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Surface‐enhanced Raman scattering (SERS) is a sensitive and fast technique for sensing applications such as chemical trace analysis. However, a successful, high‐throughput practical implementation necessitates the availability of simple‐to‐use and economical SERS substrates. In this work, we present a robust, reproducible, flexible and yet cost‐effective SERS substrate suited for the sensitive detection of analytes at near‐infrared (NIR) excitation wavelengths. The fabrication is based on a simple dropcast deposition of silver or gold nanomaterials on an aluminium foil support, making the design suitable for mass production. The fabricated SERS substrates can withstand very high average Raman laser power of up to 400 mW in the NIR wavelength range while maintaining a linear signal response of the analyte. This enables a combined high signal enhancement potential provided by (i) the field enhancement via the localized surface plasmon resonance introduced by the noble metal nanomaterials and (ii) additional enhancement proportional to an increase of the applicable Raman laser power without causing the thermal decomposition of the analyte. The application of the SERS substrates for the trace detection of melamine and rhodamine 6G is demonstrated, which shows limits of detection smaller than 0.1 ppm and analytical enhancement factors on the order of 104 as compared to bare aluminium foil. [ABSTRACT FROM AUTHOR]

Four pinaceae pine resins analyzed in this study: black pine, shore pine, Baltic amber, and rosin demonstrate excellent dielectric properties, outstanding film forming, and ease of processability from ethyl alcohol solutions. Their trap‐free nature allows fabrication of virtually hysteresis‐free organic field effect transistors operating in a low voltage window with excellent stability under bias stress. Such green constituents represent an excellent choice of materials for applications targeting biocompatibility and biodegradability of electronics and sensors, within the overall effort of sustainable electronics development and environmental friendliness. [ABSTRACT FROM AUTHOR]

Natural dielectrics are emerging nowadays as a niche selection of materials for applications targeting biocompatibility and biodegradability for electronics and sensors within the overall effort of scientific community to achieve sustainable development and to build environmental consciousness. The two natural resins analyzed in this study, silver fir and Rocky mountain fir demonstrate robust dielectric properties and excellent film forming capabilities, while being trap free dielectrics in high‐performance organic field effect transistors (OFETs) operating at voltages as low as 1 V. Immense research possibilities are demonstrated through the avenue of inorganic nanofillers insertions in the natural resins film, that opens the door for fabrication of very low voltage OFETs with high dielectric constant insulating layers. [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]

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]

The majority of energy storage devices like batteries, fuel cells or electrolyzers require heterogeneous electrodes. Immobilization of redox‐active organic molecules by a polymeric approach seems to be a promising route towards organic electrodes for electrocatalytic energy storage or in batteries. Although numerous reports on synthesis and application of new poly‐anthraquinones exist, a universal guideline or tool for selection of the best polymer, concerning several energy storage applications, is still underdeveloped. Moving into the direction of developing such a tool, we have selected and synthesized three poly(anthraquinones). NMR, FTIR, UV‐Vis, TGA, contact angle measurement and SEM revealed certain structure‐property trends, which can be correlated with the performance in the electrochemical investigation. The insights gained within this work demonstrate correlations between the FTIR frequencies and the electrochemical reduction potential, as well as between the polymer hydrophobicity and the electrochemical performance. [ABSTRACT FROM AUTHOR]

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]

Here, a simple method for controlling the size of the perovskite nanoparticles (PNPs) during preparation is reported. Metal halide PNPs have great potential for application in optoelectronic devices, such as light-emitting diodes, lasers, photodetectors, etc. They have exceptionally high photoluminescence quantum yields (PLQYs) and exhibit chemical tunability for versatile modifications of the perovskite structural composition, enabling the synthesis of nanoparticles with controlled size, shape, and optical properties. In this work, methylammonium lead bromide PNPs were prepared using a hygroscopic stabilizing ligand, tert-butoxycarbonyl-Lysine (tboc-Lysine). Water was used as an additive in the precursor solution, which resulted in the formation of highly mobile species and, thus, the nhancement of perovskite lattice growth. This method allowed the preparation of PNPs with controlled size between 4 and 7 nm. The quantum confinement effect led to a fine-tuned optical band gap of the nanoparticles. Increasing the amount of water added from 0 to 32 mol equiv with respect to Lead-(II) bromide (PbBr2) increased the PLQY to 70% in colloidal solutions and to 87% in thin films. Therefore, because of control over the size and high luminescent yields, the above-mentioned nanoparticles are targeted for use in optoelectronic devices. [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]

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]

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]

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 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]

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]

Review: [62 refs. [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]

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 at 10.1002/chem.202004792., (© 2021 Wiley-VCH GmbH.)

Biocompatible ZnS-based nanocrystals capped with 4-mercaptophenylboronic acid (ZnS@B) have been size-designed as excellent pH-responsive gatekeepers on mesoporous silica nanoparticles (MSNs), which encapsulate fluorophore safranin O (S2-Saf) or anticancer drug epirubicin hydrochloride (S2-Epi) for delivery applications in cancer cells. In this novel hybrid system, the gate mechanism consists of reversible pH-sensitive boronate ester moieties linking the nanocrystals directly to the alcohol groups from silica surface scaffold, avoiding tedious intermediate functionalization steps. The ∼3 nm size of the ZnS@B nanocrystals was tailored to allow efficient sealing of the pore voids and achieve a "zero premature cargo release" at neutral pH (7.4). The system selectively released the cargo in acidic conditions (pH 5.4 and 3.0) because of the hydrolysis of the boronate esters, which unblocked the pore voids. Delivery of the cargo by off-on cycles was demonstrated by changes in pH from 7.4 to 3.0, showing its potential pH-switching behavior. Cellular uptake of these nanocarriers within human cervix adenocarcinoma (HeLa) cells was achieved and the controlled release of the chemotherapeutic drug epirubicin was shown to occur within the endogenous endosomal/lysosomal acidified cancer cell microenvironment and further diffused into the cytosol. Cytotoxicity tests done on the mesoporous support without cargo and covalently linked with ZnS@B nanocrystals as caps were negative, suggesting that the proposed system is biocompatible and can be considered as a very promising drug nanocarrier.