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Hollow microparticles are important materials, offering a larger surface area and lower density than their solid counterparts. Furthermore, their inner void space can be exploited for the encapsulation and release of guest species in a variety of applications. Herein, we present phosphazene-based silica hollow microparticles prepared via a surfactant-free sol-gel process through self-assembly of the alkoxysilyl-containing polymer in water–ethanol solution. Solely, a silane-derived polyphosphazene was used as the precursor for the microparticle formation, without additional classical silica sources. These novel hollow silica-based microparticles were prepared without surfactant, using a designed amphiphilic polyphosphazene for the particle formation made by two components, a hydrophilic unit consisting of 3-mercaptopropyl(trimethoxysilane), and a hydrophobic unit (dodecanethiol) attached to the double bonds from the poly(allylamine)phosphazene backbone via a thiol-ene photoreaction. Due to these two functionalities, a "vesicle"-like self-assembled structure was formed in the reaction medium, which could be then utilized for the microparticle preparation. The influence of NaOH during the synthesis was shown to affect the size and the wall thickness of the microparticles. This effect may enhance the possibilities to tailor such microparticles for drug delivery purposes or for future controlled release of other substances, such as drugs, fragrances, or anticorrosive pigments. [ABSTRACT FROM AUTHOR]

Strategies for production and use of nanomaterials have rapidly moved towards safety and sustainability. Beyond these requirements, the novel routes must prove to be able to preserve and even improve the performance of the resulting nanomaterials. Increasing demand of high-performance nanomaterials is mostly related to electronic components, solar energy harvesting devices, pharmaceutical industries, biosensors, and photocatalysis. Among nanomaterials, Zinc oxide (ZnO) is of special interest, mainly due to its environmental compatibility and vast myriad of possibilities related to the tuning and the enhancement of ZnO properties. Doping plays a crucial role in this scenario. In this work we report and discuss the properties of undoped ZnO as well as lanthanide (Eu, Tb, and La)-doped ZnO nanoparticles obtained by using whey, a by-product of milk processing, as a chelating agent, without using citrate nor any other chelators. The route showed to be very effective and feasible for the affordable large-scale production of both pristine and doped ZnO nanoparticles in powder form. [ABSTRACT FROM AUTHOR]

Advanced tools for cell imaging are of great interest for the detection, localization, and quantification of molecular biomarkers of cancer or infection. We describe a novel photopolymerization method to coat quantum dots (QDs) with polymer shells, in particular, molecularly imprinted polymers (MIPs), by using the visible light emitted from QDs excited by UV light. Fluorescent core-shell particles specifically recognizing glucuronic acid (GlcA) or N-acetylneuraminic acid (NANA) were prepared. Simultaneous multiplexed labeling of human keratinocytes with green QDs conjugated with MIPGlcA and red QDs conjugated with MIP-NANA was demonstrated by fluorescence imaging. The specificity of binding was verified with a non-imprinted control polymer and by enzymatic cleavage of the terminal GlcA and NANA moieties. The coating strategy is potentially a generic method for the functionalization of QDs to address a much wider range of biocompatibility and biorecognition issues. [ABSTRACT FROM AUTHOR]

Advanced tools for cell imaging are of great interest for the detection, localization, and quantification of molecular biomarkers of cancer or infection. We describe a novel photopolymerization method to coat quantum dots (QDs) with polymer shells, in particular, molecularly imprinted polymers (MIPs), by using the visible light emitted from QDs excited by UV light. Fluorescent core-shell particles specifically recognizing glucuronic acid (GlcA) or N-acetylneuraminic acid (NANA) were prepared. Simultaneous multiplexed labeling of human keratinocytes with green QDs conjugated with MIPGlcA and red QDs conjugated with MIP-NANAwas demonstrated by fluorescence imaging. The specificity of binding was verified with a non-imprinted control polymer and by enzymatic cleavage of the terminal GlcA and NANA moieties. The coating strategy is potentially a generic method for the functionalization of QDs to address a much wider range of biocompatibility and biorecognition issues. [ABSTRACT FROM AUTHOR]

The field of imaging has developed considerably over the past decade and recent advances in the area of nanotechnology, in particular nanomaterials, have opened new opportunities. Polymeric nanoparticles are particularly interesting and a number of novel materials, characterized by stimuli-responsive characteristics and fluorescent tagging, have allowed visualization, intracellular labeling and real-time tracking. In some of the latest applications the nanoparticles have been used for imagining of tumor cells, both in vivo and ex vivo. [ABSTRACT FROM AUTHOR]

Three new hybrid gated mesoporous materials ( SN3-1, SNH2-2, and SN3-3) loaded with the dye [Ru(bipy)3]2+ (bipy=bipyridine) and capped with different tetrathiafulvalene (TTF) derivatives (having different sizes and shapes and incorporating different numbers of sulfur atoms) have been prepared. The materials SN3-1 and SN3-3 are functionalized on their external surfaces with the TTF derivatives 1 and 3, respectively, which were attached by employing the 'click' chemistry reaction, whereas SNH2-2 incorporates the TTF derivative 2, which was anchored to the solid through an amidation reaction. The final gated materials have been characterized by standard techniques. Suspensions of these solids in acetonitrile showed 'zero release', most likely because of the formation of dense TTF networks around the pore outlets. The release of the entrapped [Ru(bipy)3]2+ dye from SN3-1, SNH2-2, and SN3-3 was studied in the presence of selected explosives (Tetryl, TNT, TNB, DNT, RDX, PETN, PA, and TATP). SNH2-2 showed a fairly selective response to Tetryl, whereas for SN3-1 and SN3-3 dye release was found to occur with Tetryl, TNT, and TNB. The uncapping process in the three materials can be ascribed to the formation of charge-transfer complexes between the electron-donating TTF units and the electron-accepting nitroaromatic explosives. Finally, solids SNH2-2 and SN3-1 have been tested for Tetryl detection in soil with good results, pointing toward a possible use of these or similar hybrid capped materials as probes for the selective chromo-fluorogenic detection of nitroaromatic explosives. [ABSTRACT FROM AUTHOR]

Abstract: We report herein the development of a new optoelectronic nose composed of seven sensing materials prepared by the incorporation of pH indicators and chromogenic reagents selective to metabolites into inorganic materials (UVM-7 and alumina). The nose has been applied to monitor fresh pork sausage ageing. Sausages were packaged together with the disposable array in a modified packaging atmosphere (30% CO2, 70% N2) and colour changes were measured at seven day intervals. Simultaneously, microbiological and sensory analyses were performed. Colour modulations of the chromogenic array were processed with standard analytical tools, including principal component analysis (PCA) and partial least squares (PLS). According to the PCA, the array was able to monitor the sausage spoilage process and to distinguish between each sampled day. Moreover, the PLS statistical analysis of the chromogenic data displayed a linear correlation between the predicted and measured values of the storage days, mesophilic bacteria (cfu g−1) and the sensory score with regression coefficients of 0.9300, 0.9472 and 0.9381, respectively. [Copyright &y& Elsevier]

Abstract: A chromogenic array for monitoring boiled marinated turkey meat freshness in a modified packaging atmosphere (30% CO2, 70% N2) has been developed. The chromogenic array was combined with commodity tools such as digital camera and Photoshop to extract and analyse the colour changes. The array was composed of 16 sensing materials prepared through the combination of 13 indicators (including pH indicators, nucleophilic sensing dyes, etc.) and three different inorganic supports (i.e., UVM-7, alumina and silica gel). The chromogenic data obtained from the array showed characteristic fingerprints for each sampling day (0, 3, 10, 17, 24, 31, 38 and 45 days post-package). Statistical analysis by HCA of the chromogenic data allowed classifying the samples as “fresh”, “not fresh” and “not edible”. Besides, microbiological and sensorial determinations on the packaged samples were also carried out. From these studies a shelf life of 38 days at 4°C was determined. Colour differences from the chromogenic array were employed to create PLS models for aerobic mesophilic bacteria count, sensory score and storage time with quite good results. [Copyright &y& Elsevier]

Fluorescent organic-inorganic mesoporous hybrid materials have been prepared and characterised, and their behaviour against nitroaromatic explosives have been tested. MCM-41 silica was used as an inorganic scaffold and pyrene ( P derivative containing trialkoxysilane moieties), dansyl and fluorescein ( D and F derivatives also containing trialkoxysilane groups, respectively) fluorophores have been anchored on hybrid materials by a co-condensation method to obtain a homogenous distribution of dyes into the pores of the support. Six sensing materials have been prepared, of which SP, SD, SF were hydrophilic and SPh, SDh, SFh were hydrophobic. Template-free hydrophilic materials ( SP, SD, SF) were obtained after repeated NH4NO3/ethanol extractions under temperature from as-synthesised ( MP, MD and MF supports, respectively) solids. Hydrophobic materials (SPh, SDh, SFh) were prepared by using excess 1,1,1,3,3,3-hexamethyldisilazane with template-free hydrophilic ( SP, SD and SF) materials. The six final materials displayed the typical emission bands of the grafted fluorophores. In particular, SP and SPh show the typical pyrene monomer (370-420 nm) and excimer (430-600 nm) emissions. SD and SDh exhibit the broad dansyl fluorescence band in the 450-600 nm range, whereas solids SF and SFh present sharp fluorescein emission centred at 525 nm. The fluorescent behaviour of the six final materials was tested in the presence of explosives (pentaerythritol tetranitrate (PETN), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), nitrobenzene (NB), 1,3,5-trinitrobenzene (TNB), 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), 2,4,6-trinitrophenylmethylnitramine (Tetryl) and picric acid (PA)). Only nitroaromatic compounds were able to induce emission quenching. As a general trend, the quenching degree depended on the nature of the final material. The best response was obtained with explosives PA and Tetryl, which were able to significantly quench the emission of the sensing supports. The observed quenching was ascribed to the π-π stacking interactions between the electron-donor fluorophores and the electron-withdrawing nitroaromatic explosives. When using SPh for Tetryl and PA, the limits of detection were 8.5 and 1.4 ppm, respectively, whereas they were 14.4 and 1.2 ppm for SDh. Principal component analysis algorithms were applied to the fluorescence measurements taken with the six hybrid materials and the seven explosives. The obtained score plot showed well-defined clusters for the seven explosives tested. Finally, solid SDh was applied to detect trace amounts of Tetryl in soil samples with good results. [ABSTRACT FROM AUTHOR]

The last few years of enhancing the design of hybrid mesoporous organosilica nanoparticles has allowed their degradation under specific pathologic conditions, which finally is showing a light in their potential use as drug delivery systems towards clinical trials. Nevertheless, the issue of controlling the degradation on-demand at cellular level still remains a major challenge, even if it has lately been addressed through the incorporation of degradable organo-bridged alkoxysilanes into the silica framework. On this basis, this mini review covers some of the most recent examples of different degradable organosilica nanomaterials with potential application in nanomedicine, from degradable non-porous to mesoporous organosilica nanoparticles (MONs), functionalized with responsive molecular gates, and also the very promising degradable periodic mesoporous organosilica materials (PMOs) only consisting of organosilica bridges. [ABSTRACT FROM AUTHOR]

Herein we present hybrid mesoporous silica nanomaterials (MSN) with visible light-sensitive ruthenium complexes acting as gates. Two different [Ru(bpy)2L1L2]2+ complexes were investigated by grafting [Ru(bpy)2(4AMP)2](PF6)2 (RC1) and [Ru(bpy)2(PPh3)Cl]Cl (RC2) via two or one ligands onto the surface of mesoporous silica nanoparticles (MSNs), to give MSN1-RC1 and MSN2-RC2, respectively. The pores were previously loaded with a common dye, safranin O, and release studies were conducted. The number and position of the ligands were shown to influence the photocages behavior and thus the release of the cargo. Release studies from MSN1-RC1 in acetonitrile showed that in the dark the amount of dye released was minimal after 300 min, whereas a significant increase was measured upon visible light irradiation (ca. 90%). While successful as a photochemically-controlled gated system, RC1 was restricted to organic solvents since it required cleavage of two ligands in order to be cleaved from the surface, and in water only one is cleaved. Release studies from the second nanomaterial MSN2-RC2, where the complex RC2 was bound to the MSN via only one ligand, showed stability under darkness and in aqueous solution up to 180 min and, rapid release of the dye when irradiated with visible light. Furthermore, this system was demonstrated to be reversible, since, upon heating to 80 °C, the system could effectively re-close the pores and re-open it again upon visible light irradiation. This work, thus, demonstrates the potential reversible gate mechanism of the ruthenium-gated nanomaterials upon visible light irradiation, and could be envisioned as a future design of photochemically-driven drug delivery nanosystems or on/off switches for nanorelease systems. [ABSTRACT FROM AUTHOR]

Combining the unique properties of peptides as versatile tools for nano- and biotechnology with lead halide perovskite nanoparticles can bring exceptional opportunities for the development of optoelectronics, photonics, and bioelectronics. As a first step towards this challenge sub 10 nm methylammonium lead bromide perovskite colloidal nanoparticles have been synthetizes using commercial cyclic peptide Cyclo(RGDFK), containing 5 amino acids, as a surface stabilizer. Perovskite nanoparticles passivated with Cyclo(RGDFK) possess charge transfer from the perovskite core to the peptide shell, resulting in lower photoluminescence quantum yields, which however opens a path for the application where charge transfer is favorable. [ABSTRACT FROM AUTHOR]

Review: [62 refs. [ABSTRACT FROM AUTHOR]

The natural occurrence of precious opals, consisting of highly organized silica particles, has prompted interest in the synthesis and formation of these structures. Previous research has shown that a highly organized photonic crystal (PhC) array is only possible when it is based on a low polydispersity index (PDI) sample of particles. In this study, a solvent-only variation method is used to synthesize different sizes of silica particles (SiPs) by following the traditional sol-gel Stöber approach. The controlled rate of the addition of the reagents promoted the homogeneity of the nucleation and growth of the spherical silica particles, which in turn yielded a low PDI. The opalescent PhC were obtained via self-assembly of these particles using a solvent evaporation method. Analysis of the spatial statistics, using Voronoi tessellations, pair correlation functions, and bond order analysis showed that the successfully formed arrays showed a high degree of quasi-hexagonal (hexatic) organization, with both global and local order. Highly organized PhC show potential for developing future materials with tunable structural reflective properties, such as solar cells, sensing materials, and coatings, among others. [ABSTRACT FROM AUTHOR]

Despite the current advancements, yet improving the intrinsic structure and external environmental stability of hybrid metal halide perovskite nanomaterials is required for developing efficient perovskite‐based devices. Up‐to‐date, a very attractive method is growing and/or embedding perovskite nanocrystals within organic polymeric matrices, or into porous inorganic and hybrid nano/micromaterials (e. g. metal‐organic frameworks, mesoporous silica, zeolites, and others), favored through confinement effect within the pores. In this review, we highlighted the last two years of research progress on enhancing the stabilization of perovskite nanoparticles based on methylammonium cations. In the future generation of optoelectronic and photovoltaic devices along with other interesting applied fields, it is predicted that an effective way to trigger the widespread use of this type of perovskite nanocrystals may involve combining different functional host materials, acting as a smarter protection method for the guest nanocrystals. [ABSTRACT FROM AUTHOR]

Abstract: Kafirins are stored proteins that negatively affect the nutritional quality of sorghum grain. Kafirin concentration and other chemical characteristics were determined in 12 sorghum hybrids and varied significantly, from 58% (HB1) to 42% (HB12) as percent total protein. Kafirin concentration correlated negatively with crude protein (CP) (−0.49), with acid detergent fiber (−0.40), apparent metabolizable energy (−0.61), and true metabolizable energy corrected for N (−0.63). HB12 was the hybrid with the lowest content of kafirins, amylose and tannins, and the highest content of apparent metabolizable energy. No differences were observed in the concentration of starch, but differences were found in apparent metabolizable energy (3325–2944kcalkg−1) probably due to a greater availability of starch, related to differences in kafirin concentration. [Copyright &y& Elsevier]

This work reports a reversible braking system for micromotors that can be controlled by small temperature changes (≈5 °C). To achieve this, gated‐mesoporous organosilica microparticles are internally loaded with metal catalysts (to form the motor) and the exterior (partially) grafted with thermosensitive bottle‐brush polyphosphazenes to form Janus particles. When placed in an aqueous solution of H2O2 (the fuel), rapid forward propulsion of the motors ensues due to decomposition of the fuel. Conformational changes of the polymers at defined temperatures regulate the bubble formation rate and thus act as brakes with considerable deceleration/acceleration observed. As the components can be easily varied, this represents a versatile, modular platform for the exogenous velocity control of micromotors. [ABSTRACT FROM AUTHOR]

Mesoporous silica nanoparticles loaded with fluorescein and capped by a pseudorotaxane, formed between a naphthalene derivative and cyclobis(paraquat-p-phenylene) (CBPQT4+), were used for the selective and sensitive fluorogenic detection of 3,4-methylenedioxymethamphetamine (MDMA). [ABSTRACT FROM AUTHOR]

Invited for the cover of this issue is the group of Ian Teasdale and Yolanda Salinas at the Johannes Kepler University Linz. The image depicts the self‐propelled Janus micromotors reported in this work. Read the full text of the article at10.1002/chem.202004792. [ABSTRACT FROM AUTHOR]

Manganese ions are embedded in microporous silica nanoparticles to catalyse the degradation of the H SB 2 sb O SB 2 sb "fuel" to water and gaseous oxygen. Keywords: bottle-brush polymers; mesoporous silica; micromotors; microparticles; polyphosphazenes EN bottle-brush polymers mesoporous silica micromotors microparticles polyphosphazenes 3187 3187 1 02/17/21 20210215 NES 210215 B Self-propelled micromotors b with a reversible braking system are shown. Manganese ions are embedded in microporous silica nanoparticles to catalyse the degradation of the H SB 2 sb O SB 2 sb "fuel" to water and gaseous oxygen. [Extracted from the article]

Porous organosilica microparticles consisting of silane-derived cyclophosphazene bridges were synthesized by a surfactant-mediated sol-gel process. Starting from the substitution of hexachlorocyclotriphosphazene with allylamine, two different precursors were obtained by anchoring three or six alkoxysilane units, via a thiol-ene photoaddition reaction. In both cases, spherical, microparticles (size average of ca. 1000 nm) with large pores were obtained, confirmed by both, scanning and transmission electron microscopy. Particles synthesized using the partially functionalized precursor containing free vinyl groups were further functionalized with a thiol-containing molecule. While most other reported mesoporous organosilica particles are essentially hybrids with tetraethyl orthosilicate (TEOS), a unique feature of these particles is that structural control is achieved by exclusively using organosilane precursors. This allows an increase in the proportion of the co-components and could springboard these novel phosphorus-containing organosilica microparticles for different areas of technology. [ABSTRACT FROM AUTHOR]

This work reports on an optimized procedure to synthesize methylammonium bromide perovskite nanoparticles. The ligand-assisted precipitation synthetic pathway for preparing nanoparticles is a cost-effective and promising method due to its ease of scalability, affordable equipment requirements and convenient operational temperatures. Nevertheless, there are several parameters that influence the resulting optical properties of the final nanomaterials. Here, the influence of the choice of solvent system, capping agents, temperature during precipitation and ratios of precursor chemicals is described, among other factors. Moreover, the colloidal stability and stability of the precursor solution is studied. All of the above-mentioned parameters were observed to strongly affect the resulting optical properties of the colloidal solutions. Various solvents, dispersion media, and selection of capping agents affected the formation of the perovskite structure, and thus qualitative and quantitative optimization of the synthetic procedure conditions resulted in nanoparticles of different dimensions and optical properties. The emission maxima of the nanoparticles were in the 508–519 nm range due to quantum confinement, as confirmed by transmission electron microscopy. This detailed study allows the selection of the best optimal conditions when using the ligand-assisted precipitation method as a powerful tool to fine-tune nanostructured perovskite features targeted for specific applications. [ABSTRACT FROM AUTHOR]

The incorporation of an extraneous on–off braking system is necessary for the effective motion control of the next generation of micrometer‐sized motors. Here, the design and synthesis of micromotors is reported based on mesoporous silica particles containing bipyridine groups, introduced by cocondensation, for entrapping catalytic cobalt(II) ions within the mesochannels, and functionalized on the surface with silane‐derived temperature responsive bottle‐brush polyphosphazene. Switching the polymers in a narrow temperature window of 25–30 °C between the swollen and collapsed state, allows the access for the fuel H2O2 contained in the dispersion medium to cobalt(II) bipyridinato catalyst sites. The decomposition of hydrogen peroxide is monitored by optical microscopy, and effectively operated by reversibly closing or opening the pores by the grafted gate‐like polyphosphazene, to control on demand the oxygen bubble generation. This design represents one of the few examples using temperature as a trigger for the reversible on–off external switching of mesoporous silica micromotors. [ABSTRACT FROM AUTHOR]

Herein, the impact of thin layer of polyphosphazene derivatives, as a buffer layer between the electron‐transporting layer and the back metal‐contact in mixed‐cation mixed‐halide perovskite solar cells (PSCs), is explored. PSCs with a poly[bis(allylamino)phosphazene] (PPz) interlayer exhibit enhanced rectification in the photo‐induced current density–voltage (J–V) curves, which show improved photovoltaic performance and photostability with reduced hysteresis. The thickness of the interlayer is optimized and the optimized PSCs with PPz buffer layer shows an average open‐circuit voltage (VOC) of ≈1.05 V, a short‐circuit current density (JSC) of around 23.5 mA cm−2, a fill factor of ≈72%, and a power conversion efficiency of about 17.3% for the forward and reverse scans under simulated AM1.5G illumination. Moreover, the application of PPz as an electron‐transporting interlayer in organic solar cells reveals that PPz interfacial layer improves the electron extraction at the cathode. The merit of applying PPz interlayer extends to the possibility of using different metals (such as aluminum, gold, copper, and silver) as the top contact in the prepared PCSs. In general, these experiments reveal a very promising approach to tackle the issue of interfacing, and to improve the performance and stability of PSCs. [ABSTRACT FROM AUTHOR]

To celebrate International Women′s Day on March 8th 2016, Chemistry – A European Journal is publishing a special issue dedicated to women around the world currently working in chemical research. The cover picture shows the frontispieces of the Concept, Review, and Minireview articles published in this issue, highlighting the broad range of chemistry that is currently being carried out by female researchers. In the top row from left to right: S. Harutyunyan et al. (page 3558 ff.), J. Sponer et al. (page 3572 ff.), and M. Brimble et al. (page 3622 ff.). In the middle row from left to right: M. Resmini et al. (page 3612 ff.), the logo for International Women′s Day 2016 (http://www. internationalwomensday.com/), and Y. Xie and J. Xie (page 3588 ff.). In the bottom row from left to right: I. Beletskaya and P. Sazonov (page 3644 ff.), T. Gaich and M. Pfaffenbach (page 3600 ff.), and A. Lattanzi and S. Meninno (page 3632 ff.). [ABSTRACT FROM AUTHOR]