Search

[EN] Synthetic cathinones are a class of new psychoactive substances whose consumption has increased a lot and is widespread throughout the world. Thus, there is currently a need for rapid and simple detection of these drugs. In particular, detection of synthetic cathinones in oral fluid in drivers can be of great importance in preventing traffic accidents. Herein, we report two probes, based on BODIPY derivatives combined with Cu(ii), which are able to detect these drugs both in water and in oral fluid, by changes in color and fluorescence. The determined limits of detection for ephedrone (as a model drug) are lower than the usual concentrations in saliva after intake of this type of drug. The sensing mechanism seems to be related to the cathinone induced reduction of Cu(ii) to Cu(i) with concomitants changes in the BODIPY structure., We thank the Spanish Government, MCIN/AEI/10.13039/501100011033 and "ERDF A way of making Europe" (fund RTL2018-100910-B-C42), the Spanish Ministry of Health, Consumer Affairs and Social Welfare (Project 2020I040 PNSD 2020) and Generalitat Valenciana (PROMETEO 2018/024) for financial support. SCSIE (Universitat de Valencia) is gratefully acknowledged for all the equipment employed. NMR was registered at the U26 facility of ICTS "NAMBIOSIS" at the Universitat of Valencia.

Biogenic polyamines, especially spermine and spermidine, are associated with cell growth and development. These amines can be found at high concentrations in the tumor cells, tissues, and urine of cancer patients. In contrast, spermidine levels drop with age, and a possible connection between low endogenous spermidine concentrations and age-related deterioration has been suggested. Thus, the quantification of these amines in body fluids like urine could be used in the diagnosis of different pathological situations. Here a new fluorescent molecular probe based on a tetraphenylethylene derivative is reported. This probe is able to selectively detect these amines through the enhancement of the fluorescence emission of the resulting complex. This fluorescence enhancement may be related to restricted intramolecular rotations of TPE phenyl rings induced by the analyte. Theoretical studies were carried out to shed light on the observed selectivity. Finally, the detection of these amines in urine was performed with limits of detection of 0.70 µM and 1.17 µM for spermine and spermidine, respectively.

Synthetic cathinones are a class of new psychoactive substances whose consumption has increased a lot and is widespread throughout the world. Thus, there is currently a need for rapid and simple detection of these drugs. In particular, detection of synthetic cathinones in oral fluid in drivers can be of great importance in preventing traffic accidents. Herein, we report two probes, based on BODIPY derivatives combined with Cu(ii), which are able to detect these drugs both in water and in oral fluid, by changes in color and fluorescence. The determined limits of detection for ephedrone (as a model drug) are lower than the usual concentrations in saliva after intake of this type of drug. The sensing mechanism seems to be related to the cathinone induced reduction of Cu(ii) to Cu(i) with concomitants changes in the BODIPY structure.

Consumption and abuse of drugs is a general problem, which concerns our entire society. In some cases, drugs are used for recreational purposes; but in others, they are used to commit crimes such as Drug-Facilitated Sexual Assault (DFSA). In other cases, this consumption alters the consumer mood in such a way that risky situations can rise. In any case, detection of drugs in different environment is worthwhile. Here, two new chromogenic and fluorescent probes are reported. Detection of both cathinone derivatives and γ-hydroxybutyric acid (GHB) can be carried out with naked-eye with limits of detection of 0.4 μM and 0.3 μM for GHB and 2.0 μM for ephedrone. Selectivity in the presence of other drugs has been tested. Sensing mechanisms have been studied using different spectroscopic techniques and they have been also corroborated through theoretical calculations.

Drug-Facilitated Sexual Assault (DFSA) is a problem of considerable dimensions on a global scale. Among the different compounds used in DFSA assaults, 4-hydroxybutyric acid (GHB) is one of the most elusive due to its physical and biological characteristics. Therefore, the development of real-time detection methods to detect GHB not only in drinks but also in urine is very important for personal and social security. Here, we report two new heteroditopic chemosensors capable of recognizing and detecting GHB in soft drinks, alcoholic beverages and synthetic urine. The compounds have two moieties: a trifluoroacetyl group and a thiourea, which are able to interact respectively with the hydroxyl and the carboxylic groups present in the GHB structure. In addition, the distance between these two groups has been optimized to allow a double interaction which guarantees the recognition even in very competitive media such as beverages or urine samples.

[EN] A simple colorimetric probe for the selective and sensitive detection of neurotransmitter norepinephrine (NE), an important biomarker in the detection of tumors such as pheochromocytoma and paraganglioma, is described. The sensing strategy is based on the use of spherical gold nanoparticles functionalized with benzaldehyde and boronic acid-terminated moieties. A double molecular recognition involving on one hand the aromatic aldehyde and the aminoalcohol group of NE, and on the other hand the boronic acid and the catechol moiety of the neurotransmitter, results in analyte triggered aggregation of the gold nanoparticles, leading to a bathochromic shift of the SPR band in the UV-vis spectrum of the probe and a clear change in the color of the solution from red to blue. Probe P1 shows a remarkable selectivity toward NE versus other catecholamine neurotransmitters (dopamine and epinephrine) and selected biomolecules (S-HIAA, L-Tyr, glucose, uric acid, Lys and glutamic acid). Moreover, a linear response to NE in the 0-1 mu M concentration range was observed and a limit of detection of 0.07 mu M in aqueous media was determined by UV-vis spectroscopy. The sensitivity of the probe toward NE in synthetic urine was also evaluated. In this medium, a limit of detection of 0.09 mu M was obtained which falls within the range of clinical interest, Financial support from the Spanish Government (Projects MAT2015-64139-C4-1-R and MAT2015-64139-C4-4-R) and the Generalitat Valencia (Projects PROMETEOII/2014/047 and AICO/2017/093) is gratefully acknowledged. T. Godoy-Reyes is grateful to the Generalitat Valenciana for her Santiago Grisolia fellowship.

We report herein a L-glutamate (L-Glu)-responsive delivery system. It consists of Janus Au–mesoporous silica (MS) nanoparticles functionalized with L-glutamate oxidase on the Au face and with self-immolative arylboronate derivatives as caps on the MS face. The MS face is additionally loaded with a cargo. The delivery paradigm is based on the recognition of L-Glu by the enzyme and the subsequent formation of H2O2, which induces the cleavage of the self-immolative gate and the uncapping of the pores. Given the importance of L-Glu as a key neurotransmitter, we hope that these findings will help in designing new therapeutic strategies for nervous system diseases.

The increase in the number of drug-facilitated sexual assault (DFSA) cases in recent years has become a major concern. Consequently, there is a need to develop methods for the real-time detection of these substances. We report herein a colorimetric chemosensor for the real-time in situ detection of the “date rape” drug GHB. The sensor is based on gold nanoparticles functionalized with both a 2-aminonaphthoxazole and phenanthroline derivative. Its ability to act as “naked-eye” colorimetric sensor for the detection of the drug in soft drinks and alcoholic beverages was studied. The detection process is based on the double recognition of both the hydroxyl and the carboxylate groups present in GHB, which triggers the aggregation of the AuNPs, with the resulting change in the color of the solution.

A new hybrid organic–inorganic material for sensing spermine (Spm) and spermidine (Spd) has been prepared and characterized. The material is based on MCM-41 particles functionalized with an N-hydroxysuccinimide derivative and loaded with Rhodamine 6G. The cargo is kept inside the porous material due to the formation of a double layer of organic matter. The inner layer is covalently bound to the silica particles, while the external layer is formed through hydrogen and hydrophobic interactions. The limits of detection determined by fluorimetric titration are 27 µM and 45 µM for Spm and Spd, respectively. The sensor remains silent in the presence of other biologically important amines and is able to detect Spm and Spd in both aqueous solution and cells.

[EN] Osteoporosis is an illness which appears when the osteoblast/osteoclast activities are unbalanced taking place bone resorption (caused by osteoclasts) in higher extension than bone formation (induced by osteoblasts). Alendronate is one of the most used drugs for osteoporosis treatment despite its scarce bioavailability. Here we present the synthesis and characterization of mesoporous gated nanoparticles (two sets) for the controlled release of alendronate. The first set of nanoparticles (S1) were loaded with sulforhodamine B and capped with a peptide that could be selectively hydrolyzed by cathepsin K enzyme (overexpressed in osteoclasts). The second set (S2) was functionalized with aminopropyl moieties, loaded with nitrobenzofurazan labelled alendronate and capped with the same peptide. Both nanoparticles were internalized by RAW 264.7 macrophages (which could differentiate in osteoclasts) and were able to release its entrapped cargo in the presence of cathepsin K added in the macrophage lysates. Using S2 nanoparticles 4.2% of the total alendronate amount in contact with the cells is liberated inside them and could produce its therapeutic effect., We thank the Spanish Government (RTI2018-100910-B-C41, RTI2018-100910-B-C42 (MCUI/AEI/FEDER, UE)) and the Generalitat Valenciana (PROMETEU/2018/024) for support. SCSIE (Universitat de Valencia) is gratefully acknowledged for all the equipment employed. NMR was registered at the U26 facility of ICTS "NANBIOSIS" at the Universitat of Valencia.

[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.

A recompilation of applications of mesoporous silica nanoparticles in sensing from the last five years is presented. Its high potential, especially as hybrid materials combined with organic or bio-molecules, is shown. Adding to the multiplying effect of loading high amounts of the transducer into the pores, the selectivity attained by the interaction of the analyte with the layer decorating the material is described. Examples of the different methodologies are presented.

Herein, we report the synthesis, X-ray crystal structure and photophysical studies of six new 8-amino-BODIPY derivatives containing crown or azo-crown ether moieties. The influence of steric hindrance, caused by the crown ether, on the planarity of the BODIPY core and its relationship with the fluorescent properties has been established. 1H NMR spectroscopic studies were undertaken to clarify the changes in fluorescence observed in the presence of ZnII.

[EN] Cargo delivery from mesoporous silica nanoparticles loaded with sulforhodamine B and capped with a difluoroboron-dipyrromethene (BODIPY) derivative was triggered by a NO2-induced oxidative process., The authors thank the financial support from the Spanish Government (project MAT2015-64139-C4-R) and the Generalitat Valenciana (project GVA/2014/13).

[EN] Gold nanoparticles functionalized with resorcinol moieties have been prepared and used for detecting formaldehyde both in solution and gas phases. The detection mechanism is based on the color change of the probe upon the aggregation of the nanoparticles induced by the polymerization of the resorcinol moieties in the presence of formaldehyde. A limit of detection of 0.5 ppm in solution has been determined. The probe can be deployed for the detection of formaldehyde emissions from composite wood boards., We thank the Spanish Government (projects MAT2015-64139-C4-4-R and AGL2015-70235-C2-2-R (MINECO/FEDER)) and the Generalitat Valenciana (project PROMETEOII/2014/047) for support.

Four types of calcined MCM-41 silica nanoparticles, loaded with dyes and capped with different gating ensembles are prepared and characterized. N1 and N2 nanoparticles are loaded with rhodamine 6G and capped with bulky poly(ethylene glycol) derivatives bearing ester groups (1 and 2). N3-N4 nanoparticles are loaded with sulforhodamine B and capped with self-immolative derivatives bearing ester moieties. In the absence of esterase enzyme negligible cargo release from N1, N3 and N4 nanoparticles is observed whereas a remarkable release for N2 is obtained most likely due to the formation of an irregular coating on the outer surface of the nanoparticles. In contrast, a marked delivery is found in N1, N3, and N4 in the presence of esterase enzyme. The delivery rate is related to the hydrophilic/hydrophobic character of the coating shell. The use of hydrophilic poly(ethylene glycol) derivatives as gating ensembles on N1 and N2 enables an easy access of esterase to the ester moieties with subsequent fast cargo release. On the other hand, the presence of a hydrophobic monolayer on N3 and N4 partially hinders esterase enzyme access to the ester groups and the rate of cargo release was decreased., GRAPHICAL ABSTRACT

[EN] Silica mesoporous microparticles loaded with both rhodamine B fluorophore (S1) or hydrocortisone (S2), and capped with an olsalazine derivative, are prepared and fully characterized. Suspensions of Si and S2 in water at an acidic and a neutral pH show negligible dye/drug release, yet a notable delivery took place when the reducing agent sodium dithionite is added because of hydrolysis of an azo bond in the capping ensemble. Additionally, olsalazine fragmentation induced 5-aminosalicylic acid (5-ASA) release. In vitro digestion models show that S1 and S2 solids are suitable systems to specifically release a pharmaceutical agent in the colon. In vivo pharmacokinetic studies in rats show a preferential rhodamine B release from Si in the colon. Moreover, a model of ulcerative colitis is induced in rats by oral administration of 2,4,6-trinitrobenzenesulfonic acid (TNBS) solutions, which was also used to prove the efficacy of S2 for colitis treatment. The specific delivery of hydrocortisone and 5-ASA from S2 material to the colon tissue in injured rats markedly lowers the colon/body weight ratio and the clinical activity score. Histological studies showed a remarkable reduction in inflammation, as well as an intensive regeneration of the affected tissues., We thank the Generalitat Valenciana (Project PROMETE02018/024) and the Spanish Government (Projects AGL2015-70235-C2-2-R and MAT2015-64139-C4-1-R (MINECO/FEDER)) for support. A.H.T. thanks the Spanish MEC for his FPU fellowship. The authors also thank the support of the Electron Microscopy Service at the UPV. The SCSIE (of the Universitat de Valencia) is also gratefully acknowledged for all the equipment used. NMR spectra were measured at the U26 facility of ICTS "NANBIOSIS" at the Universitat de Valencia.

[EN] Mesoporous silica nanoparticles capped with acetylcholinesterase, through boronic ester linkages, selectively release an entrapped cargo in the presence of acetylcholine., The authors acknowledge financial support from the Spanish Government (MAT2015-64139-C4-1-R, MAT2015-64139-C4-4-R and AGL2015-70235-C2-2-R) and the Generalitat Valenciana (PROMETEO2018/024). T. Godoy-Reyes is grateful to Generalitat Valenciana for her Santiago Grisollía fellowship. A. García-Fernández is grateful to the Spanish Government for her FPU fellowship

Mesoporous silica nanoparticles loaded with rhodamine B and capped with acetylcholinesterase are able to be selectively opened and deliver their cargo in the presence of nerve agent simulant diisopropyl fluorophosphate (DFP)., Financial support from the Spanish Government and FEDER funds (Project MAT2015-64139-C4-1) and the Generalitat Valenciana (Project PROMETEOII/2014/047) is gratefully acknowledged. L.P. is grateful to the Universitat Politecnica de Valencia for his grant.

Gold nanoparticles functionalized with thiourea moieties have been used as selective colorimetric sensors for the naked-eye detection of succinate versus other aliphatic dicarboxylates, all of them as their TBA salts. The detection process is based on the interparticle aggregation triggered by coordination of the end-carboxylates to the thiourea moieties of two different nanoparticles. This nanoparticle aggregation results in a batochromic shift of the plasmon resonance band and a visual color change from red to blue.

A colon targeted drug delivery system for inflammatory bowel diseases (IBD), consisting in budesonide loaded mesoporous silica microparticles functionalized with a selective azo-molecular gate (M-Bud), has been evaluated for in vivo efficacy. Experimental colitis in male Wistar rats was induced by rectal instillation of 2,4,6-trinitrobenzenesulfonic acid (TNBS). M-Bud was orally administered to the rats as a suspension in water. Colon/body weight ratio, clinical activity score, and histological evaluation were used as inflammatory indices to measure the performance of the microparticles. The formulation was compared with a suspension prepared from the commercial drug Entocord®. Statistical analyses of all scores indicate that the controlled release of budesonide in colon from M-Bud showed efficacy similar to that of Entocord in the healing of induced colitis in rats.

[EN] A new environmentally-friendly, simple, selective and sensitive probe for detecting formaldehyde, based on naturally-occurring compounds, through either colorimetric or fluorescence changes, is described. The probe is able to detect formaldehyde in both solution and the gas phase with limits of detection of 0.24 mM and 0.7 ppm, respectively. The probe has been tested to study formaldehyde emission in contaminated real atmospheres. The supported probe is easy to use and to dispose, and is safe and suitable as an individual chemodosimeter., This research was funded by the Spanish Government (projects MAT2015-64139-C4-4-R and AGL2015-70235-C2-2-R (MINECO/FEDER)) and the Generalitat Valenciana (project PROMETEOII/2014/047).

[EN] A simple and effective colorimetric method for the detection of normetanephrine (NMN), an O-methylated metabolite of norepinephrine, using functionalised gold nanoparticles is described. This metabolite is an important biomarker in the diagnosis of adrenal tumours such as pheocromocytoma or paraganglioma. The colorimetric probe consists of spherical gold nanoparticles (AuNPs) functionalised with two different ligands, which specifically recognize different functional groups in normetanephrine. Thus, a benzaldehyde-terminated ligand was used for the recognition of the amino alcohol moiety in NMN, by forming the corresponding oxazolidine. On the other hand, N-acetyl-cysteine was chosen for the recognition of the phenolic hydroxyl group through the formation of hydrogen bonds. The selective double molecular recognition between the probe and the hydroxyl and the amino-alcohol moieties of normetanephrine led to interparticle-crosslinking aggregation resulting in a change in the color of the solution, from red to blue, which could be observed by naked eye. The probe was highly selective towards normetanephrine and no color changes were observed in the presence of other neurotransmitter metabolites such as homovanillic acid (HVA) (dopamine metabolite), 5-hydroxyindoleacetic acid (5-HIAA) (serotonin metabolite), or other biomolecules present in urine such as glucose (Glc), uric acid (U.A), and urea. Finally, the probe was evaluated in synthetic urine with constituents that mimic human urine, where a limit of detection of 0.5 mu M was achieved., Financial support from the Spanish Government (project MAT2015-64139-C4) and Generalitat Valenciana (Project PROMETEOII/2014/047 and AICO/2017/093) is gratefully acknowledged. T. Godoy-Reyes is grateful to Generalitat Valenciana for her Santiago Grisolia fellowship.

[EN] Mesoporous silica microparticles were prepared, loaded with the dye safranin O (M-Saf) or with the drug budesonide (M-Bud) and capped by the grafting of a bulky azo derivative. Cargo release from M-Saf at different pH values (mimicking those found in the gastrointestinal tract) in the absence or presence of sodium dithionite (a reducing agent mimicking azoreductase enzyme present in the colon) was tested. Negligible safranin O release was observed at pH 6.8 and 4.5, whereas a moderate delivery at pH 1.2 was noted and attributed to the hydrolysis of the urea bond that linked the azo derivative onto the external surface of the inorganic scaffold. Moreover, a marked release was observed when sodium dithionite was present and was ascribed to the rupture of the azo bond in the molecular gate. Budesonide release from M-Bud in the presence of sodium dithionite was also assessed by ultraviolet-visible spectroscopy and high performance liquid chromatography measurements. In addition, preliminary in vivo experiments with M-Saf carried out in mice indicated that the chemical integrity of the microparticles remained unaltered in the stomach and the small intestine, and safranin O seemed to be released in the colon., We thank the Spanish Government (projects MAT2015-64139-C4-4-R, MAT2015-64139-C4-2-R and MAT2015-64139-C4-1-R) and Generalitat Valenciana (project PROMETEOII/2014/047 and project AICO/2017/093) for financial support.

[EN] Magnetic mesoporous silica microparticles were loaded with safranin O (S1) and with hydrocortisone (S2) and the outer surface functionalized with a bulky azo derivative bearing urea moieties. Aqueous suspensions of both solids at pH 7.4 showed negligible payload release whereas a marked delivery was observed in the presence of sodium dithionite due to the rupture of the azo bonds. Besides, a moderate cargo release was observed at acidic pH due to the hydrolysis of the urea bonds that linked the azo derivative onto the external surface of the inorganic scaffolds. In vitro digestion models showed that S1 and S2 microparticles could be used for the controlled release of payload in the reducing colon environment (in which azoreductase enzymes are present). On the other hand, in vivo pharmacokinetic studies in rats showed that safranine O release from S1 microparticles was concentrated in colon. The performance of S2 microparticles for the treatment of colitis in rats (induced by oral administration of a 2,4,6-trinitrobenzenesulfonic acid solution) was tested. The controlled release of hydrocortisone from S2 in the colon of injured rats induced marked reduction in colon/body weight ratio and in clinical activity score. Also, histological studies showed a marked decrease in inflammation followed by intensive regeneration and almost normal mucosal structure of the individuals treated with S2. Besides, the use of a magnetic belt increased the therapeutic performances of S2 due to an enhanced retention time of the particles in the colon., 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. 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 Dr. L. A. Villaescusa for his helpful discussion about the 1H NMR analysis of the composition of loaded and functionalized supports.

[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] We report a simple, sensitive and selective method for the colorimetric detection of serotonin (5-HT) in aqueous media using bifunctionalized gold nanoparticles (AuNPs). The probe (1) consisted of AuNPs functionalised with dithiobis(succinimidylpropionate) (DSP) and N-acetyl-l-cysteine (NALC). DSP was chosen to react with the amino group of 5-HT, whereas NALC was chosen to bind the hydroxyl group in 5-HT through hydrogen bonding and electrostatic interactions. A double interaction between nanoparticles and the hydroxyl and the amino group of serotonin led to interparticle-crosslinking aggregation. This, resulted in a colour change from red to blue that can be observed by the naked eye. The probe was selective to 5-HT and no colour modulation was observed in the presence of other neurotransmitters (i.e. dopamine, epinephrine, norepinephrine), selected biomolecules (i.e. L-tyrosine, gamma-aminobutyric acid, L-cysteine, uric acid, oxalic acid, aspartic acid and glutamic acid) and common inorganic species. A limit of detection as low as 0.1 mu M was determined in buffered water at pH 7 by UV-vis titrations. Similar response of the probe to 5-HT was observed in simulated blood serum, with a limit of detection of 0.12 mu M, and a linear response within the 0-3 mu M concentration range, which is within the range of the 5-HT concentrations of clinical interest. Finally, the performance of probe (1) in real human blood samples was evaluated, and showed a remarkable ability to distinguish between normal 5-HT levels and 5-HT levels indicative of disease. (c) 2017 Elsevier B.V. All rights reserved., Financial support from the Spanish Government (Projects MAT2015-64139-C4-1-R and MAT2015-64139-C4-4-R) and the Generalitat Valenciana (Project PROMETEOII/2014/047) is gratefully acknowledged. T. Godoy-Reyes is grateful to the Generalitat Valenciana for her Santiago Grisolia fellowship. A. Llopis-Lorente thanks "La Caixa" Banking Foundation for his PhD grant. SCSIE (Universitat de Valencia) is gratefully acknowledged for all the equipment employed. NMR was registered at the U26 facility of ICTS "NANBIOSIS" at the Universitat de Valencia. Support from the Juana Portaceli Health Centre of the Universitat Politecnica de Valencia to obtain blood samples from a healthy volunteer is gratefully acknowledged.

[EN] Two dansyl-modified beta-cyclodextrin derivatives (1 and 2) have been synthesized as host-guest sensory systems for the direct fluorescent detection of the peroxide explosives diacetone diperoxide (DADP) and triacetone triperoxide (TATP) in aqueous media. The sensing is based on the displacement of the dansyl moiety from the cavity of the cyclodextrin by the peroxide guest resulting in a decrease of the intensity of the fluorescence of the dye. Both systems showed similar fluorescent responses and were more sensitive towards TATP than DADP., We thank the Spanish Government (MAT2015-64139-C4-4-R) and Generalitat Valenciana (PROMETEOII/2014/047) for financial support.

A thiourea-modified fluorescein derivative was synthesized by reaction of fluorescein isothiocyanate with 2-(2-aminoethoxy)ethan-1-ol. UV/Vis absorption and fluorescence emission spectroscopy studies demonstrated that this heteroditopic receptor was able to discriminate among linear aliphatic ω-amino acids with different chain lengths.

An Au(III)–amino alcohol complex has been used to cleave organophosphorous pesticides of the dithiophosphate family. P–S bond breaking was readily demonstrated by 1H NMR, 31P NMR and MS. Thiol fragment release was also demonstrated using 2,4-dinitrobenzenesulfonyl fluorescein ethyl ester as a fluorescent sensor.

A new chromo-fluorogenic probe based on the borondipyrromethene dye has been synthesized. The dye has been attached to a sensing unit for the diethylcyanophosphonate and di-isopropylfluorophosphate detection. The new probe has been fully characterized, and its optical properties in front of these simulants have been evaluated. No interference from other organo-phosphorous or other common contaminants compounds has been observed in the detection conditions. A portable kit has been developed and tested to demonstrate its practical application in real-time monitoring not only in solution but also in gas phase., We thank the Spanish Government and the European FEDER funds (project MAT2012-38429-C04-02 and 01). SCSIE and ICMOL (Universidad de Valencia) are gratefully acknowledged for all the equipment employed. R.G. is grateful to the Spanish Ministry of Education for its FPU grant. Knut Rurack is gratefully acknowledged for the life-time measurements performed at his lab.

A fluorescent heteroditopic host for ion pairs and zwitterionic species has been synthesized. Its affinity towards a series of anions, cations and ion pairs in acetonitrile has been assessed, and the spectroscopic response has been evaluated. Solid–liquid extraction experiments of inorganic salts, α-amino acids and γ-aminobutyric acid (GABA) into acetonitrile solutions were performed, and the resulting complexes were analyzed by UV/Vis absorption, fluorescence and 1H NMR spectroscopy. The discrimination patterns observed have been rationalized in terms of the molecular topologies of the host and guests.

[EN] Gold nanoparticles functionalized with a triarylcarbinol derivative have been used as colorimetric molecular probes for the naked-eye detection of the nerve agent simulants DCNP and DFP. The detection process is based on the compensation of charges at the surface of the nanoparticles which triggers their aggregation in solution with the resulting change in their plasmon band. (C) 2014 Elsevier Ltd. All rights reserved., We thank the Spanish Government and the European FEDER funds (project MAT2012-38429-C04-02) for support. A.M. is grateful to the Spanish Government for a fellowship. SCSIE (Universidad de Valencia) is also gratefully acknowledged for all the equipment employed.

The present work reports the introduction of pyridine bisamine terdentate ligands in the structure of a pirouetting copper rotaxane. Rotaxane 2[PF6] constitutes the first example of the incorporation of imine-based dynamic covalent chemistry in the synthesis of switchable copper-complexed interlocked systems. In this rotaxane, the substitution of the classical terpyridine terdentate unit by a pyridine bisamine moiety has led to a significant stabilization of the pentacoordinated site. That fact has been evidenced by EPR spectroscopy and cyclic voltammetry. Regarding the tetracoordinated site, the congestion around the coordination sphere has been reduced to accelerate the typically slow reorganization of the Cu(II). Ethynyl-3,8-substitution on the axis phenanthroline along with the 2,9-diphenyl-1,10-phenanthroline (dpp) present in the macrocycle afforded a very stable coordination environment for Cu(I), which is at the same time labile upon oxidation. In summary, the incorporation of a pyridine bisamine unit as a terdentate ligand and the optimization of the bidentate ligand of the axle not only has led to a simplification of the synthetic procedures, but it has also given rise to a bistable systems with an enhanced energetic separation between states and an acceleration of the reorganization processes. Thus far, rotaxane 2[PF6] presents the fastest switching cycle reported to date in copper-interlocked dynamic systems.

[EN] Two OFF-ON fluorescent chemodosimeters based on a BODIPY core for the detection of nerve agent mimics have been synthesized. Their reactivity towards diethylcyanophosphonate (DCNP) and diisopropylfluorophosphate (DFP) has been tested in organic and aqueous phase. These chemodosimeters selectively detect the nerve agent mimics with good LODs. The chemodosimeters hold their sensing properties on solid supports, allowing the preparation of a hand held sensing kit. The sensing in solid-liquid phase has been demonstrated. The X-ray structure of compound 2 has been resolved., We thank the Spanish Government and the European FEDER funds (project MAT2012-38429-C04-02 and 01). SCSIE and ICMOL (Universidad de Valencia) are gratefully acknowledged for all the equipment employed. R.G. is grateful to the Spanish Ministry of Education for its FPU grant. Dr Knut Rurack is gratefully acknowledged for instrumental support and fruitful discussion.

Fast shuttling motions in solution have been observed by cyclic voltammetry in a Cu(I/II)-based [2] rotaxane. In the reported system, the different coordination preferences of both copper oxidation states are exploited to promote the electrochemically-triggered gliding of the ring from a tetra to a pentacoordinated site and vice versa. The thread of this rotaxane consists of a tridentate 2,2':6',2''-terpyridine chelating unit directly bonded through its 5-position to the 3-position of the bidentate 1,10-phenanthroline unit. This distribution reduces to a minimum the distance between the two coordination sites and lessens the congestion around the tetrahedral environment. These two factors have been demonstrated to highly increase the kinetics of the switching process. In addition, the electrochemical experiments carried out in different solvent mixtures evidenced the influence of the solvent on the shuttling mechanism.

[EN] A new colorimetric system for NO(g) detection is described. The detection method is based on the aggregation of modified AuNPs through a Cu(I) catalyzed click reaction promoted by the in situ reduction of Cu(II) by NO, We acknowledge the Spanish Government (MAT2009-14564-C04-03 and MAT2012-38429-C04-02) for financial support. A. M. is grateful to the Spanish Government for a fellowship. SCSIE (Universidad de Valencia) is gratefully acknowledged for all the equipment employed.

New functionalized gold nanoparticles have been synthesized and their ability to act as colorimetric molecular probes for the naked-eye detection of nerve agent simulant DCNP has been studied. The detection process is based on the com

A bis(calix[4]pyrrole)-substituted BODIPY ditopic receptor 1 has been synthesised and characterised. The binding and sensing properties of 1 towards several aliphatic and aromatic dicarboxylates have been evaluated by using UV/Vis fluorescence and 1H NMR spectroscopy. The receptor strongly binds linear α,ω-dicarboxylates of appropriate lengths (C9 and C10) by acting as a cleft. For all dicarboxylates, the binding event is detected by a bathochromic shift in the UV/Vis spectra of the receptor and by strong quenching of its fluorescence.

Cargo delivery from mesoporous silica nanoparticles loaded with sulforhodamine B and capped with a difluoroboron-dipyrromethene (BODIPY) derivative was triggered by a NO

A new hybrid material based on sulforhodamine-B dye-loaded silica mesoporous nanoparticles capped with a self-immolative gate has been synthesized and characterized. The gated material's controlled release behavior is monitored under different pH conditions. Under acidic and neutral conditions, a low level of dye release is detected. However, at slightly basic pH, significant dye release occurs owing to deprotonation of the phenol moiety in the capping molecule, which results in its disassembly., We thank MINECO/FEDER (MAT2015-64139-C4-1-R and MAT2015-64139-C4-4-R) and Generalitat Valenciana (PROMETEOII/2014/047) for support. SCSIE (Universidad de Valencia) is gratefully acknowledged for all the equipment employed.

Anew colorimetric and fluorogenic probe,based on a3-formyl boron dipyrromethene (BODIPY)phe-nylhydrazone, for the sensitive and selectivedetectionNO2(g) has been prepared. The probeinsolution experi-ences aremarkablehypsochromic shift of its absorptionand fluorescence emission bands in the presence gaseousNO2(g), leading to limits of detectio noffew ppb. Theprobe also works in the solid phase, adsorbed on filterpaper strips, or chemically immobilized on the surfaceofsilica nanop articles, with limitsofdetection to the nakedeye of about 0.5 ppm., We thank the Spanish Government and FEDER founds (MAT2012-38429-C04) and Generalitat Valenciana (PROME-TEOII/2014/047) for support. SCSIE (Universidad de Valencia) is gratefully acknowledged for all the equipment employed.

The sensing properties towards aliphatic α,ω-dicarboxylates of five cyclohexane-based ligands are described. The studied ligands have been designed following the binding site-signalling unit approach and they all possess thiourea groups as recognition moieties. Ligands 1 and 3 containing naphthalene units can be used as fluorescent sensors as they form intra- or intermolecular excimers in the presence of appropriate dicarboxylates. Selective sensing of succinate and malonate versus their longer or shorter homologues has been observed.

The self-assembly of a 1:1 mixture of copper(II) ions and a rigid heteroditopic ligand L containing phen and terpy binding units gives rise in the solid state to green crystals of a hexanuclear metallamacrocycle 1. X-ray crystallography reveals that 1 consists of molecular hexagons of the grid-type family in which each metal ion is bound to two different ligands through the phen and terpy units, plus a weakly coordinated PF6 (-) anion in a highly distorted octahedral geometry. ES-MS studies of acetonitrile solutions of L and copper(II) in a 1:1 ratio show mixtures of polynuclear complexes in which trinuclear L3Cu3 species are predominant.

Five heteroditopic ligands have been prepared to be used in solid–liquid extraction of ω-amino acids into DMSO solutions. The prepared ligands contain crown ethers as cation binding sites and thiourea or amide groups for anion recognition. The aliphatic zone of the 1H NMR spectra suggests that two different species related to the amino acid are present in solution. One of these species is the complexed zwitterionic form and the other seems to be free non-zwitterionic amino acid. The presence of these two species allows extraction efficiencies higher than 100%.