Effect of Crystal Defect on Gas Sensing Properties of Co3O4 Nanoparticles.

Crystal growth-controlled Co3O4 nanoparticles were prepared to examine gas sensing properties. A cube-like, an irregular shaped, and three kinds of raspberry-type structures were observed by morphology analysis. The raspberry-type structures have an expanded lattice volume with a large oxygen deficiency area, and the cube-like structure has a contracted lattice volume as compared to the irregular shaped structure. The raspberry-type structures exhibited a higher sensor signal response than the others. A relationship between sensor properties and crystal defect was investigated, and it was revealed that the gas selectivity to a high dipole moment value of a reducing gas molecule increased with increasing oxygen deficiency area of the Co3O4 nanoparticle. It was considered that the oxygen deficiency area acted as an important reaction site, which can be attributed to the selective reaction of the Co3O4 nanoparticle with gas molecules.

Spiky-shaped niobium pentoxide nano-architecture: highly stable and recoverable Lewis acid catalyst.

Niobium pentoxide particles with a complex three-dimensional (3D) nanostructure consisting of a spiky structure have been developed as recyclable and recoverable Lewis acid catalysts. The morphology of the niobium pentoxide was successfully controlled from 1D to 3D via a bridging-ligand-assisted hydrothermal treatment, without changing the crystal structure. Compared with dispersed one-dimensional (1D) niobium pentoxide nanorods with a major-axis length and minor-axis length of 20 nm and 5-8 nm, respectively, the spiky-shaped niobium pentoxide composed of 300 nm spherical cores and nanorods with a minor-axis length of 5 nm maintained its surface nanostructure even after calcination at 400 °C in air. The 400 °C-calcined spiky particles exhibited the highest production rate of 2-((4-methoxyphenyl)amino)-2-phenylacetonitrile (0.115 mmol m-2) in a Strecker reaction, resulting in a nanoscale and ordered surface structure of spiky particles that simultaneously exhibit high specific reactivity and high structural stability. Acid site analysis and Raman spectroscopy revealed that stable nanorods that grew in the (001) orientation functioned as Lewis acid catalysts and that the origin of the acidity was a flexible Nb-O polyhedral structure in the single-nanoscale (<10 nm) niobium oxide rods. This study proposes that the spiky-shaped niobium pentoxide exhibits sintering resistivity and high activity and has potential applications as a recoverable and recyclable solid acid catalyst.

Formation and Thermal Behaviors of Ternary Silicon Oxycarbides derived from Silsesquioxane Derivatives.

Silsesquioxane (SQ) derivatives possessing intramolecular H2C = CH- groups and Si-H groups were designed as precursors for ternary silicon oxycarbide (SiOC). By using R-Si(OMe)3, H-Si(OEt)3 and (H-Si(Me)2)2O as starting compounds, SQ derivatives of VH-SQ (R = vinyl) and St-H-SQ (R = stylyl) were successfully synthesized through the conventional sol-gel route. Simultaneous thermogravimetric and mass spectroscopic analyses up to 1000 °C revealed that in situ cross-linking via hydrosilylation and demethanation of VH-SQ suppressed the evolution of gaseous hydrocarbon species to afford amorphous SiOC having a composition close to the desired stoichiometric SiO2(1-x)Cx (x = ca. 0.3) with a high yield. The effect of carbon content on the phase separation and crystallization of the SQ-derived amorphous SiOC was studied by several spectroscopic analyses and TEM observation. The results were discussed aiming to develop a novel polymer-derived ceramics (PDCs) route for in situ formation of binary ß-SiC-amorphous SiO2 nanocomposites with enhanced thermal and mechanical stability.

Complex Three-Dimensional Co3O4 Nano-Raspberry: Highly Stable and Active Low-temperature CO Oxidation Catalyst.

Highly stable and active low-temperature CO oxidation catalysts without noble metals are desirable to achieve a sustainable society. While zero-dimensional to three-dimensional Co3O4 nanoparticles show high catalytic activity, simple-structured nanocrystals easily self-aggregate and become sintered during catalytic reaction. Thus, complex three-dimensional nanostructures with high stability are of considerable interest. However, the controlled synthesis of complex nanoscale shapes remains a great challenge as no synthesis theory has been established. In this study, 100 nm raspberry-shaped nanoparticles composed of 7⁻8 nm Co3O4 nanoparticles were synthesized by hydrothermally treating cobalt glycolate solution with sodium sulfate. Surface single nanometer-scale structures with large surface areas of 89 m²·g-1 and abundant oxygen vacancies were produced. The sulfate ions functioned as bridging ligands to promote self-assembly and suppress particle growth. The Co3O4 nano-raspberry was highly stable under catalytic tests at 350 °C and achieved nearly 100% CO conversion at room temperature. The addition of bridging ligands is an effective method to control the formation of complex but ordered three-dimensional nanostructures that possessed extreme thermal and chemical stability and exhibited high performance.

High-throughput full-length single-cell mRNA-seq of rare cells.

Single-cell characterization techniques, such as mRNA-seq, have been applied to a diverse range of applications in cancer biology, yielding great insight into mechanisms leading to therapy resistance and tumor clonality. While single-cell techniques can yield a wealth of information, a common bottleneck is the lack of throughput, with many current processing methods being limited to the analysis of small volumes of single cell suspensions with cell densities on the order of 107 per mL. In this work, we present a high-throughput full-length mRNA-seq protocol incorporating a magnetic sifter and magnetic nanoparticle-antibody conjugates for rare cell enrichment, and Smart-seq2 chemistry for sequencing. We evaluate the efficiency and quality of this protocol with a simulated circulating tumor cell system, whereby non-small-cell lung cancer cell lines (NCI-H1650 and NCI-H1975) are spiked into whole blood, before being enriched for single-cell mRNA-seq by EpCAM-functionalized magnetic nanoparticles and the magnetic sifter. We obtain high efficiency (> 90%) capture and release of these simulated rare cells via the magnetic sifter, with reproducible transcriptome data. In addition, while mRNA-seq data is typically only used for gene expression analysis of transcriptomic data, we demonstrate the use of full-length mRNA-seq chemistries like Smart-seq2 to facilitate variant analysis of expressed genes. This enables the use of mRNA-seq data for differentiating cells in a heterogeneous population by both their phenotypic and variant profile. In a simulated heterogeneous mixture of circulating tumor cells in whole blood, we utilize this high-throughput protocol to differentiate these heterogeneous cells by both their phenotype (lung cancer versus white blood cells), and mutational profile (H1650 versus H1975 cells), in a single sequencing run. This high-throughput method can help facilitate single-cell analysis of rare cell populations, such as circulating tumor or endothelial cells, with demonstrably high-quality transcriptomic data.

Size-tunable drug-delivery capsules composed of a magnetic nanoshell.

Nano-sized FePt capsules with two types of ultrathin shell were fabricated using a template method for use in a nano-scale drug delivery system. One capsule was composed of an inorganic-organic hybrid shell of a water-soluble polymer and FePt nanoparticles, and the other capsule was composed of a network of fused FePt nanoparticles. We demonstrated that FePt nanoparticles selectively accumulated on the polymer molecules adsorbed on the template silica particles, and investigated the morphologies of the particle accumulation by changing the concentration of the polymer solution with which the template particles were treated. Capsular size was reduced from 340 to less than 90 nm by changing the size of the silica template particles, and the shell thickness was controlled by changing the amount of FePt nanoparticles adsorbed on the template particles. The hybrid shell was maintained by the connection of FePt nanoparticles and polymer molecules, and the shell thickness was 10 nm at the maximum. The FePt network shell was fabricated by hydrothermal treatment of the FePt/polymer-modified silica composite particles. The FePt network shell was produced from only the FePt alloy, and the shell thickness was 3 nm. Water-soluble anti-cancer drugs could be loaded into the hollow space of FePt network capsules, and lipid-coated FePt network capsules loaded with anti-cancer drugs showed cellular toxicity. The nano-sized capsular structure and the ultrathin shell suggest applicability as a drug carrier in magnetically guided drug delivery systems.

A magnetically guided anti-cancer drug delivery system using porous FePt capsules.

Magnetic carriers with efficient loading, delivery, and release of drugs are required for magnetically guided drug delivery system (DDS) as the potential cancer therapy. The present article describes the fabrication of porous FePt capsules approximately 340 nm in diameter with large pores of 20 nm in an ultrathin shell of 10 nm and demonstrates their application to a magnetically guided DDS in vitro. An aqueous anti-cancer drug is easily introduced in the hollow space of the capsules without external stimuli and released to cancer cells on cue through the magnetic shell composed of an ordered-alloy FePt network structure, which exhibits superparamagnetic features at approximately body temperature. The drug-loaded magnetic capsules coated with a lipid membrane are efficiently guided to the cancer cells within 15 min using a NdFeB magnet (0.2 T), and more than 70% of the cancer cells are destroyed.

Nanomedicine for cancer: lipid-based nanostructures for drug delivery and monitoring.

Recent advances in nanotechnology, materials science, and biotechnology have led to innovations in the field of nanomedicine. Improvements in the diagnosis and treatment of cancer are urgently needed, and it may now be possible to achieve marked improvements in both of these areas using nanomedicine. Lipid-coated nanoparticles containing diagnostic or therapeutic agents have been developed and studied for biomedical applications and provide a nanomedicine strategy with great potential. Lipid nanoparticles have cationic headgroups on their surfaces that bind anionic nucleic acids and contain hydrophobic drugs at the lipid membrane and hydrophilic drugs inside the hollow space in the interior. Moreover, researchers can design nanoparticles to work in combination with external stimuli such as magnetic field, light, and ionizing radiation, which adds further utility in biomedical applications. In this Account, we review several examples of lipid-based nanoparticles and describe their potential for cancer treatment and diagnosis. (1) The development of a lipid-based nanoparticle that included a promoter-enhancer and transcriptional activator greatly improved gene therapy. (2) The addition of a radiosensitive promoter to lipid nanoparticles was sufficient to confer radioisotope-activated expression of the genes delivered by the nanoparticles. (3) We successfully tailored lipid nanoparticle composition to increase gene transduction in scirrhous gastric cancer cells. (4) When lipophilic photosensitizing molecules were incorporated into lipid nanoparticles, those particles showed an increased photodynamic cytotoxic effect on the target cancer. (5) Coating an Fe(3)O(4) nanocrystal with lipids proved to be an efficient strategy for magnetically guided gene-silencing in tumor tissues. (6) An Fe(16)N(2)/lipid nanocomposite displayed effective magnetism and gene delivery in cancer cells. (7) Lipid-coated magnetic hollow capsules carried aqueous anticancer drugs and delivered them in response to a magnetic field. (8) Fluorescent lipid-coated and antibody-conjugated magnetic nanoparticles detected cancer-associated antigen in a microfluidic channel. We believe that the continuing development of lipid-based nanomedicine will lead to the sensitive minimally invasive treatment of cancer. Moreover, the fusion of different scientific fields is accelerating these developments, and we expect these interdisciplinary efforts to have considerable ripple effects on various fields of research.

Ferromagnetic FePt-nanoparticles/polycation hybrid capsules designed for a magnetically guided drug delivery system.

The present Article describes the synthesis of ferromagnetic capsules approximately 330 nm in diameter with a nanometer-thick shell to apply to magnetic carriers in a magnetically guided drug delivery system. The magnetic shell of 5 nm in thickness is a nanohybrid, composed of ordered alloy FePt nanoparticles of approximately 3-4 nm in size and a polymer layer of a cationic polyelectrolyte, poly(diaryldimethylammonium chloride) (PDDA). The magnetic capsules have an excellent capacity for carrying medical drugs and genes. Surface-modified silica particles with PDDA were used as a template for the capsules. FePt nanoparticles were deposited on the PDDA-modified silica particles through a polyol method followed by dissolving the silica particles with a NaOH solution, resulting in the formation of the magnetic capsules as the final product. A three-dimensional hollow structure is maintained by the nanohybrid shell. The FePt-nanoparticles/PDDA nanohybrid shell also exhibits a ferromagnetic feature at room temperature because the FePt nanoparticles of an ordered-alloy phase are formed with the aid of PDDA despite the small size (3-4 nm).