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A new catalyst has been synthesized from the precursor [Pd2{μ-(C6H4) PPh2}2 {μ-O2C(C6H5)}2] immobilized on a carboxypolystyrene polymer that exhibits an excellent dispersion of the Pd (II) centers, reusability, and catalytic activity in front of phenyl bromides. The activity of this new material was studied in detail for the Suzuki-Miyaura reaction and compared to that of Pd nanoparticles (NPs) supported on UVM-7 (a mesoporous silica), and Pd NPs stabilized with polyvinylpirrolydone. The homogeneous/heterogeneous character of the catalytic process was determined from the results of the hot-filtration, centrifugation, poisoning, three phases tests, and from differential sensitivity kinetic assays. Changes in the palladium oxidation state, and the size and morphology of the Pd NPs formed during several reusing catalytic cycles were determined by XPS, and by SEM and STEM-HAADF respectively. Kinetic and structural analyses concluded that the new material behaved as a supplier of active Pd(0) NPs to the Suzuki-Miyaura catalytic cycle, which was determined to be driven mainly by the palladium fraction present in solution.

In this work we present a synthesis strategy for the preparation of Stöber-type mesoporous particles functionalized with inorganic species. The procedure is based on a combination of the Atrane and the Stöber methods. Both as a source of silicon and of the incorporated heteroelements (Fe, Zn, Al, Ti) the corresponding atrane complexes are used as hydrolytic reagents. These complexes are easily formed by reaction with triethanolamine. Mesoporosity is achieved using surfactant micelles as templates. Obtaining uniform spherical particles is achieved by optimizing the amount of water-ethanol in the reaction medium. The particle sizes have been modulated by controlling simple parameters such as reaction time or temperature. The incorporation of inorganic species is on many occasions incompatible with the preservation of spherical morphology, resulting in heterogeneous particles in shape and size and even phase segregation for high functionalization degrees. The methodology that we propose makes it possible to achieve a high concentration of highly dispersed heteroelements (even at molecular level), maintaining, to a large extent, both sphericity and particle size homogeneity. The Si/M molar ratios achieved are significantly lower (greater functionalization) than those usually reported in the literature. The strategy is generalizable for the incorporation of a great variety of elements, and specially for first row transition elements.

[EN] We report herein the design of a strip-based rapid test utilizing bio-inspired hybrid nanomaterials for the in situ and at site detection of the drug scopolamine (SCP) using a smartphone for readout, allowing SCP identification in diluted saliva down to 40 nM in less than 15 min. For this purpose, we prepared a nanosensor based on mesoporous silica nanoparticles loaded with a fluorescent reporter (rhodamine B) and functionalized with bethanechol, a potent agonist of recombinant human muscarinic acetylcholine receptor M-2 (M-2-AChR). M-2-AChR interaction with the anchored bethanechol derivative leads to capping of the pores. The sensing mechanism relies on binding of SCP to M-2-AChR resulting in pore opening and delivery of the entrapped rhodamine B reporter. Moreover, the material was incorporated into strips for lateral-flow assays coupled to smartphone readout, giving fast response time, good selectivity, and exceptional sensitivity. In an attempt to a mobile analytical test system for law enforcement services, we have also developed a dualplex lateral flow assay for SCP and 3,4-methylenedioxypyrovalerone (MDPV) also known as the so-called "cannibal drug"., This research was funded by the Ministerio de Ciencia, Innovacion y Universidades (Spanish Government), the Agencia Estatal de Investigacion (AEI), the European Union (projects RTI2018-100910-B-C41 and RTI2018-101599-B-C22-AR (MCIU/AEI/FEDER, EU), the Conselleria de Innovacion, Universidades, Ciencia y Sociedad Digital, Generalitat Valenciana (Project PROMETEO 2018/024) and the German Research Foundation (DFG; CL 761/1-19). E. G. is grateful to the Spanish MEC for her FPU grant (FPU16/02464).

Silica-based UVM-7-type bimodal mesoporous materials with high gadolinium content (∞ ≥ Si/Gd ≥ 13) have been synthesized through a one-pot surfactant-assisted procedure from hydroalcoholic solution using a cationic surfactant as template, and starting from atrane complexes of Gd and Si as inorganic precursors. The novel synthetic pathway developed in the study preserves the UVM-7-type architecture while optimizing the dispersion of the Gd-guest species at the nanoscale and even at atomic level. It has been determined that the number of Gd atoms forming clusters is always less than 10. The behaviour under exposure to ultra-high magnetic fields reveals a significant increase in the transversal relaxivity value when compared with related materials in the bibliography. Their activity as T2 instead of T1 contrast agents is discussed and explained considering the high Gd-dispersion and concentration, nature of the materials as well as due to the high magnetic fields used, typical of MRM studies. The absence of toxicity has been confirmed in preliminary cell cultures “in vitro” and the degradation of the solids studied under biological conditions. Results suggest that the atrane route could be a suitable synthesis approach for the preparation of Gd containing contrast agents.

[EN] We report herein an evaluation of the effect of several mesoporous silica nanoparticles (MSNs) on the cellular uptake and in vitro cytotoxicity in human cells. Bare MSNs and MSNs functionalized with polyethylene glycol or hyaluronic acid are employed to evaluate uptake efficiency and mechanisms of endocytosis in cancer (MDA-MB-231) and non-cancer (MCF10A) cells. Moreover, changes in viability, cell cycle, oxidative stress, and mitochondrial membrane potential are evaluated. Our results confirm that MSNs are internalized efficiently by human cells and that uptake mechanisms differ for cell types and particles. We also confirm that MSNs are biocompatible materials that do not induce ROS/RNS production, nor changes on mitochondrial membrane potential or cell cycle., The authors want to thank the Spanish Government RTI2018-100910-B-C41 (MCUI/AEI/FEDER, UE) and PI18/01219 (ISCIII), the Generalitat Valenciana (PROMETEO/2018/024 and ACIF/2016/030), and CIBER-BBN (CB07/01/2012) and CIBER-ONC (CB16/12/00481) for support.

[EN] Nanoparticle-cell-nanoparticle communication by stigmergy was demonstrated using two capped nanodevices. The first community of nanoparticles (i.e.S(RA)(IFN)) is loaded with 9-cis-retinoic acid and capped with interferon-gamma, whereas the second community of nanoparticles (i.e.S(sulf)(PIC)) is loaded with sulforhodamine B and capped with poly(I:C). The uptake ofS(RA)(IFN)by SK-BR-3 breast cancer cells enhanced the expression of TLR3 receptor facilitating the subsequent uptake ofS(sulf)(PIC)and cell killing., We thank the Spanish Government (projects RTI2018-100910-B-C41 and RTI2018-101599-B-C22 (MCUI/FEDER, EU)), Generalitat Valenciana (project PROMETEO2018/024) and CIBER-BBN (project NANOCOMMUNITY) for support. A. U. and C. G are grateful to the Ministry of Education, Culture and Sport for her doctoral FPU grant.

[EN] Oncolytic adenoviruses are a therapeutic alternative to treat cancer based on their ability to replicate selectively in tumor cells. However, their use is limited mainly by the neutralizing antibody (Nab) immune response that prevents repeated dosing. An alternative to facilitate the DNA access to the tumor even in the presence of anti-viral Nabs could be gold nanoparticles able to transfer DNA molecules. However, the ability of these nanoparticles to carry large DNA molecules, such as an oncolytic adenovirus genome, has not been studied. In this work, gold nanoparticles were functionalized with different amounts of polyethylenimine to transfer in a safe and efficient manner a large oncolytic virus genome. Their transfer efficacy and final effect of the oncolytic virus in cancer cells are studied. For each synthesized nanoparticle, (a) DNA loading capacity, (b) complex size, (c) DNA protection ability, (d) transfection efficacy and (e) cytotoxic effect were studied. We observed that small gold nanoparticles (70-80 nm in diameter) protected DNA against nucleases and were able to transfect the ICOVIR-15 oncolytic virus genome encoded in pLR1 plasmid. In the present work, efficient transgene RNA expression, luciferase activity and viral cytopathic effect on cancer cells are reported. These results suggest gold nanoparticles to be an efficient and safe vector for oncolytic adenovirus genome transfer., This research was supported by University of Valencia 'Ayuda a la Investigacion', Asociacion Pablo Ugarte and European Regional Development Fund (VLC-CAMPUS).

The addition of light ceramic particles to bulk technological materials as reinforcement to improve their mechanical properties has attracted increasing interest in the last years. The metal matrix composites obtained using nanoparticles have been reported to exhibit an improvement of their properties due to the decrease in the size of the ceramic additives to the nanoscale. Additionally, important effects such as the dispersion of the nanoparticles, wettability, and low reactivity can be controlled by the modification of the nanoparticles&rsquo, surface. In this work, we present the preparation of core&ndash, shell MxOm@SiC nanoparticles with different shell compositions. The accurate and reproducible preparation is developed both at the lab and pilot scale. The synthesis of these core&ndash, shell nanoparticles and their scale-up production are fundamental steps for their industrial use as additives in metal matrix composites and alloys. Powder X-ray diffraction and energy dispersive X-ray (EDX) coupled with scanning transmission electron microscopy (STEM) are used to corroborate the formation of the core&ndash, shell systems, whereas line scan-EDX analysis allows measuring the average shell thickness.

[EN] This work reports the synthesis, characterization, and sensing behavior of a hybrid nanodevice for the detection of the potent abuse drug 25I-NBOMe. The system is based on mesoporous silica nanoparticles, loaded with a fluorescent dye, functionalized with a serotonin derivative and capped with the 5-HT2A receptor antibody. In the presence of 25I-NBOMe the capping antibody is displaced, leading to pore opening and rhodamine B release. This delivery was ascribed to 5-HT2A receptor antibody detachment from the surface due to its stronger coordination with 25I-NBOMe present in the solution. The prepared nanodevice allowed the sensitive (limit of detection of 0.6 mm) and selective recognition of the 25I-NBOMe drug (cocaine, heroin, mescaline, lysergic acid diethylamide, MDMA, and morphine were unable to induce pore opening and rhodamine B release). This nanodevice acts as a highly sensitive and selective fluorometric probe for the 25I-NBOMe illicit drug in artificial saliva and in sweets., The authors thank the Spanish Government (projects RTI2018-100910-B-C41 (MCUI/AEI/FEDER, UE) and CTQ2017-87954-P) and the Generalitat Valencia (PROMETEO/2018/024) for support. E.G. is grateful to the Spanish MEC for her FPU grant. The authors also thank the Electron Microscopy Service at the UPV for support.

[EN] In recent decades, the versatility of mesoporous silica particles and their relevance to develop controlled release systems have been demonstrated. Within them, gated materials able to modulate payload delivery represent great advantages. However, the role played by the porous matrix in this kind of systems is scarce. In this work, different mesoporous silica materials (MCM-41, MCM-48, SBA-15 and UVM-7) are functionalized with oleic acid as a molecular gate. All systems are fully characterized and their ability to confine the entrapped cargo and release it in the presence of bile salts is validated with release assays and in vitro digestion experiments. The cargo release profile of each synthesized support is studied, paying attention to the inorganic scaffold. Obtained release profiles fit to Korsmeyer-Peppas model, which explains the differences among the studied supports. Based on the results, UVM-7 material was the most appropriate system for duodenal delivery and was tested in an in vivo model of the Wistar rat. Payload confinement and its complete release after gastric emptying is achieved, establishing the possible use of mesoporous silica particles as protection and direct release agents into the duodenum and, hence, demonstrating that these systems could serve as an alternative to the administration methods employed until now., This research was funded by the Spanish Government (projects RTI2018-100910-B-C41 and RTI2018-101599-B-C22-AR (MCUI/FEDER, EU)) and the Generalitat Valenciana (project PROMETEO/2018/024 and ACIF/2016/023 grant).

[EN] A new Pd(0) catalyst supported on silica UVM-7 has been synthesized from the organometallic [Pd-2(mu-(C6H4) Pp(2))(2)(CH3CN)(4)](BF4)(2) precursor, characterized by the high dispersion, activity, and small size of the palladium nanoclusters fixed on the silica surface. The catalyst was tested for the Suzuki-Miyaura (SM) reaction of different 4-substitutedphenyl halides with phenylboronic acid. The kinetic study concurs with most of the catalytic action was carried out by Pd species originated by the partial solubilization of Pd immobilized on mesoporous silica. The Schmidt's analysis of differential selectivity (SADS) in several competitive SM reactions, together the STEM-HAADF and HRTEM images of the catalyst surface taken along several reuse cycles support the conclusions of the kinetic study. Furthermore, this hypothesis was critically investigated using different classic approaches to distinguish between homogeneous and heterogeneous catalysis as the three phases test, poisoning, and hot filtrate experiments. (C) 2018 Elsevier Inc. All rights reserved., We thank the Spanish Ministerio de Economía y Competitividad and European Feder Funds (MAT2015-64139-C4-2-R) for funding this research.

[EN] Mesoporous silica nanoparticles loaded with rhodamine B and capped with a bisphenol A aptamer were used for the selective and sensitive detection of this lethal chemical. The pores of the nanoparticles are selectively opened in the presence of bisphenol A (through its selective coordination with the aptamer) with subsequent rhodamine B delivery. With this capped material a limit of detection as low as 3.5 mu m of bisphenol A was measured., We thank the Spanish Government (projects MAT2015-64139-C4-1-R and AGL2015-70235-C2-2-R (MINECO/FEDER)) and the Generalitat Valenciana (project PROMETEOII/2014/047) for support. A.R. thanks UPV for her predoctoral fellowship. A.B. thanks the Spanish Government for the finantial support "Juan de la Cierva-Incorporacion" (IJCI-2014-21534). The authors also thank the Electron Microscopy Service at the UPV for support.

[EN] Here, a new bio-inspired nanoarchitectonics approach for the design of optical probes is presented. It is based on nanodevices that combine 1) an enzymatic receptor subunit, 2) a signaling subunit (consisting of a labeled reporter attached to a silica surface), and 3) a mechanism of communication between the two sites based on the production of chemical messengers by the enzymatic subunit, which induces the detachment of the reporter molecules from the silica surface. As a proof of concept, a urea nanosensor based on the release of Alexa-Fluor-647-labeled oligonucleotide from enzyme-functionalized Janus gold-mesoporous-silica nanoparticles (Au-MSNPs) was developed. The Janus particles were functionalized on the silica face with amino groups to which the labeled oligonucleotides were attached by electrostatic interactions, whereas the gold face was used for grafting urease enzymes. The nanodevice was able to release the fluorescent oligonucleotide through the enzyme-mediated hydrolysis of urea to ammonia and the subsequent deprotonation of amino groups on the silica face. This simple nanodevice was applied for the fluorometric detection of urea in real human blood samples and for the identification of adulterated milk. Given the large variety of enzymes and reporter species that could be combined, this is a general new paradigm that could be applied to the design of a number of optical probes for the detection of target analytes., A.L.-L. is grateful to "La Caixa" Banking Foundation for his Ph.D. fellowship. The authors thank to the Spanish Government (MINECO Projects MAT2015-64139-C4-1, AGL2015-70235-C2-2-R, CTQ2014-58989-P and CTQ2015-71936-REDT) and the Generalitat Valencia (Projects PROMETEOII/2014/047, PROMETEO2018/024) for support. The Comunidad de Madrid (S2013/MIT-3029, Programme NANOAVANSENS) is also gratefully acknowledged.

New catalysts based on Pd(0) nanoparticles (Pd NPs) on a bimodal porous silica of the UVM-7/polydopamine (PDA) support have been synthesized following two preparative strategies based on the sequential or joint incorporation of two components of the composite (Pd and PDA). We analyzed the role played by the PDA as &lsquo, interfacial glue&rsquo, between the silica scaffold and the Pd NPs. The catalysts were tested for the hydrogenation of 4-nitrophenol using (NEt4)BH4 as the hydrogenating agent. In addition to the palladium content, the characterization of the catalysts at the micro and nanoscale has highlighted the importance of different parameters, such as the size and dispersion of the Pd NPs, as well as their accessibility to the substrate (greater or lesser depending on their entrapment level in the PDA) on the catalytic efficiency. Staged sequential synthesis has led to better catalytic results. The most active Pd(0) centers seem to be Pd NPs of less than 1 nm on the PDA surface. The efficiency of the catalysts obtained is superior to that of similar materials without PDA. A comprehensive comparison has been made with other catalysts based on Pd NPs in a wide variety of supports. The TOF values achieved are among the best described in the literature.

[EN] Magnetic micro-sized mesoporous silica particles were used for the preparation of a gated material able to release an entrapped cargo in the presence of an azo-reducing agent and, to some extent, at acidic pH. The magnetic mesoporous microparticles were loaded with safranin O and the external surface was functionalized with an azo derivative 1 (bearing a carbamate linkage) yielding solid S1. Aqueous suspensions of S1 at pH 7.4 showed negligible safranin O release due to the presence of the bulky azo derivative attached onto the external surface of the inorganic scaffold. However, in the presence of sodium dithionite (azoreductive agent), a remarkable safranin O delivery was observed. At acidic pH, a certain safranin O release from S1 was also found. The pH-triggered safranin O delivery was ascribed to the acid-induced hydrolysis of the carbamate moiety that linked the bulky azo derivatives onto the mesoporous inorganic magnetic support. The controlled release behavior of S1 was also tested using a model that simulated the gastro intestinal tract., We thank the Spanish Government (projects MAT2015-64139-C4-1-R and AGL2015-70235C2-2-R (MINECO/FEDER)) and the Generalitat Valenciana (project PROMETEOII/2014/047) for support. AHT thanks to the Spanish MEC for his FPU grant. The authors also thank the Electron Microscopy Service at the Universitat Politecnica de Valencia for support. SCSIE (Universitat de Valencia) is also gratefully acknowledged for all the equipment employed. NMR was registered at the U26 facility of ICTS "NANBIOSIS" at the Universitat de Valencia. The authors thanks L.A. Villaescusa for his helpful discussion about the 1H-NMR analysis of the composition of loaded and functionalized supports.

[EN] Probe 1, which contains an anilinopyridine chromophore and an aza-oxa macrocyclic subunit, presented an absorption band centered at 340 nm in acetonitrile. Addition of Fe(III), Cr(III) and Hg(II) induced the growth of a new absorption band at 430 nm (with color change from colorless to yellow), whereas in the presence of Cu(II), Zn(II) and Pb(II), less marked changes were observed. The color changes observed upon addition of Fe(III), Cr(III) and Hg(II) were ascribed to the formation of 1:1 stoichiometry complexes with probe 1. Coordination of Fe(III), Cr(III) and Hg(II) with the pyridine fragment of 1 induced an enhancement of the charge transfer character accompanied with a marked bathochromic shift that was reflected in a color change from colorless to yellow. The strength of the interaction between probe 1 and Fe(III) cation was modulated upon interaction with anions. Of all the anions tested, only cyanide was able to induce the bleaching of the yellow 1Fe(III) complex solution. This bleaching was ascribed to the formation of 1Fe(III)-CN complex that restored, to some extent, the optical features of the free probe allowing the chromogenic sensing of cyanide. Besides, 1Fe(III) complex was used to detect cyanide in acetonitrile-water 90:10 v/v mixtures with good recoveries., This work was supported by the Generalitat Valenciana [grant number PROMETEOII/2014/047]; Ministerio de Economia y Competitividad [grant number MAT2015-64139-C4-1-R], [grant number AGL2015-70235-C2-2-R (MINECO/FEDER)].

[EN] Apoptotic signaling pathways are altered in numerous pathologies such as cancer. In this scenario, caspase-9/PP2Ac alpha interaction constitutes a key target with pharmacological interest to re-establish apoptosis in tumor cells. Very recently, a short peptide (C9h) known to disrupt caspase-9/PP2Ac alpha interaction with subsequent apoptosis induction was described. Here, we prepared two sets of mesoporous silica nanoparticles loaded with safraninO (S2) or with C9h peptide (S4) and functionalized with epsilon-polylysine as capping unit. Aqueous suspensions of both nanoparticles showed negligible cargo release whereas in the presence of pronase, a marked delivery of safraninO or C9h was observed. Confocal microscopy studies carried out with HeLa cells indicated that both materials were internalized and were able to release their entrapped cargos. Besides, a marked decrease in HeLa cell viability (ca. 50%) was observed when treated with C9h-loaded S4 nanoparticles. Moreover, S4 provides peptide protection from degradation additionally allowing for a dose reduction to observe an apoptotic effect when compared with C9h alone or in combination with a cell-penetrating peptide (i.e., Mut3DPT-C9h). Flow cytometry studies, by means of Annexin V-FITC staining, showed the activation of apoptotic pathways in HeLa as a consequence of S4 internalization, release of C9h peptide and disruption of caspase-9/PP2Ac alpha interaction., The authors wish to express their gratitude to the Spanish government (Projects MAT2015-64139-C4-1, SAF2012-31405, SAF2015-67077-R, AGL2015-70235-C2-2-R (MINECO/FEDER)), the Generalitat Valencia (Projects PROMETEOII/2014/047, PROMETEO/2012/061) and the CIBER-BBN for their support. C.T. is grateful to the Spanish Ministry of Science and Innovation for her Ph.D. fellowship.

[EN] Boron chemistry has raised much interest because, despite the difference between necessities and toxicity being very narrow, it is still widely used in industrial processes. In a previous work we reported an adsorbent for boron extraction from water by the functionalisation of a UVM-7 mesoporous silica matrix with gluconamide moieties. The ability of this material to adsorb boron is based on its well-known affinity for coordinating the cis-diols present in attached saccharide. Although much research on the formation of boron esters with sugars and sugar derivatives in solution has been done, very few reports have dealt with the adsorption mechanism of boron onto functionalised materials in the solid state. Hence an in-depth study of the adsorption process was conducted in this paper. For this purpose, several solids with increasing boron contents were prepared from the gluconamide-functionalised UVM-7 material and an isothermal boron adsorption curve was obtained. The B-11 and C-13 MAS NMR techniques were used to characterise the obtained solids, and the simulation of the boron NMR and isothermal adsorption combined data was accomplished to enlighten the boron adsorption process. A model with three different coordination environments, two possible adsorption sites and the presence of oligomeric boron species allowed us to reproduce not only the isothermal boron adsorption curve, but also the evolution of the integrated areas for the signals in the B-11 MAS NMR spectra obtained for the different boron-containing gluconamide-functionalised UVM-7 materials., Financial support from the Spanish Government (Project MAT2009-14564-C04-01 and MAT2012-38429-C04-01) and the Generalitat Valenciana (Project PROMETEO/2009/016) is gratefully acknowledged. C.S. thanks the MICINN for a predoctoral fellowship.

Due to the narrowrange between boron necessities and toxicity in the environment, there is a high interest in the design of effective boron remediation procedures. We have previously reported a promising boron adsorptionmaterial based on the affinity of boron aqueous species for cis-diol groups that were anchored on differentmesoporous silica matrices.However, the small particle size of these systemsmakes themdifficult to be applied on real remediation situations. In this context we report herein a novel systemfor boron adsorption fromaqueous solutions inwhich the high boron affinity for functionalized mesoporousmaterials is combined with themechanical properties of ceramic foams as macroscopic supports. The efficiency of these new composites for boron removal is very high and comparable with the parent microparticulated adsorbent., Financial support from the Spanish Government (Project MAT2009-14564-C04-01 and MAT2009-14564-C04-04, and MAT2012-38429-C04-01 and MAT2012-38429-C04-02) and the Generalitat Valenciana (Project PROMETEO/2009/016) is gratefully acknowledged. C.S. thanks the MICINN for a predoctoral fellowship.

[EN] Aptamers have been used as recognition elements for several molecules due to their great affinity and selectivity. Additionally, mesoporous nanomaterials have demonstrated great potential in sensing applications. Based on these concepts, we report herein the use of two aptamer¿capped mesoporous silica materials for the selective detection of ochratoxin¿A (OTA). A specific aptamer for OTA was used to block the pores of rhodamine¿B¿loaded mesoporous silica nanoparticles. Two solids were prepared in which the aptamer capped the porous scaffolds by using a covalent or electrostatic approach. Whereas the prepared materials remained capped in water, dye delivery was selectively observed in the presence of OTA. The protocol showed excellent analytical performance in terms of sensitivity (limit of detection: 0.5¿0.05¿nm), reproducibility, and selectivity. Moreover, the aptasensors were tested for OTA detection in commercial foodstuff matrices, which demonstrated their potential applicability in real samples, We thank the Spanish Government (projects MAT2015-64139-C4-1-R and AGL2015-70235-C2-2-R (MINECO/FEDER)) and the Generalitat Valenciana (project PROMETEOII/2014/047) for support. A.R. thanks UPV for her predoctoral fellowship. S.S. thanks the Instituto de Salud Carlos III and the European Social Fund for the financial support "Sara Borrell" (CD16/000237). A.B. thanks the Spanish Government for financial support by the "Juan de la Cierva-Incorporacion" (IJCI-2014-21534). The authors also thank the Electron Microscopy Service at UPV for support.

[EN] We report a delivery system based on Au-mesoporous silica (MS) nanoparticles functionalized with acetylcholinesterase on the Au face as a control unit and with disulfide-containing oligo(ethylene glycol) chains on the MS face as caps. The control unit handles the chemical information in the environment (the presence of acetyl-thiocholine or enzyme inhibitors) that results in a tuned cargo delivery from the nanocarrier. The nanodevice displayed an enhanced cargo delivery in cancer cells (safranin O and doxorubicin) in the presence of acetylthiocholine., A. Llopis-Lorente thanks "La Caixa" Banking Foundation for his PhD fellowship. A. Garcia-Fernandez is grateful to the Spanish government for an FPU grant. The authors are grateful to the Spanish Government (MINECO Projects MAT2015-64139-C4-1, CTQ2014-58989-P and CTQ2015-71936-REDT) and the Generalitat Valencia (Project PROMETEOII/2014/047) for support. The Comunidad de Madrid (S2013/MIT-3029, Programme NANOAVANSENS) is also gratefully acknowledged.

[EN] New hybrid oligonucleotide-capped mesoporous silica nanoparticles able to detect genomic DNA were designed., Financial support from the Spanish Government (Project MAT2012-38429-C04) and the Generalitat Valencia (Project PROMETEOII/2014/047) is gratefully acknowledged. Ll. P. is grateful to the Universidad Politecnica de Valencia for his grant.

[DE] Mit DNA verschlossene und mit Farbstoff beladene mesoporöse Siliciumdioxid-Nanopartikel wurden zum Nachweis von Mycoplasma bis zu einer Nachweisgrenze von ca. 70 genomischen DNA-Kopien pro mu-L in real kontaminierten Zellkulturmedien ohne die Hilfe von PCR-Techniken eingesetzt., Diese Arbeit wurde durch die Spanische Regierung (MAT2009-14564-C04-01 und SAF2010 15512) und die Generalitat Valenciana (PROMETEO/2009/016 und 2010/005) unterstützt. E.C. dankt dem Spanischen Bildungsministerium für ein Stipendium

The coupling of gated-indicator delivery with highly specific biochemical recognition is an innovative strategy for the detection of DNA sequences, able to compete with classical methods which need PCR amplification, in important areas such as point-of-care diagnostics or detection of specific biological contaminations with pathogens. Such comparatively simple and cheap yet highly selective and sensitive assays hold promise for use in less-developed areas of the world., Financial support from the Spanish Government (MAT2009-14564-C04-01 and SAF2010 15512), the Generalitat Valenciana (PROM-ETEO/2009/016 and 2010/005) is gratefully acknowledged. E. C. thanks the Ministerio de Educacion for a fellowship. L. M. thanks Generalitat Valenciana for her Post-Doc VALI + D contract.

[EN] A nanoporous anodic alumina (NAA)-based sensor system for the detection of Mycoplasma was developed through the implementation of "molecular gates" selective to the presence of this bacterium. The capped support showed a negligible cargo release, while presence of Mycoplasma genomic DNA resulted in the release of rhodamine B fluorescent dye. This sensor system presents a limit of detection of 20 genomic DNA copies mu L-1 and was applied to the detection of Mycoplasma bacteria in competitive environments, such as culture cell media., We thank the Spanish Government (projects MAT2015-64139-C41-R, AGL2015-70235-C2-2-R, and TEC2015-71324-R (MINECO/FEDER, UE)), the Generalitat Valenciana (project PROMETEOII/2014/047), the Catalan authority (project AGAUR 2014SGR1344), and ICREA under the 2014 ICREA Academia Award for support. L.P. thanks to PROMETEOII/2014/047 for his contract. We thank the Electron Microscopy Service at the UPV for support.

[EN] The possibility of achieving sophisticated actions in complex biological environments using gated nanoparticles is an exciting prospect with much potential. We herein describe new gated mesoporous silica nanoparticles (MSN) loaded with an anticoagulant drug and capped with a peptide containing a thrombin-specific cleavage site. When the coagulation cascade was triggered, active thrombin degraded the capping peptidic sequence and induced the-release of anticoagulant drugs to delay the clotting process. The thrombin-dependent response was assessed and a significant increase in coagulation time in plasma from 2.6 min to 5 min was found. This work broadens the application of gated silica nanoparticles and demonstrates their ability to act as controllers in a complex scenario such as hemostasis., Authors thank Spanish Government (Project Nos. MAT2012-38429-C04, AGL2012-39597-C02-02) and Generalitat Valenciana (Project No. PROMETEOII/2014/047) for support. R.B. is thankful to Svagata.eu (Erasmus Mundus Action-II program) for his fellowship. A.R. thanks UPV for her predoctoral fellowship. N.M. thanks Spanish MINECO for her FPI fellowship. The authors also thank the Electron Microscopy Service at the UPV for support.

[EN] The synthesis of capped mesoporous silica nanoparticles (MSN) conjugated with an antibody (AB) as a gatekeeper has been carried out in order to obtain a delivery system able to release an entrapped cargo (dye) in the presence of a target molecule (antigen) to which the conjugated antibody binds selectively. In particular, MSN loaded with rhodamine B and functionalized on the external surface with a suitable derivative of N-(t-butyl)- 3-oxo-(5a,17b)-4-aza-androst-1-ene-17-carboxamide (finasteride) have been prepared (S1). The addition of polyclonal antibodies against finasteride induced capping of the pores due to the interaction with the anchored hapten-like finasteride derivative to give a MSN¿hapten¿AB nanoparticle S1-AB. It was found that the addition of capped material S1-AB to water solutions containing finasteride resulted in displacement of the antibody, pore uncapping and entrapped-dye release. The response of the gated material is highly selective, and only finasteride, among other steroids, was able to induce a significant uncapping process. Compared with finasteride, the finasteride metabolite was able to release 17% of the dye, whereas the exogen steroids testosterone, metenolone and 16-b-hydroxystanozolol only induced very little release of rhodamine B (lower than 10%) from aqueous suspensions containing sensing solid S1-AB. A detection limit as low as 20 ppb was found for the fluorimetric detection of finasteride. In order to evaluate a possible application of the material for label-free detection of finasteride, the capped material was isolated and stored to give final sensing solid S1-AB-i. It was found to display a similar behavior towards finasteride as to that shown by freshly prepared S1-AB; even after a period of two months, no significant loss of selectivity or sensitivity was noted. Moreover, to study the application for the detection of finasteride in biological samples, this ¿aged¿ material, S1-AB-i, was tested using commercially available blank urine as matrix. Samples containing 70 and 90% blank urine were spiked with a defined amount of finasteride, and the concentration was determined using capped S1-AB-i. Recovery ranges from 94% to 118% were reached., Financial support from the Spanish Government (project MAT2009-14564-C04-01) and the Generalitat Valenciana (Spain) (projects PROMETEO/2009/016 and PROMETEO/2010/008) is gratefully acknowledged. E. C. thanks the Minesterio de Ciencia e Innovacion (MICINN, Spain) for her fellowship.

[EN] Trapped: Mesoporous silica nanoparticles were loaded with a fluorescent guest and functionalized with octadecyltrimethoxysilane. The alkyl chains interact with paraffins, which build a hydrophobic layer around the particle (see picture). Upon melting of the paraffin, the guest molecule is released, as demonstrated in cells for the guest doxorubicin. The release temperature can be tuned by choosing an appropriate paraffin. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim., Financial support from the Spanish Government (projects MAT2009-14564-C04-01 and SAF2010-15512) and the Generalitat Valenciana (projects PROMETEO/2009/016 and PROMETEO/2010/005) is gratefully acknowledged. L.M. thanks the Generalitat Valenciana for a VALi+d postdoctoral contract. We thank UPV electron microscopy and CIPF confocal microscopy services for technical support.

In recent years, mesoporous silica nanoparticles (MSNs) have been used as effective supports for the development of controlled-release nanodevices that are able to act as multifunctional delivery platforms for the encapsulation of therapeutic agents, enhancing their bioavailability and overcoming common issues such as poor water solubility and poor stability of some drugs. In particular, redox-responsive delivery systems have attracted the attention of scientists because of the intracellular reductive environment related to a high concentration of glutathione (GSH). In this context, we describe herein the development of a GSH-responsive delivery system based on poly(ethylene glycol)- (PEG-) capped MSNs that are able to deliver safranin O and doxorubicin in a controlled manner. The results showed that the PEG-capped systems designed in this work can be maintained closed at low GSH concentrations, yet the cargo can be delivered when the concentration of GSH is increased. Moreover, the efficacy of the PEG-capped system in delivering the cytotoxic agent doxorubicin in cells was also demonstrated., The authors thank the Spanish Government (Project MAT2012-38429-C04-01), the Generalitat Valenciana (Project PROMETEOII/2014/047), and the Universitat Politecnica de Valencia (Project SP20120795) for support. C.G. and C.d.l.T also thank the Spanish Ministry of Education for their FPU grants. The authors also thank UPV electron microscopy and CIPF confocal microscopy services for technical support.

[EN] Gated community: Peptides anchored to the surface of silica mesoporous supports by a valid procedure act as gatekeepers. In this way, "zero release" supports that selectively deliver the cargo in the presence of a suitable peptidase are obtained (see picture, red spheres: cargo, colored chains: peptides). © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim., We thank the Spanish Government (projects MAT2009-14564-C04, CB07/01/2012, and BIO2007 60066), the Generalitat Valencia (project PROMETEO/2009/016, PROMETEO/2010/005), and the CIBER-BBN for their support.

The design of comparatively simple and modularly configurable artificial systems able to communicate through the exchange of chemical messengers is, to the best of our knowledge, an unexplored field. As a proof-of-concept, we present here a family of nanoparticles that have been designed to communicate with one another in a hierarchical manner. The concept involves the use of capped mesoporous silica supports in which the messenger delivered by a first type of gated nanoparticle is used to open a second type of nanoparticle, which delivers another messenger that opens a third group of gated nanoobjects.We believe that the conceptual idea that nanodevices can be designed to communicate with one another may result in novel applications and will boost further advances towards cooperative systems with complex behavior as a result of the communication between simple abiotic individual components., Financial support from the Spanish government (project MAT2012-38429-C04-01) and the Generalitat Valencia (project PROMETEO/2009/016) is gratefully acknowledged. E.A. thanks the Universitat Politecnica de Valencia (project SP20120795) for support. C.G. is grateful to the Spanish Ministry of Science and Innovation for a grant. E.C. is grateful to the Adolf-Martens-Fonds for a fellowship. We are indebted to M. Dinter (LTB Lasertechnik Berlin GmbH) for assistance with the graphics.

A new approach towards the design of "gated scaffolds" based on the combination of capped mesoporous silica nanoparticles (MSNs) with porous biomaterials is reported. Using this approach, a 3D gelatin-based scaffold able to selectively deliver cargo in the presence of an APase enzyme is prepared and tested. This new design opens up the possibility of developing new smart biomaterials with advanced drug-delivery features., The authors thank the Spanish Government (projects MAT2012-38429-C04-01, AGL2012-39597-C02-02, MAT2012-35556, and CSO2010-11384-E), the Generalitat Valenciana (Project PRO-METEO/2009/016) and the CIBER-BBN (BIO-GATES Project) for their support. N. M. also thanks the Spanish Ministry of Science and Innovation for her FPI grant.

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., The financial support from the Spanish Government (projects CIT-060000-2008-14 and MAT2009-14564-004-01), the Generalitat Valenciana (PROMETEO/2009/016) and UPV (PAID 2414) is gratefully acknowledged. Y.S. also thanks the Spanish Ministry of Science for a PhD fellowship.

[EN] 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., Financial support from the Spanish Government (project MAT2012-38429-C04-01) and the Generalitat Valencia (project PROMETEO/2009/016) is gratefully acknowledged. J.O. Jeppesen gratefully acknowledges financial support provided by the EC FP7 ITN "FUNMOLS" Project No. 212942), the Villum Foundation, the Carlsberg Foundation, and the Danish Natural Science Research Council (#11-106744). Y. Salinas thanks the Spanish Ministry of Science and Innovation for her grant. We also thank Stephen Boyer, School of Human Sciences, Science Centre, London Metropolitan University, for carrying out the elemental analyses.

Das Design von vergleichsweise einfachen und modular konfigurierbaren k nstlichen Systemen, die ber den Austausch von chemischen Botenstoffen miteinander kommunizieren kçnnen, ist unseres Wissens ein bislang unerforschtes Gebiet. In einer grundlegenden Arbeit pr sentieren wir hier eine Serie von Nanopartikeln, die in hierarchischer Art und Weise miteinander kommunizieren kçnnen. Das Konzept beruht auf gedeckelten mesoporçsen Silikat-Tr gern, bei denen der aus einem ersten Typ von gesteuerten Nanopartikeln freigesetzte chemische Botenstoff einen zweiten Typ von gedeckelten Nanopartikeln çffnet, welche wiederum einen anderen Botenstoff freisetzen, die eine dritte Gruppe von gesteuerten Nanoobjekten çffnen. Dieses Konzept, das nanoskopische Objekte so aufgebaut werden kçnnen, dass sie miteinander Informationen austauschen, kann unserer Meinung nach zu einer Reihe neuartiger Anwendungen f hren und wird Fortschritte im Bereich kooperativer Systeme mit komplexen Eigenschaften, die auf der Kommunikation einfacher individueller abiotischer Komponenten basieren, befçrdern.

On the basis of the industrial interest of the oxovanadium phosphate catalysts, current research effort in this field is focused mainly on the development of synthetic strategies directed towards obtaining open-framework materials. There is a growing body of work describing preparations using hydrothermal procedures under a diversity of conditions. A great number of new solids, whose nets range from lamellar arrays to micro- and mesostructured organizations, has been prepared in last years. In this context, the applicability of concepts and procedures from the zeolites chemistry to systems involving transition elements is critically analyzed.

[EN] A new gated nanodevice design able to control cargo delivery using glucose as a trigger and cyclodextrin-modified glucose oxidase as a capping agent is reported., Financial support from the Spanish Government (projects MAT2012-38429-C04-01 and CTQ2011-24355), Generalitat Valenciana (project PROMETEO/2009/016), UPV (project SP20120795) and Ramon y Cajal Programme (to R. V.) is gratefully acknowledged.

The present study reports a novel approach for the chromogenic sensing of CO2 using silica nanoparticles N1 functionalized with amino and thiol moieties. The reaction of CO2 present in air with the hybrid silica nanoparticles controlled the access of a squaraine dye to the surface of nanoparticles, due to formation of carbamates between amino groups and carbon dioxide. This competitive reaction results in a simple chromogenic response to CO2. By using these bifunctionalized nanoparticles CO2 detection was achieved using suspensions of N1 in phosphate buffer or by using N1 directly in contact with air containing CO2. The use of nanoparticles that can be easily functionalized with two or more individual groups that are able to react with dyes and CO2, and the possible use of a wide range of different dyes (for signalling), makes this approach highly appealing and versatile for the design of chromo¿fluorogenic dosimeters for the evaluation of the accumulative exposure to CO2 in different environments, Financial support from the Spanish Government (project MAT2012-38429-C04-01) and the Generalitat Valencia (project PROMETEO/2009/016) is gratefully acknowledged. A. A. thanks the Generalitat Valencia for a Santiago Grisolia fellowship. M. E. M. is grateful to the Spanish Ministerio de Ciencia e Innovacion for an FPU grant.

[EN] A hybrid capped mesoporous material, which was selectively opened in the presence of Tetryl and TNT, has been synthesised and used for the fluorogenic recognition of these nitroaromatic explosives., Financial support from the Spanish Government (project MAT2012-38429-C04-01) and the Generalitat Valencia (project PROMETEO/2009/016) is gratefully acknowledged. Y.S. and E.P. are grateful to the Spanish Ministry of Science and Innovation for their grants. A. A. also thanks the Generalitat Valenciana for his Santiago Grisolia fellowship.

The dumortierite-family structuresM12X2(SeO3)8(OH)6(M= Co2+and Ni2+;X= OH−and F−) have been synthesized. The crystal structures of the hydroxo-derivatives have been refined from X?ray powder diffraction data in the space groupP63mc(Z= 1) witha= 12.887(3) A andc= 4.981(4) A (M= Co2+,X= OH−or F−) anda= 12.704(5) A andc= 4.925(6) A (M= Ni2+,X= OH−or F−). Application of the Partial Charge Transference Model allows the understanding of the selenite derivatives crystal chemistry.

This article focuses on the study of the release rate in a family of modified silica mesoporous supports. A collection of solids containing ethyl, butyl, hexyl, octyl, decyl, octadecyl, docosyl, and triacontyl groups anchored on the pore outlets of mesoporous MCM-41 has been prepared and characterized. Controlled release from pore voids has been studied through the delivery of the dye complex tris(2,2¿-bipyridyl)ruthenium(II). Delivery rates were found to be dependent on the alkyl chain length anchored on the pore outlets of the mesoporous scaffolding. Moreover, release rates follow a Higuchi diffusion model, and Higuchi constants for the different hybrid solids have been calculated. A decrease of the Higuchi constants was observed as the alkyl chain used to tune the release profile is longer, confirming the effect that the different alkyl chains anchored into the pore mouths exerted on the delivery of the cargo. Furthermore, to better understand the relation between pore outlets decoration and release rate, studies using molecular dynamics simulations employing force-field methods have been carried out. A good agreement between the calculations and the experimental observations was observed., Financial support from the Spanish Government (projects MAT2009-14564-C04-01 and MAT2009-14564-C04-04) and the Generalitat Valencia (project PROMETEO/2009/016) is gratefully acknowledged.

A new optoelectronic nose to monitor chicken meat ageing has been developed. It is based on 16 pigments prepared by the incorporation of different dyes (pH indicators, Lewis acids, hydrogenbonding derivatives, selective probes and natural dyes) into inorganic materials (UVM-7, silica and alumina). The colour changes of the sensor array were characteristic of chicken ageing in a modi¿ed packaging atmosphere (30% CO2¿70% N2). The chromogenic array data were processed with qualitative (PCA) and quantitative (PLS) tools. The PCA statistical analysis showed a high degree of dispersion, with nine dimensions required to explain 95% of variance. Despite this high dimensionality, a tridimensional representation of the three principal components was able to differentiate ageing with 2-day intervals. Moreover, the PLS statistical analysis allows the creation of a model to correlate the chromogenic data with chicken meat ageing. The model offers a PLS prediction model for ageing with values of 0.9937, 0.0389 and 0.994 for the slope, the intercept and the regression coef¿cient, respectively, and is in agreement with the perfect ¿t between the predicted and measured values observed. The results suggest the feasibility of this system to help develop optoelectronic noses that monitor food freshness.

Learning to let go with age: Intracellular controlled release of molecules within senescent cells was achieved using mesoporous silica nanoparticles (MSNs) capped with a galacto-oligosaccharide (GOS) to contain the cargo molecules (magenta spheres; see scheme). The GOS is a substrate of the senescent biomarker, senescence-associated β-galactosidase (SA-β-gal), and releases the cargo upon entry into SA-β-gal expressing cells., We thank the Spanish Government (projects MAT2009-14564-C04 and FIS PI11-0949) the Generalitat Valencia (project PROMETEO/2009/016), and the Universidad Politécnica de Valencia (UPV PAID-05-09) for support. We thank Fundación Ramón Areces for support. C.M.-G. is supported by CIBERER. L.M. thanks the Generalitat Valenciana for her VALI+D postdoctoral contract.