticles were homogeneously incorporated into electrospun nanofiber membranes depicting a proportional increase of hydrophobicity to the particle contents.

Biodegradable Magnetic Silica@Iron Oxide Nanovectors with Ultra-Large Mesopores for High Protein Loading, Magnetothermal Release, and Delivery.

The delivery of large cargos of diameter above 15nm for biomedical applications has proved challenging since it requires biocompatible, stably-loaded, and biodegradable nanomaterials. In this study, we describe the design of biodegradable silica-iron oxide hybrid nanovectors with large mesopores for large protein delivery in cancer cells. The mesopores of the nanomaterials spanned from 20 to 60nm in diameter and post-functionalization allowed the electrostatic immobilization of large proteins (e.

Organosilica hybrid nanomaterials with a high organic content: syntheses and applications of silsesquioxanes.

Organic-inorganic hybrid materials garner properties from their organic and inorganic matrices as well as synergistic features, and therefore have recently attracted much attention at the nanoscale. Non-porous organosilica hybrid nanomaterials with a high organic content such as silsesquioxanes (R-SiO, with R organic groups) and bridged silsesquioxanes (OSi-R-SiO) are especially attractive hybrids since they provide 20 to 80 weight percent of organic functional groups in addition to the known chemistry and stability of silica. In the organosilica family, silsesquioxanes (R-SiO) stand between silicas (SiO) and silicones (RSiO), and are variously called organosilicas, ormosil (organically-modified silica), polysilsesquioxanes and silica hybrids.

Nanodiamond-PMO for two-photon PDT and drug delivery.

In this article, we highlight the properties of nanodiamonds (ND), which were encapsulated in periodic mesoporous organosilica nanoparticles (PMO) and were able to generate reactive oxygen species for photodynamic applications upon two-photon excitation (TPE). The ND@PMO nanoparticles were characterized by various techniques and were then loaded with the anti-cancer drug doxorubicin. The release of the drug was pH sensitive and a synergistic cancer cell killing effect was observed when cancer cells were incubated with doxorubicin-loaded ND@PMO and irradiated with two-photon excitation at 800 nm.

Fluorescent periodic mesoporous organosilica nanoparticles dual-functionalized via click chemistry for two-photon photodynamic therapy in cells.

The synthesis of ethenylene-based periodic mesoporous organosilica nanoparticles for two-photon imaging and photodynamic therapy of breast cancer cells is described. A dedicated two-photon absorbing fluorophore possessing four triethoxysilyl groups and having large two-photon absorption in the near IR region, and azidopropyltriethoxysilane were incorporated into the structure. The mesoporous nanoparticles of 100 nm diameter were further functionalized by means of click chemistry with a propargylated fluorescent bromo-quinoline photosensitizer able to generate singlet oxygen.

Biodegradable Oxamide-Phenylene-Based Mesoporous Organosilica Nanoparticles with Unprecedented Drug Payloads for Delivery in Cells.

We describe biodegradable mesoporous hybrid nanoparticles (NPs) in the presence of proteins and their applications for drug delivery. We synthesized oxamide phenylene-based mesoporous organosilica nanoparticles (MON) in the absence of a silica source which had remarkably high organic content and high surface areas. Oxamide functions provided biodegradability in the presence of trypsin model proteins.

Periodic Mesoporous Organosilica Nanoparticles with Controlled Morphologies and High Drug/Dye Loadings for Multicargo Delivery in Cancer Cells.

Despite the worldwide interest generated by periodic mesoporous organosilica (PMO) bulk materials, the design of PMO nanomaterials with controlled morphology remains largely unexplored and their properties unknown. In this work, we describe the first study of PMO nanoparticles (NPs) based on meta-phenylene bridges, and we conducted a comparative structure-property relationship investigation with para-phenylene-bridged PMO NPs. Our findings indicate that the change of the isomer drastically affects the structure, morphology, size, porosity and thermal stability of PMO materials.

Protein-gold clusters-capped mesoporous silica nanoparticles for high drug loading, autonomous gemcitabine/doxorubicin co-delivery, and in-vivo tumor imaging.

Functional nanocarriers capable of transporting high drug contents without premature leakage and to controllably deliver several drugs are needed for better cancer treatments. To address this clinical need, gold cluster bovine serum albumin (AuNC@BSA) nanogates were engineered on mesoporous silica nanoparticles (MSN) for high drug loadings and co-delivery of two different anticancer drugs. The first drug, gemcitabine (GEM, 40wt%), was loaded in positively-charged ammonium-functionalized MSN (MSN-NH3(+)).

Multifunctional Gold-Mesoporous Silica Nanocomposites for Enhanced Two-Photon Imaging and Therapy of Cancer Cells.

Three dimensional sub-micron resolution has made two-photon nanomedicine a very promising medical tool for cancer treatment since current techniques cause significant side effects for lack of spatial selectivity. Two-photon-excited (TPE) photodynamic therapy (PDT) has been achieved via mesoporous nanoscaffolds, but the efficiency of the treatment could still be improved. Herein, we demonstrate the enhancement of the treatment efficiency via gold-mesoporous organosilica nanocomposites for TPE-PDT in cancer cells when compared to mesoporous organosilica particles.