Internally bridged nanosilica for loadings and release of sparsely soluble compounds.

The engineering of a new monodisperse colloid with a sea urchin-like structure with a large complex internal structure is reported, in which silica surfaces are bridged by an aromatic organic cross-linker to serve as a nanocarrier host for drugs such as doxorubicin (DOX) against breast cancer cells. While dendritic fibrous nanosilica (DFNS) was employed and we do not observe a dendritic structure, these particles are referred to as sea urchin-like nanostructured silica (SNS). Since the structure of SNS consists of many silica fibrils protruding from the core, similar to the hairs of a sea urchin. For the aromatic structured cross-linker, bis(propyliminomethyl)benzene (b(PIM)B-S or silanated terephtaldehyde) were employed, which are prepared with terephtaldehyde and 3-aminopropyltriethoxy-silane (APTES) through a simple Schiff base reaction. b(PIM)B-S bridges were introduced into SNS under open vessel reflux conditions. SPS refers to the product obtained by incorporating the cross-linker b(PIM)B-S in ultra-small colloidal SNS particles. In-situ incorporation of DOX molecules resulted in SPS-DOX. The pH-responsive SPS nanocomposites were tested as biocompatible nanocarriers for controllable doxorubicin (DOX) delivery. We conclude that SPS is a unique colloid which has promising potential for technological applications such as advanced drug delivery systems, wastewater remediation and as a catalyst for green organic reactions in water.

Enhanced Photocatalytic Coupling of Benzylamine to N-Benzylidene Benzylamine over the Organic-Inorganic Composites F70-TiO2 Based on Fullerenes Derivatives and TiO2.

The organic-inorganic composites F70-TiO2, based on fullerene with carboxyl group derivatives and TiO2 semiconductor, have been designed and constructed to become an optical-functional photocatalyst via the facile sol-gel method. The composite photocatalyst obtained shows excellent photocatalytic activity for the high-efficiency conversion of benzylamine (BA) to N-benzylidene benzylamine (NBBA) with air pressure at a normal temperature under visible light irradiation. By optimizing the composition, the composites with the 1:15 mass ratio of F70 and TiO2, denoted as F70-TiO2(1:15), demonstrated the highest reaction efficiency for benzylamine (>98% conversion) to N-benzylidene benzylamine (>93% selectivity) in this study. However, pure TiO2 and fullerene derivatives (F70) exhibit decreased conversion (56.3% and 89.7%, respectively) and selectivity (83.8% and 86.0%, respectively). The UV-vis diffuse reflectance spectra (DRS) and Mott-Schottky experiment's results indicate that the introduction of fullerene derivatives into anatase TiO2 would greatly broaden the visible light response range and adjust the energy band positions of the composites, enhancing the sunlight utilization and promoting the photogenerated charge (e--h+) separation and transfer. Specifically, a series of results on the in situ EPR tests and the photo-electrophysical experiment indicate that the separated charges from the hybrid could effectively activate benzylamine and O2 to accelerate the formation of active intermediates, and then couple with free BA molecules to form the desired production of N-BBA. The effective combination, on a molecular scale, between fullerene and titanium dioxide has provided a profound understanding of the photocatalysis mechanism. This work elaborates and makes clear the relationship between the structure and the performance of functional photocatalysts.

Second near-infrared window fluorescence nanoprobes for deep-tissue in vivo multiplexed bioimaging.

In vivo multiplexed bioimaging in the second near-infrared window (NIR-II, 1000-1700 nm), owing to its superiorities of simultaneous multi-channel (multicolor) observations for multiple intrinsic biomarkers, high sensitivity, deeper penetration and high spatiotemporal resolution, and high throughput, has been a growing technology in fundamental medical diagnosis and clinical applications. Among several NIR-II nanoprobes for multiplexed bioimaging, the inorganic nanoprobes based on quantum dots (QDs) and lanthanide downconversion nanoparticles (DCNPs), as well as organic fluorophores based on donor-acceptor-donor (D-A-D) chromophores, polymethine dyes, and lanthanide complexes are extensively suitable for intravital imaging and diagnosis of disease, exhibiting excellent accomplishments. Here, we summarize recent advances in NIR-II-emitted nanoprobes for intravital multiplexed bioimaging. Furthermore, the current challenges and potential opportunities in designing novel long-wavelength nanoprobes for deep-tissue intravital multiplexed bioimaging are discussed.

Improved 3D Printing and Cell Biology Characterization of Inorganic-Filler Containing Alginate-Based Composites for Bone Regeneration: Particle Shape and Effective Surface Area Are the Dominant Factors for Printing Performance.

The use of organic-inorganic 3D printed composites with enhanced properties in biomedical applications continues to increase. The present study focuses on the development of 3D printed alginate-based composites incorporating inorganic fillers with different shapes (angular and round), for bone regeneration. Reactive fillers (bioactive glass 13-93 and hydroxyapatite) and non-reactive fillers (inert soda-lime glass) were investigated. Rheological studies and the characterization of various extrusion-based parameters, including material throughput, printability, shape fidelity and filament fusion, were carried out to identify the parameters dominating the printing process. It was shown that the effective surface area of the filler particle has the highest impact on the printing behavior, while the filler reactivity presents a side aspect. Composites with angular particle morphologies showed the same high resolution during the printing process, almost independent from their reactivity, while composites with comparable amounts of round filler particles lacked stackability after printing. Further, it could be shown that a higher effective surface area of the particles can circumvent the need for a higher filler content for obtaining convincing printing results. In addition, it was proven that, by changing the particle shape, the critical filler content for the obtained adequate printability can be altered. Preliminary in vitro biocompatibility investigations were carried out with the bioactive glass containing ink. The 3D printed ink, forming an interconnected porous scaffold, was analyzed regarding its biocompatibility in direct or indirect contact with the pre-osteoblast cell line MC3T3-E1. Both kinds of cell tests showed increased viability and a high rate of proliferation, with complete coverage of the 3D scaffolds' surface already after 7 d post cell-seeding.

Wearable Thermoelectric Devices Based on Three-Dimensional PEDOT:Tosylate/CuI Paper Composites.

Thermoelectric composites of organic and inorganic materials exhibit significantly enhanced thermoelectric properties compared with pristine organic thermoelectrics so they might be better suited as core materials of wearable thermoelectric devices. This study describes the development of three-dimensional (3D) paper PEDOT:tosylate/CuI composites that could be shaped as 3 mm thick blocks to convert a temperature difference between their bottom and top sides into power; the majority of organic thermoelectric materials are shaped as thin strips usually on a planar substrate and convert a temperature difference between the opposite edges of the strips into power. The 3D paper PEDOT:tosylate/CuI composites can produce a power density equal to 4.8 nW/cm2 (ΔΤ = 6 Κ) that is 10 times higher than that of the pristine paper PEDOT:Tos composites. The enhanced thermoelectric properties of the paper PEDOT:tosylate/CuI composites are attributed to the CuI nanocrystals entrapped inside the composite that increases the Seebeck coefficient of the composite to 225 µV K-1; the Seebeck coefficient of paper PEDOT:Tos is 65 µV K-1. A proof-of-concept wearable thermoelectric device that uses 36 blocks of the paper PEDOT:tosylate/CuI composites (as p-type elements) and 36 wires of monel (as n-type elements) can produce up to 4.7 µW of power at ΔΤ = 20 K. The device has a footprint of 64 cm2 and can be placed directly over the skin or can be embedded into clothing.

A 43 Ca nuclear magnetic resonance perspective on octacalcium phosphate and its hybrid derivatives.

43 Ca nuclear magnetic resonance (NMR) spectroscopy has been extensively applied to the detailed study of octacalcium phosphate (OCP), Ca8 (HPO4 )2 (PO4 )4 .5H2 O, and hybrid derivatives involving intercalated metabolic acids (viz., citrate, succinate, formate, and adipate). Such phases are of importance in the development of a better understanding of bone structure. High-resolution 43 Ca magic angle spinning (MAS) experiments, including double-rotation (DOR) 43 Ca NMR, as well as 43 Ca{1 H} rotational echo DOR (REDOR) and 31 P{43 Ca} REAPDOR NMR spectra, were recorded on a 43 Ca-labeled OCP phase at very high magnetic field (20 T), and complemented by ab initio calculations of NMR parameters using the Gauge-Including Projector Augmented Wave-density functional theory (GIPAW-DFT) method. This enabled a partial assignment of the eight inequivalent Ca2+ sites of OCP. Natural-abundance 43 Ca MAS NMR spectra were then recorded for the hybrid organic-inorganic derivatives, revealing changes in the 43 Ca lineshape. In the case of the citrate derivative, these could be interpreted on the basis of computational models of the structure. Overall, this study highlights the advantages of combining high-resolution 43 Ca NMR experiments and computational modeling for studying complex hybrid biomaterials.

A Facile One-Pot Synthesis of Hierarchically Organized Carbon/TiO2 Monoliths with Ordered Mesopores.

Sol-gel processing combined with soft templating and gelation-induced phase separation is very sensitive to the precursor sol composition. In this work we present a straightforward synthesis towards hierarchically structured, macroporous carbon/titania monoliths with ordered mesopores derived from resorcinol/formaldehyde monoliths and a glycolated titanium precursor. We demonstrate the influence of various reaction solvents, where diol-based media and the proportion of the catalyst seem to be essential in controlling spinodal decomposition, obtaining similar monolithic structures under different synthesis conditions. Based on these observations, we further homogeneously incorporated TiO2 into the carbon structure by an in situ synthesis approach, obtaining structural features similar to pure carbon materials with surface areas of about 400 m2 g-1 , periodically arranged mesopores with a mean distance of 10-11 nm and cellular macroporosity.

Immunoassay for foodborne pathogenic bacteria using magnetic composites Ab@Fe3O4, signal composites Ap@PtNp, and thermometer readings.

A point-of-care (POC) immunoassay was established for the sensitive and rapid detection of pathogenic Escherichia coli O157:H7, using magnetic Fe3O4 organic-inorganic composites (Ab@Fe3O4) for immunomagnetic separation, nanozyme platinum nanoparticle (PtNp) organic-inorganic composites (Ap@PtNp) for signal amplification, and thermometer readings. Antibodies and Fe3O4 were incubated in Cu2+ phosphate buffer to synthesize the magnetic composite Ab@Fe3O4 with antibodies, to specifically capture E. coli O157:H7. Antimicrobial peptides and PtNp were incubated in Cu2+ phosphate buffer to synthesize the signal composites Ap@PtNp with antimicrobial peptides (magainin I), recognizing and labeling E. coli O157:H7. In the presence of E. coli O157:H7, magnetic microcomposites targeted bacteria and signal microcomposites to form the sandwich structure: Ab@Fe3O4-bacteria-Ap@PtNp for magnetic separation. Ap@PtNp of signal composites catalyzed H2O2 to generate thermo-signals (temperature rise), which were determined by a thermometer. This point-of-care bioassay detected E. coli O157:H7 in the linear range of 101-107 CFU mL-1 and with a detection limit of 14 CFU mL-1. One-pot process magnetic Fe3O4 organic-inorganic composites (Ab@Fe3O4, magnetic microcomposites, MMC) for immunomagnetic separation and nanozyme platinum nanoparticle (PtNp) organic-inorganic composites (Ap@PtNp, signal microcomposites, SMC) were used as signal amplification and thermometer readings for E. coli O157:H7 detection.

Mini-Review: Mixed Ionic-Electronic Charge Carrier Localization and Transport in Hybrid Organic-Inorganic Nanomaterials.

In this mini-review, a comprehensive discussion on the state of the art of hybrid organic-inorganic mixed ionic-electronic conductors (hOI-MIECs) is given, focusing on conducting polymer nanocomposites comprising inorganic nanoparticles ranging from ceramic-in-polymer to polymer-in-ceramic concentration regimes. First, a brief discussion on fundamental aspects of mixed ionic-electronic transport phenomena considering the charge carrier transport at bulk regions together with the effect of the organic-inorganic interphase of hybrid nanocomposites is presented. We also make a recount of updated instrumentation techniques to characterize structure, microstructure, chemical composition, and mixed ionic-electronic transport with special focus on those relevant for hOI-MIECs. Raman imaging and impedance spectroscopy instrumentation techniques are particularly discussed as relatively simple and versatile tools to study the charge carrier localization and transport at different regions of hOI-MIECs including both bulk and interphase regions to shed some light on the mixed ionic-electronic transport mechanism. In addition, we will also refer to different device assembly configurations and in situ/operando measurements experiments to analyze mixed ionic-electronic conduction phenomena for different specific applications. Finally, we will also review the broad range of promising applications of hOI-MIECs, mainly in the field of energy storage and conversion, but also in the emerging field of electronics and bioelectronics.

HFIP-Functionalized Co3 O4 Micro-Nano-Octahedra/rGO as a Double-Layer Sensing Material for Chemical Warfare Agents.

Semiconductor metal oxides (SMO)-based gas-sensing materials suffer from insufficient detection of a specific target gas. Reliable selectivity, high sensitivity, and rapid response-recovery times under various working conditions are the main requirements for optimal gas sensors. Chemical warfare agents (CWA) such as sarin are fatal inhibitors of acetylcholinesterase in the nerve system. So, sensing materials with high sensitivity and selectivity toward CWA are urgently needed. Herein, micro-nano octahedral Co3 O4 functionalized with hexafluoroisopropanol (HFIP) were deposited on a layer of reduced graphene oxide (rGO) as a double-layer sensing materials. The Co3 O4 micro-nano octahedra were synthesized by direct growth from electrospun fiber templates calcined in ambient air. The double-layer rGO/Co3 O4 -HFIP sensing materials presented high selectivity toward DMMP (sarin agent simulant, dimethyl methyl phosphonate) versus rGO/Co3 O4 and Co3 O4 sensors after the exposure to various gases owing to hydrogen bonding between the DMMP molecules and Co3 O4 -HFIP. The rGO/Co3 O4 -HFIP sensors showed high stability with a response signal around 11.8 toward 0.5 ppm DMMP at 125 °C, and more than 75 % of the initial response was maintained under a saturated humid environment (85 % relative humidity). These results prove that these double-layer inorganic-organic composite sensing materials are excellent candidates to serve as optimal gas-sensing materials.

Aqueous Flow Batteries: Research and Development.

Flow batteries (FBs) have become a central topic recently, due to their promising prospect of addressing the issues of the random and intermittent nature of renewable energy sources. However, the successful industrialization of current FB systems is still limited by their relatively low energy densities and high cost. Research and development into novel aqueous FB systems with high energy density, high safety, and low cost are accordingly urgently required. Some novel aqueous FB systems have been explored in recent years to overcome issues of traditional FBs and vanadium FBs, in particular. Further modifications have also been made to improve their performance. In this review, appealing novel aqueous FB systems, such as zinc- and quinone-based FB systems, are reviewed, in terms of the operating principles, advantages, drawbacks, corresponding performance, and subsequent modifications. Moreover, recent investigations and advancements, and prospective research directions for novel aqueous FB systems, are summarized. Therefore, this review will provide guidance and perspectives for developing new aqueous FB systems.

Sustained drug release and electrochemical performance of ethyl cellulose-magnesium hydrogen phosphate composite.

In this, a sol-gel method was applied to prepare ethyl cellulose-magnesium hydrogen phosphate (EC-MgHPO4) composite that can have potential applications in the sensory, pharmaceutical, and biomedical sectors. The formed composite was thoroughly characterized by making use of the instrumental analysis such as UV-Vis, FT-IR, HRTEM, EDAX, SEM and XRD. For the composite, the other parameters determined includes the water uptake, porosity, thickness, bulk and tapped densities, angle of repose, Carr's index and Hausner ratio. From the results, the material found to exhibit good flowing properties with a Carr's index of 11.11%, Hausner ratio of 1.125, and angle of response of 33°. The EDAX spectrum and HRTEM analysis confirmed for the composite formation and the particles size is investigated to be around 52nm. The surface porosity due to the EC matrices was confirmed by the SEM analysis, which further used for the loading of drug, Proguanil. In addition, the material's conductivity was studied by taking uni-univalent electrolyte solution (KCl and NaCl) indicated that the conductivity follows the order of KCl>NaCl, while the activation energy obtained from Arrhenius method resembled that the conductivity is strongly influenced by the electrolyte type used. We found from the analysis that, with a decrease in the size of hydrated radii of ions, the conductivity of EC-MgHPO4 material also observed to be decreased in the order K+>Na+ and the material proved to be mechanically stable and can be operated over a range of pHs, temperatures, and electrolyte solutions. Further, the drug loading and efficiency studies indicated that the material can trap up to 80% of Proguanil (antimalarial drug) applied for its loading. The Proguanil drug release profiles confirmed for the controlled and sustained release from the EC-MgHPO4 matrix, as the material can release up to 87% of its total loaded drug over a 90min period. Finally, the cell viability and proliferation studies tested against two different cell cultures of BRL-3A rat liver and H9c2 cardiomyoblasts indicated the non-toxic nature and safer applicability of the EC-MgHPO4 (25-500µg/mL, 24h). Overall, the results of the study confirm for the safer applicability of the composite towards biosensor, drug delivery, scaffolding, and bioanalytical (quality control) applications.

Stretchable E-Skin Apexcardiogram Sensor.

A new strategy to measure the apex cardiogram with electronic skin technology is presented. An electronic skin apexcardiogram sensor, which can compensate the conventional electrocardiogram for cardiac diagnosis, is demonstrated through a highly sensitive and stretchable strain sensor with gold-nanoparticle composites.

Altering the concentration of silica tunes the functional properties of collagen-silica composite scaffolds to suit various clinical requirements.

The success of a tissue engineering scaffold depends on a fine balance being achieved between the physicochemical and biological properties. This study attempts to understand the influence of silica concentration on the functional properties of collagen-silica (CS) composite scaffolds for soft tissue engineering applications. Increasing the ratio of silica to collagen (0.25, 0.5, 0.75, 1.0, 1.25, 1.5 and 2.0 w/w) gave a marked advantage in terms of improving the water uptake and compressive modulus of the CS scaffolds, while also enhancing the biological stability and the turnover time. With increase in silica concentration the water uptake and compressive modulus increased concurrently, whereas it was not so for surface porous architecture and biocompatibility which are crucial for cell adhesion and infiltration. Silica:collagen ratio of ≤1 exhibits favourable surface biocompatibility, and any further increase in silica concentration has a detrimental effect.

High-yield synthesis of amido-functionalized polyoctahedral oligomeric silsesquioxanes by using acyl chlorides.

Homosubstituted amido-functionalized polyoctahedral oligomeric silsesquioxanes (POSS) have been synthesized by using acyl chlorides in high yields (ca. 95%). The method proved to be superior over "conventional" syntheses applying carboxylic acids or acid anhydrides, which are much less efficient (ca. 60% yield). A palette of aryl and alkyl groups has been used as side-chains. The structures of the resulting amide-POSS are supported by multinuclear (1)H, (13)C, (29)Si NMR and FTIR spectroscopy and their full conversion into octasubstituted derivatives was confirmed using mass spectrometry. We also demonstrate that the functionalized silsesquioxanes with bulky organic side-chains attached to cubic siloxane core form spherical-like, well-separated nanoparticles with a size of approximately 5 nm.

Dumbbells, trikes and quads: organic-inorganic hybrid nanoarchitectures based on "clicked" gold nanoparticles.

The controlled assembly of gold nanoparticles in terms of the spatial arrangement and number of particles is essential for many future applications like electronic devices, sensors and labeling. Here an approach is presented to build up oligomers of mono functionalized gold nanoparticles by the use of 1,3-bipolar azide alkyne cycloaddition click chemistry. The gold nanoparticles of 1.3 nm diameter are stabilized by one dendritic thioether ligand comprising an alkyne function. Together with di-, tri- and tetra-azide linker molecules the gold nanoparticle can be covalently coupled by a wet chemical protocol. The reaction is tracked with IR and UV-vis spectroscopy and the yielded organic-inorganic hybrid structures are analyzed by transmission electron microscopy. To evaluate the success of this click chemistry reaction statistical analysis of the formed oligomers is performed. The geometric and spatial arrangements of the found oligomers match perfectly the calculated values for the used linker molecules. Dimers, trimers and tetramers could be identified after the reaction with the corresponding linker molecule. The results of this model reaction suggest that the used click chemistry protocol is working well with mono functionalized gold nanoparticles.