Mesoporous silica nanoparticles as vehicles for intracellular trafficking and controlled release

Mesoporous silica nanoparticles (MSN) are introduced as vehicles for the intracellular delivery of a variety of molecular cargoes into living cells. The general synthesis of the material, the dependence of its uptake upon surface functionalization as well as its toxicity are investigated in the work

Indometacin loading and in vitro release properties from novel carbopol coated spherical mesoporous silica nanoparticles

Spherical MCM-41 silica nanosized particles were synthesized and post synthesis modified by 3-aminopropyltriethoxysilane (APTES) in order to prepare amino-functionalized carrier. Both types of silica particleswere loaded with indometacin and further coated with carbopol. The preservation of morphology and pore structure of the particles was observed by XRD, TEM and N2 physisorption. FT-IR spectroscopy revealed the interaction between carboxyl groups of indometacin and the amino groups of the functionalized MCM-41. Amino-functionalization of the carrier resulted in higher degree of indometacin loading in comparison to the parent MCM-41, 39% vs. 30%, respectively. The coating of drug loaded amino-MCM-41 silica particles with carbopol significantly reduced the initial burst release of indometacin. Both silica carriers demonstrated no cytotoxicity on HL-60 (acute myeloid leukemia) and K-562 (chronic myeloid leukemia) cell lines

Final Report: NASA X-HAB Space Habitat Research Group Iowa State University

This document serves as the Final Report for Iowa State University's Space Habitat group to fulfill the specifications of NASA's eXploration Systems and Habitation (X-Hab) 2019 Academic Innovation Challenge for the 'Implementation of Advanced Sorbents in a Carbon Dioxide Management Unit' portion of the challenge. The scope of this document includes a description of the current Carbon Dioxide management systems implemented on ISS, a description of the groups design, a description of the operational environment and scenarios, risks and mitigations, performance and testing results of the system, outreach, and future work

Effect of Surface Functionalization of MCM-41-Type Mesoporous Silica Nanoparticles on the Endocytosis by Human Cancer Cells

We have synthesized a series of MCM-41-type mesoporous silica nanoparticles (MSN). The surface of the MSNs are functionalized with 3-aminopropyl (AP), 3-guanidinopropyl (GP), 3-[N-(2-guanidinoethyl)guanidino]propyl (GEGP), and N-folate-3-aminopropyl (FAP). In contrast to the ζ-potential of −18.4 mV for FITC-MSN, the values of ζ-potential for AP-, GP-, GEGP-, and FAP-functionalized FITC-MSNs in 100 mM PBS buffer (pH 7.4) increased positively from −11.3, −10.6, −4.0, to +4.9 mV, respectively. The uptake efficiency, endocytosis mechanism, and biocompatibility of these organically functionalized MSNs were investigated with human cervical cancer cells (HeLa). Flow cytometry results suggested that the endocytosis of MSN could be manipulated by different surface functionalization. The immunocytochemistry study indicated that the uptake of these MSNs by HeLa cells was surface functional group dependent and involved several different mechanisms of endocytosis. Confocal fluorescence micrographs showed that the different surface functionalities of MSNs could also affect their ability to escape endosomal entrapment, which is a key factor in designing effective intracellular delivery vehicles

Measuring Long-Range 13C–13C Correlations on a Surface under Natural Abundance Using Dynamic Nuclear Polarization-Enhanced Solid-State Nuclear Magnetic Resonance

We report that spatial (\u3c1 \u3enm) proximity between different molecules in solid bulk materials and, for the first time, different moieties on the surface of a catalyst, can be established without isotope enrichment by means of homonuclear CHHC solid-state nuclear magnetic resonance experiment. This 13C–13C correlation measurement, which hitherto was not possible for natural-abundance solids, was enabled by the use of dynamic nuclear polarization. Importantly, it allows the study of long-range correlations in a variety of materials with high resolution

Mesoporous Silica Nanoparticles for Intracellular Delivery of Membrane-Impermeable Proteins

An MCM-41-type mesoporous silica nanoparticle (MSN) material with a large average pore diameter (5.4 nm) is synthesized and characterized. The in vitro uptake and release profiles of cytochrome c by the MSN were investigated. The enzymatic activity of the released protein was quantitatively analyzed and compared with that of the native cytochrome c in physiological buffer solutions. We found that the enzymes released from the MSNs are still functional and highly active in catalyzing the oxidation of 2,2‘-azino-bis(3-ethylbenzthiazoline-6-sulfonate) (ABTS) by hydrogen peroxide. In contrast to the fact that cytochrome c is a cell-membrane-impermeable protein, we discovered that the cytochrome c-encapsulated MSNs could be internalized by live human cervical cancer cells (HeLa) and the protein could be released into the cytoplasm. We envision that these MSNs with large pores could serve as a transmembrane delivery vehicle for controlled release of membrane-impermeable proteins in live cells, which may lead to many important biotechnological applications including therapeutics and metabolic manipulation of cells

Deactivation of Ceria Supported Palladium through C–C Scission during Transfer Hydrogenation of Phenol with Alcohols

The stability of palladium supported on ceria (Pd/CeO2) was studied during liquid flow transfer hydrogenation using primary and secondary alcohols as hydrogen donors. For primary alcohols, the ceria support was reduced to cerium hydroxy carbonate within 14 h and was a contributing factor toward catalyst deactivation. For secondary alcohols, cerium hydroxy carbonate was not observed during the same time period and the catalyst was stable upon prolonged reaction. Regeneration through oxidation/reduction does not restore initial activity likely due to irreversible catalyst restructuring. A deactivation mechanism involving C–C scission of acyl and carboxylate intermediates is propose

High Throughput Screening of 3D Printable Resins: Adjusting the Surface and Catalytic Properties of Multifunctional Architectures

Identification of 3D printable materials is crucial to expand the breadth of physical and chemical properties attainable by additive manufacturing. Stereolithography (SLA), a widespread 3D printing method based on resin photo-polymerization, is ideally suited for exploring a large variety of monomers to produce functional three-dimensional solids of diverse properties. However, for most of the commercially available SLA 3D printers, screening monomers and resin compositions requires large volumes (~150 mL) in each printing cycle, making the process costly and inefficient. Herein, a high throughput block (HTB) adaptor was developed to screen arrays of monomers and resin compositions, consuming lower volumes (\u3c 2 mL) and less time per print (\u3c 1/16 based on a 44 matrix) than using the original hardware. Using this approach, a library of materials with different surface hydrophobicities were 3D printed by including long chain acrylates in the resins. In addition, several metal salts were dissolved in an acrylic acid-based resin, 3D printed and screened as heterogeneous catalysts for the selective aerobic oxidation of benzyl alcohol to benzaldehyde. Cu(II)-based resins produced the most active structures. Combinations of Cu(II) and long chain acrylate monomers were then used to 3D print complex catalytic architectures with varying degrees of hydrophobicity. Linear relationships were observed between 3D printed surface area, surface hydrophobicity and catalyst performance. For a high surface Schwarz P topology ca. 60 % enhancement in the catalytic activity of Cu(II) was attained by replacing the parent resin with one containing hydrophobic isodecyl groups, indicating that the immediate environment of the catalytic site affected its performance. The HTB enables fast screening of resins for 3D printing multifunctional architectures with intrinsic catalytic activity, tunable surface properties, and minimal waste

Probing surface hydrogen bonding and dynamics by natural abundance, multidimensional, 17O DNP-NMR spectroscopy

Dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (SSNMR) spectroscopy is increasingly being used as a tool for the atomic-level characterization of surface sites. DNP surface-enhanced SSNMR spectroscopy of materials has, however, been limited to studying relatively receptive nuclei, and the particularly rare 17O nuclide, which is of great interest for materials science, has not been utilized. We demonstrate that advanced 17O SSNMR experiments can be performed on surface species at natural isotopic abundance using DNP. We use 17O DNP surface-enhanced 2D SSNMR to measure 17O{1H} HETCOR spectra as well as dipolar oscillations on a series of thermally treated mesoporous silica nanoparticle samples having different pore diameters. These experiments allow for a nonintrusive and unambiguous characterization of hydrogen bonding and dynamics at the surface of the material; no other single experiment can give such details about the interactions at the surface. Our data show that, upon drying, strongly hydrogen-bonded surface silanols, whose motions are greatly restricted by the interaction when compared to lone silanols, are selectively dehydroxylated

Transfer of Individual Micro- and Nanoparticles for High- Precision 3D Analysis Using 360° Electron Tomography

A versatile approach is demonstrated, providing a general routine for an extensive and advanced 3D characterization of individually selected micro- and nanoparticles, enabling the combination of complementary and scale-bridging techniques. Quintessential to the method is the transfer of individual particles onto tailored tips using a conventional scanning electron microscope equipped with a suitable micromanipulator. The method enables a damage- and contamination-free preparation of freestanding particles. This is of significant importance for applications addressing the measurement of structural, physical, and chemical properties of specifically selected particles, such as 360° electron tomography, atom probe tomography, nano X-ray tomography, or optical near-field measurements. In this context, the method is demonstrated for 360° electron tomography of micro-/macroporous zeolite particles with sizes in the micrometer range and mesoporous alpha-hematite nanoparticles exhibiting sizes of 50–100 nm, including detailed pre- and postcharacterization on the nanoscale.“Deutsche Forschungsgemeinschaft” (DFG) within the framework of the SPP 1570 (project DFG SP 648/4-3 “3D analysis of complex pore structures using ET and high-resolution TEM”) and the research training group GRK 1896 (“In situ Microscopy with Electrons, X-rays and Scanning Probes”) as well as through the Cluster of Excellence “Engineering of Advanced Materials” at the Friedrich-Alexander-Universität Erlangen-Nürnberg (Germany)FIBJulian Losche