0000000001301901
AUTHOR
Salvador Gil
Highly Selective Detection of Nerve‐Agent Simulants with BODIPY Dyes
Two chromo-fluorogenic probes, each based on the boron dipyrromethene core, have been developed for the detection of nerve-agent mimics. These chemosensors display both a color change and a significant enhancement of fluorescence in the presence of diethylcyanophosphonate (DCNP) and diisopropylfluorophosphate (DFP). No interference from other organophosphorus compounds or acids has been observed. Two portable chemosensor kits have been developed and tested to demonstrate its practical application in real-time monitoring.
Enediolates and dienediolates of carboxylic acids in synthesis. Synthesis of β,γ-epoxyacids from α-chloroketones
Abstract Lithium dienolates of saturated or α,β-unsaturated acids react with α-chloroketones provide a convenient method for preparation of highly sustituted β,γ-epoxyacids. These highly reactive compounds lead in most cases to variable ammounts of the corresponding β-lactones and allylic alcohols.
Addition of dianions of carboxylic acids to imines. Influence of the acid in the outcome of the reaction
Gil Grau, Salvador, Salvador.Gil@uv.es, Parra Alvarez, Margarita, Margarita.Parra@uv.es, Rodriguez Abad, Pablo, roapa@alumni.uv.es
N-Biphenyl thioureas as carboxylate receptors. Effect of the ligand substituents on the geometry of the complexes
Abstract Six new biphenyl thiourea derivatives have been prepared to be used in carboxylate sensing. Experiments carried out with these ligands have demonstrated that the type of interaction with TBA carboxylates is strongly dependent on the substituents in the thiourea moiety. These interactions go from the formation of 1:1 hydrogen-bonded complexes to acid–base reactions. In addition, different geometries have been observed for the complexes being dependent on the conformations of the free ligands in solution.
Entropy-controlled diastereoselectivity in the photocyclization of rigid derivatives of o-allylaniline.
Two rigid derivatives of o-allylaniline, namely 8-allyl-2-phenyl-1,2,3,4-tetrahydroquinoline (1b) and 7-(trans-2-cinnamyl)-2-methylindoline (1c), have been chosen as suitable systems to study the potential stereoselectivity of the photocyclization process. Photolysis of 1b leads to a mixture of diastereomeric lilolidines 4 (trans/cis), while 1cproduces a mixture of 4 (trans/cis) and the tetrahydropyrrolo[3,2,1-hi]indole derivatives 5 (trans/cis). To disclose whether the diastereoselectivity could be entropy dependent, photolysis of 1b and 1c has been performed at several temperatures. In both cases, linear relationships have been observed when ln(k(t)/k(c)) (the relative reaction rate const…
A Convenient Generation of Acetic Acid Dianion
The lithium enediolate of acetic acid can be generated efficiently, as a 0.5 M solution in THF, using lithium amides prepared from n-butyllithium in THF and either diethylamine or 1,3,3-trimethyl-6-azabicyclo-(3.2.1)-octane (AZA). Its reaction with carbonyl compounds leads to the corresponding β-hydroxy acids in good to moderate yields. Better yields are usually obtained when these amines are added in sub-stoichiometric amounts. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Resorcinol Functionalized Gold Nanoparticles for Formaldehyde Colorimetric Detection
[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.
Peptide-Capped Mesoporous Nanoparticles: Toward a more Efficient Internalization of Alendronate
[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 am…
Chromogenic Detection of Nerve Agent Mimics by Mass Transport Control at the Surface of Bifunctionalized Silica Nanoparticles
Chemical warfare (CW) agents are toxic chemicals that have been used in several terrorist attacks in recent years. Among CW species, nerve agents are probably the most dangerous; their high toxicity and facile synthesis underscores the need to detect these lethal compounds with quick, reliable procedures. Analytical methods based on enzymatic assays and physical measurements have generally been used to detect these hazards. However, these protocols usually have limitations such as low selectivity, poor portability, and a certain level of complexity. In recent years, several chromogenic and fluorogenic sensors, and reagents for the detection of nerve agents have been described. For instance,…
Nerve agent simulant detection by using chromogenic triaryl methane cation probes
Two triaryl methane cations have been used as probes for colorimetric detection of nerve agent simulants. Buffered mixed aqueous solutions of 1 and 2 showed bathochromic shifts in the presence of DCNP (diethylcyanophosphonate) and DCP (diethylchlorophosphate). The colour modulation can be observed to the naked eye. Appropriate mechanisms for the recognition event are proposed. © 2012 Elsevier Ltd.
Fluorescent Sensing of Maleate versus Fumarate by a Neutral Cyclohexane Based Thiourea Receptor.
A new cyclohexyl based fluorescent anion receptor, is able to recognize maleate versus fumarate both as their TMA salts. Costero Nieto, Ana Maria, Ana.Costero@uv.es ; Colera Llavata, Manuel, Manuel.Colera@uv.es ; Gaviña Costero, Pablo, Pablo.Gavina@uv.es ; Gil Grau, Salvador, Salvador.Gil@uv.es
ChemInform Abstract: Enantioselective α-Alkylation of Unsaturated Carboxylic Acids Using a Chiral Lithium Amide.
Abstract The regio- and stereochemistry of the alkylation of dienediolates from unsaturated carboxylic acids with benzylic halides, which often results in mixtures of isomers, can be controlled by means of changes in the lithium amide, allowing the α-regioisomer to be obtained as the major diastereoisomer. In addition, when chiral amines are used, moderate enantiomeric excesses can be attained.
Chemical and electrochemical behaviour of 4,4’,4’’,4’’’-tetrakis(dimethylamino)-tetraphenylethylene in an oxidant environment: Toward a new sensor for NO2 and SO2 in gas phase
Abstract Electrochromic compounds are suitable candidates for being used in sensor design. Here we report the use of 4,4’,4’’,4’’’-tetrakis(dimethylamino)-tetraphenylethylene for detecting both NO2 and SO2. Whereas the sensing mechanism in the case of nitrogen dioxide is a simple chemical oxidation reaction, in the case of sulfur dioxide, the mechanism is much more complex and the reaction requires the presence of t-butylhydroperoxide to take place. By modifying the detection conditions both compounds can be detected in gas phase. Additionally, a wide electrochemical study has been carried out to understand the role played by the t-butylhydroperoxide in the reaction with sulfur dioxide.
ChemInform Abstract: Components of the Sex Pheromone of Chilo supressalis: Efficient Syntheses of (Z)-11-Hexadecenal and (Z)-13-Octadecenal.
Abstract (Z)-11-Hexedecenal 1a and (Z)-13-octadecenenal 2a, components of the sex attractant pheromone of Chilo supressalis, have been synthesized as their ethylene acetals 1b and 2b from cyclododecanone 3, through intermediacy of the C12 ω functionalized acetals 8 and 12.
A new selective fluorogenic probe for trivalent cations.
[EN] A new selective chromo-fluorogenic probe for Fe 3+, Cr 3+ and Al 3+ is reported. Detection limits are in the ¿M range and the fluorogenic sensing ability could be observed by the naked eye when illuminated with UV-light. No response is observed with divalent cations. © 2012 The Royal Society of Chemistry.
Alkene epoxidations catalysed by Mo(VI) supported on Merrifield's polymer
High conversion and epoxide selectivity from alkenes is achieved with tert-butyl hydroperoxide and a polystyrene-grafted Mo(VI) catalyst, with no noticeable leaching of Mo from the support.
Chromogenic Chemodosimeter Based on Capped Silica Particles to Detect Spermine and Spermidine
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 a…
Intramolecular Interactions in the Triplet Excited States of Benzophenone–Thymine Dyads
Time-resolved and product studies on the synthesized dyads 1 and 2 have provided evidence that the benzophenone-to-thymine orientation strongly influences intramolecular photophysical and photochemical processes. The prevailing reaction mechanism has been established as a Paterno-Büchi cycloaddition to give oxetanes 3-6; however, the ability of benzophenone to achieve a formal hydrogen abstraction from the methyl group of thymidine has also been evidenced by the formation of photoproducts 7 and 8. These processes have been observed only in the case of the cisoid dyad 1. Adiabatic photochemical cycloreversion of the oxetane ring is achieved upon direct photolysis to give the starting dyad 1 …
Highly selective and sensitive chromo-fluorogenic detection of the Tetryl explosive using functional silica nanoparticles
Silica nanoparticles containing polyamines and thiol groups have been used as probes for the selective detection of Tetryl. © 2011 The Royal Society of Chemistry.
Alkylation of lithium dienediolates of butenoic acids. Regioselectivity effects of structure and leaving group of the alkylating agent
Abstract Regioselectivity of alkylation of but-2-enoic acids 1 and 2 by alkyl halides strongly depends on the reactivity of the electrophile. High α selectivity results for saturated alkyl halides, whereas poor α-selectivity is obtained for highly reactive allyl and benzyl halides. For reactive alkylating halides selectivity is partly governed by the ion pairing aggregates of the dienediolates. Lithium bromide and the carboxylate generated in the ongoing reaction cause opposite effects on regioselectivity.
Hg2+ and Cu2+ selective detection using a dual channel receptor based on thiopyrylium scaffoldings
2,4,6-Triphenylthiopyrylium functionalized with an aza-oxa-thia macrocycle is able to selectively recognize Hg2+ cation by a color change and Cu2+ cation by a remarkable significant emission enhancement.
Towards the fluorogenic detection of peroxide explosives through host-guest chemistry
[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.
Polymer-supported molybdenyl thioglycolate as oxygen atom transfer reagent
Abstract Oxo-transfer reactions of a variety of substrates in DMF or methanol using polymer-supported molybdenyl thioglycolate (PSMT) have been investigated. The clean oxidation of Me 2 PhP, n -butanethiol or benzoin to yield Me 2 PhPO, disulfide or benzil, respectively, occurs in high yield. In the presence of air or pyridine N-oxide, a catalytic cycle is accomplished which goes on until the completion of the substrate.
Integrative Metabolomic and Transcriptomic Analysis for the Study of Bladder Cancer
Metabolism reprogramming is considered a hallmark of cancer. The study of bladder cancer (BC) metabolism could be the key to developing new strategies for diagnosis and therapy. This work aimed to identify tissue and urinary metabolic signatures as biomarkers of BC and get further insight into BC tumor biology through the study of gene-metabolite networks and the integration of metabolomics and transcriptomics data. BC and control tissue samples (n = 44) from the same patients were analyzed by High-Resolution Magic Angle Spinning Nuclear Magnetic Resonance and microarrays techniques. Besides, urinary profiling study (n = 35) was performed in the same patients to identify a metabolomic profi…
Crown ethers derived from cyclohexane. Influence of their stereochemistry in complexation and transport
Abstract Crown ethers derived from cyclohexane have been prepared. The trans stereochemistry of the substituents on the carbocyclic ring makes that only one conformation can complex cations. The influence of the stereochemistry in complexation has been studied.
Experimental evidence for the homochiral aggregation of ammonium salts in solution
NMR and X-ray evidence for the homochiral aggregation of chiral ammonium picrates from racemic solutions is presented.
A Chromogenic Probe for the Selective Recognition of Sarin and Soman Mimic DFP
The synthesis, characterization and sensing features of a novel probe 1 for the selective chromogenic recognition of diisopropylfluorophosphate (DFP), a sarin and soman mimic, in 99:1 (v/ v) water/acetonitrile and in the gas phase is reported. Colour modulation is based on the combined reaction of phosphorylation of 1 and fluoride-induced hydrolysis of a silyl ether moiety. As fluoride is a specific reaction product of the reaction between DFP and the OH group, the probe shows a selective colour modulation in the presence of this chemical. Other nerve agent simulants, certain anions, oxidant species and other organophosphorous compounds were unable to induce colour changes in 1. This is one…
Colorimetric and fluorescent hydrazone-BODIPY probes for the detection of γ-hydroxybutyric acid (GHB) and cathinones
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 othe…
Singlet Excited-State Interactions in Naphthalene-Thymine Dyads
Two thymidine-derived nucleosides 1 and 2 were prepared by attaching a chiral naphthalene to the positions 5′ and 3′ of the sugar. The resulting dyads, which contain key substructures present in drugs and nucleic acids, exhibit different spatial arrangements (transoid or cisoid) of the fluorophore relative to the thymine unit. Emission measurements on these compounds in the presence of ROH molecules revealed a remarkable intramolecular fluorescence quenching for dyad 1. The obtained results are consistent with quenching of the singlet excited state of 1 by hydrogen-bond donor solvents. Thus, a physical deactivation process (vibronically induced internal conversion) would be the pathway resp…
ChemInform Abstract: Trienediolates of Hexadienoic Acids in Synthesis. Synthesis of Retinoic and nor-Retinoic Acids.
Abstract Double deprotonation of either (E,E)-3-methyl-2,4-hexadienoic acid 2, or 4,6-dimethyldihydro-2-pyrone 3 generates apparently the same lithium trienediolate, which affords ω-hydroxy acids 9 on reaction with ketones 7. Hydroxy acids 9 are easily dehydrated to octatrienoic acids 5, which are structurally related to retinoic acid. Similarly, sorbic acid 1 leads to nor-retinoic acid analogs 6.
Chromogenic detection of nerve agent mimics
The current rise in international concern over criminal terrorist attacks via chemical warfare (CW) agents has resulted in an increasing interest in the detection of these lethal chemicals. Among CW species, nerve agents are extremely dangerous and their high toxicity and ease of production underscore the need to detect these deadly chemicals via quick and reliable procedures. A number of detection systems have been developed, most of them based on enzymatic and physical methodologies. However, these usually show limitations such as low selectivity, lack of portability and a certain complexity in their use. An alternative to these classical methods that has been gaining interest in recent y…
Synthesis and In Vitro Evaluation of a Photosensitizer-BODIPY Derivative for Potential Photodynamic Therapy Applications
A new photosensitizer (1) based on the 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) scaffold has been synthesized. 1 is water soluble and showed an intense absorption band at 490 nm (e=77600 cm-1M-1) and an emission at 514 nm. In vitro toxicity of 1 in the presence of light and in darkness has been studied with HeLa, HaCaT, MCF-7, and SCC-13 cell lines. Moreover, internalization studies of 1 in these cell lines were also performed. These results suggested that 1 is more toxic for SCC-13 and HeLa carcinoma cells than for the HaCaT noncancerous immortal human keratinocytes. Toxicity upon light irradiation was due to the formation of singlet oxygen and reactive oxygen species (ROS). Cel…
A simple synthesis of γ-aminoacids
The addition of dianions of carboxylic acids to bromoacetonitrile, leads, in good yields, to the corresponding γ-cyanoacids that give γ-aminoacids on hydrogenation. This two-step methodology improves the results previously described.
Acetylcholinesterase-Capped Mesoporous Silica Nanoparticles That Open in the Presence of Diisopropylfluorophosphate (a Sarin or Soman Simulant)
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).
Enantioselective sensing of dicarboxylates. Influence of the stoichiometry of the complexes on the sensing mechanism
Two new cyclohexane-based thiourea chiral ligands have been synthesized in their enantiomerically pure forms. Both the ability of these ligands in the complexation of chiral dicarboxylates and their sensing properties have been studied. The influence of the stoichiometry of the formed complexes on the fluorescent properties of the systems has been established. The effect of additional substitution in the cyclohexyl moiety was considered by comparing the properties of the newly prepared ligands with those of similar compounds previously described.
Supplementary Material from Towards the fluorogenic detection of peroxide explosives through host–guest chemistry
Towards the fluorogenic detection of peroxide explosives through host-guest chemistry
Surfactant-assisted chromogenic sensing of cyanide in water
Chromogenic cyanide recognition in water was achieved by the use of a hydrophobic dye in micellar containers.
Mesoporous Silica Nanoparticles in Chemical Detection: From Small Species to Large Bio-Molecules
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.
ChemInform Abstract: Optical Chemosensors and Reagents to Detect Explosives
This critical review is focused on examples reported from 1947 to 2010 related to the design of chromo-fluorogenic chemosensors and reagents for explosives (141 references).
Photocyclization of a bichromophoric phenol/olefi system substituted at the methylene spacer - Zwitterions versus H-bridged intermediates in the excited state proton transfer
Photolysis of (E)- and (Z)-2-(1-ethyl-3-phenylpropenyl)phenol (1 and 2) under a variety of conditions produces a mixture of dihydrobenzopyrans 3 and 4, dihydrobenzofuran 5, cyclopropanes 6 and 7, and rearranged olefin 8. Acidic treatment of 1 and 2 gives a mixture of the six-membered ring products 3 and 4. Remarkable differences, associated with the nature of the precursor and the reaction conditions, are observed in the regiochemistry of cyclization and in the stereochemistry of the dihydrobenzopyrans (3/4 ratio). This points in favour of an H-bridged intermediate, rather than a fully zwitterionic species, as the direct precursor of the photocyclized products.
Fluorescent chemosensors based on cyclohexane: selective sensing of succinate and malonate versus their longer or shorter homologues
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.
Unexplored nucleophilic ring opening of aziridines.
The reactivity of dianions of carboxylic acids towards aziridines has been studied. Although, a similar reactivity to that of enolates from ketones, esters or amides has been observed, the method directly yields g-aminoacids in one step. The method is complementary of previous results of enenediolate reactivity with other electrophiles. A comparative study with the reactivity of this enediolates with epoxides is included.
On the Ion-Pair Recognition and Indication Features of a Fluorescent Heteroditopic Host Based on a BODIPY Core
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.
Sex Pheromone of Chilo Suppressalis: Efficient Syntheses of (Z)-11-Hexadecenal, (Z)-13-Octadecenal And (Z)-9-Hexadecenal
Abstract The constituents of the sex attractant pheromone of Chilo suppressalis: (Z)-11-Hexedecenal 1, (Z)-13-octadecenenal 2 and (Z)-9-Hexadecenal 3 have been synthesized as their ethylene acetals 19, 15 and 13, in six steps from easily available compounds. The synthetic methodology can be applied to preparative scale.
Iodine oxidative coupling of diene and triene-diolates of unsaturated carboxylic acids.
Abstract Oxidative Coupling of the dianions of unsaturated carboxylic acids 1 , and 4 with iodine, which provides a convenient and facile preparation of γ,γ and e,e-dicarboxylic acids 2 and 5, apparently occurs through SET substitution of intermediate iodo-carboxylates.
A chalcone-based highly selective and sensitive chromofluorogenic probe for trivalent metal cations
[EN] Anew chalcone-based probe for the chromofluorogenic sens-ing of trivalent (Al3 +,Fe3+,Cr3+,Ga3+,In3+and As3 +)overmono-and divalent cationsand anionsisreported. In the presence of trivalent metal cations,the probe was able to displayaremarkable color change from yellow to colorless that wasclearly visible to the naked eye. Also, the initial strongyellowemission was gradually quenched and substituted by aweaklyshifted band.
Poly(amine) biphenyl derivatives as fluorescent sensors for anions and cations
Four new ligands, derived from tetramethylbenzidine and containing additional amino groups, are described. The influence of pH on the fluorescent properties of these ligands has been studied, and the effect of the dihedral angle between the aromatic rings on the fluorescent response has been established. The behaviour of the new ligands, and that of others previously described in both the complexation and sensing of different anions and cations, are also described.
Direct evidence for neutrino flavor transformation from neutral-current interactions in the Sudbury Neutrino Observatory
Observations of neutral current neutrino interactions on deuterium in the Sudbury Neutrino Observatory are reported. Using the neutral current, elastic scattering, and charged current reactions and assuming the standard 8B shape, the electron-neutrino component of the 8B solar flux is 1.76 +/-0.05(stat.)+/-0.09(syst.) x10^6/(cm^2 s), for a kinetic energy threshold of 5 MeV. The non-electron neutrino component is 3.41+/-0.45(stat.)+0.48,-0.45(syst.) x10^6/(cm^2 s), 5.3 standard deviations greater than zero, providing strong evidence for solar electron neutrino flavor transformation. The total flux measured with the NC reaction is 5.09 +0.44,-0.43(stat.)+0.46,-0.43(syst.)x10^6/(cm^2 s), consi…
Functionalized Gold Nanoparticles as an Approach to the Direct Colorimetric Detection of DCNP Nerve Agent Simulant
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
Chromo-Fluorogenic Detection of Nerve-Agent Mimics Using Triggered Cyclization Reactions in Push-Pull Dyes
A family of azo and stilbene derivatives (1-9) are synthesized, and their chromo-fluorogenic behavior in the presence of nerve-agent simulants, diethylchlorophosphate (DCP), diisopropylfluorophosphate (DFP), and diethylcyanophosphate (DCNP) in acetonitrile and mixed solution of water/acetonitrile (3:1 v/v) buffered at pH 5.6 with MES, is investigated. The prepared compounds contain 2-(2-N,N-dimethylaminophenyl)ethanol or 2-[(2-N,N-dimethylamino)phenoxy]ethanol reactive groups, which are part of the conjugated pi-system of the dyes and are able to give acylation reactions with phosphonate substrates followed by a rapid intramolecular N-alkylation. The nerve-agent mimic-triggered cyclization …
3-Formyl-BODIPY Phenylhydrazone as a Chromo-Fluorogenic Probe for Selective Detection of NO2 (g)
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.
Efficient Addition of Acid Enediolates to Epoxides
We report new conditions to facilitate the addition of dianions of carboxylic acids to epoxides as an alternative method to the use of aluminum enolates. These conditions require the use of a sub-stoichiometric (10%) amount of amine for dianion generation and the previous activation of the epoxide with LiCl. Other Lewis acids have been shown to be less effective. Yields are good but only low diastereoselectivity is attained, which has not been controlled despite attempts at optimization. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Polyenolates of unsaturated carboxylic acids in synthesis. A straightforward synthesis of retinoic acids.
Abstract Retinoic acids are prepared in a two step procedure by addition of lithium trienediolates of sorbic acid and 3-methyl-sorbic acid to β-ionone.
Binding and Fluorescent Sensing of Dicarboxylates by a Bis(calix[4]pyrrole)-Substituted BODIPY Dye
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.
Multi-channel receptors based on thiopyrylium functionalised with macrocyclic receptors for the recognition of transition metal cations and anions.
We report herein the synthesis and characterization of a family of ligands containing different cation binding sites covalently connected to a thiopyrylium signalling reporter. The receptors L1–L6 are able to signal the presence of certain metal cations via three different channels; i.e. electrochemically, fluorogenically and chromogenically. An acetonitrile solution of L1–L6 shows a bright blue colour due to a charge-transfer band in the 575–585 nm region. The colour variation in acetonitrile of L1–L6 in the presence of the metal cations Ag+, Cd2+, Cu2+, Fe3+, Hg2+, Ni2+, Pb2+ and Zn2+ has been studied. A selective hypsochromic shift of the blue band was found for the systems L4-Pb2+ and L…
Hydrolysis of DCNP (a Tabun mimic) catalyzed by mesoporous silica nanoparticles
[EN] The hydrolysis of diethylcyanophosphonate, DCNP (a Tabun simulant) in the presence of mesoporous silica nanoparticles (MSN) has been studied in acetonitrile:water (99.5:0.5 v/v) mixtures using 31P NMR as a suitable technique to follow the DCNP hydrolysis. MSN alone was not capable to induce DCNP hydrolysis, yet MSN in combination with the presence of the bases potassium carbonate, triethylamine or DABCO enhanced DCNP degradation. When MSN was used combined with K2CO3, a hydrolysis of ca. 95% of the initial DCNP after 60 min was observed. In the presence of DABCO, MSN was able to induce the hydrolysis of ca. 90% of DCNP after the same time. However, the DCNP hydrolysis using MSN in the …
A nitric oxide induced “click” reaction to trigger the aggregation induced emission (AIE) phenomena of a tetraphenyl ethylene derivative: A new fluorescent probe for NO
Abstract An Aggregation Induced Emission (AIE) transduction mechanism has been used to detect nitric oxide (NO). A new tetraphenylethylene derivative functionalized with alkyne moieties has been prepared to work as a fluorescent probe. A “click” reaction was chosen because NO is able to generate the required catalytic species by reducing Cu(II) to Cu(I).
ChemInform Abstract: Synthesis of Dienedioic and Tetraenedioic Acids by Oxidative Coupling of Unsaturated Carboxylic Acid Dienediolates by 1,2-Diiodoethane.
Abstract Acyclic and cyclic unsaturated carboxylic acids 1 to 4 are most easily converted to unsaturated dicarboxylic acids 5 to 8 by oxidative coupling of their diene- or triene-diolates by 1,2-diiodoethane. This procedure improves formerly reported oxidations by iodine or silver salts.
Lithium enediolates and dienediolates of carboxylic acids in synthesis: Alkylation with secondary halides
Abstract High yields in the alkylation of dianions of α,β-unsaturated carboxylic acids with secondary halides can be obtained despite elimination reactions occurring. α-Regioselectivity for the alkylation of but-2-enoic acids ( 1–4 ) is seldom obtained. Although double bond stereoselectivity is higher than 99% for γ-alkylated products, stereoselectivity is rather poor for most of the α-alkylated products.
Experimental and theoretical investigations for the tandem alkylation–isomerization reactions between unsaturated carboxylic acids and allyl halides
Abstract—Alkylation of dienediolates from unsaturated carboxylic acids with allylic halides when followed by solventless thermaltreatment at 150 to 2008C afford rearranged products on a trend highly dependent on the acarbon substitution. Thus, 2,2-bisallylated acidswith H atoms at C-2 lead to its 1,3-shift, whereas 2-methyl-2,2-bisallylated acids lead to the corresponding Cope rearrangement product. Inthe latter case, this tandem allylation-Cope reaction lead, in a highly regio and diastereoselective way, to products not accessible from directalkylation. B3LYP/6-31G p energies for the compounds involved at these isomerizations are in reasonable agreement with the experiments,allowing to exp…
Urinary Metabolic Signatures Detect Recurrences in Non-Muscle Invasive Bladder Cancer
Patients with non-muscle invasive bladder cancer (NMIBC) undergo lifelong monitoring based on repeated cystoscopy and urinary cytology due to the high recurrence rate of this tumor. Nevertheless, these techniques have some drawbacks, namely, low accuracy in detection of low-grade tumors, omission of pre-neoplastic lesions and carcinomas in situ (CIS), invasiveness, and high costs. This work aims to identify a urinary metabolomic signature of recurrence by proton Nuclear Magnetic Resonance (1H NMR) spectroscopy for the follow-up of NMIBC patients. To do this, changes in the urinary metabolome before and after transurethral resection (TUR) of tumors are analyzed and a Partial Least Square Dis…
Enzyme-responsive silica mesoporous supports capped with azopyridinium salts for controlled delivery applications
11 páginas, 7 figuras, 3 tablas y 2 esquemas
Conformationally regulated fluorescent sensors. Study of the selectivity in Zn 2+ versus Cd 2+ sensing
Abstract The Zn 2+ and Cd 2+ complexing properties of four ligands containing a 4,4′-substituted biphenyl moiety are described. Ligands 1 and 3 , containing only one 1-aza-18-crown-6 cavity, lead to selective complexation of Cd 2+ versus Zn 2+ . Ligand 4 , with two crown cavities linked to a tetramethylbenzidine unit, is able to form 1:1 complexes with Zn 2+ and Cd 2+ , showing a higher complexing constant with Zn 2+ than with Cd 2+ , probably due to enthalpic factors. Several complementary experiments suggest that the 1:1 complexes formed by ligand 4 involve both crown cavities acting together to give rise to clamp structures. The formation of this type of zinc complex gives rise to red sh…
Highly selective fluorescence detection of hydrogen sulfide by using an anthracene-functionalized cyclam-CuII complex
An anthracene-functionalised cyclam-copper(II) complex for the detection of HS- in aqueous environments has been prepared. This probe displays poor fluorescence but can selectively and sensitively detect HS- anions in water over other anions, biothiols and common oxidants such as H2O2 through remarkably enhanced emission. This turn-on response in the presence of the HS- anion is ascribed to a demetallation reaction that inhibits emission quenching observed in the initial complex as a result of the presence of the paramagnetic Cu2+ centre. Moreover, real-time fluorescence imaging measurements confirm that probe [Cu(1)](2+) can be easily used to detect intracellular HS- at micromolar concentr…
Components of the Sex Pheromone of Chilo Supressalis: Efficient Syntheses of (Z)-11-Hexadecenal and (Z)-13-Octadecenal
Abstract (Z)-11-Hexedecenal 1a and (Z)-13-octadecenenal 2a, components of the sex attractant pheromone of Chilo supressalis, have been synthesized as their ethylene acetals 1b and 2b from cyclododecanone 3, through intermediacy of the C12 ω functionalized acetals 8 and 12.
ChemInform Abstract: Alkylation of Lithium Dienediolates of Butenoic Acids. Regioselectivity Effects of Structure and Leaving Group of the Alkylating Agent.
Abstract Regioselectivity of alkylation of but-2-enoic acids 1 and 2 by alkyl halides strongly depends on the reactivity of the electrophile. High α selectivity results for saturated alkyl halides, whereas poor α-selectivity is obtained for highly reactive allyl and benzyl halides. For reactive alkylating halides selectivity is partly governed by the ion pairing aggregates of the dienediolates. Lithium bromide and the carboxylate generated in the ongoing reaction cause opposite effects on regioselectivity.
Trienediolates of hexadienoic acids in synthesis. synthesis of retinoic and nor-retinoic acids.
Abstract Double deprotonation of either (E,E)-3-methyl-2,4-hexadienoic acid 2, or 4,6-dimethyldihydro-2-pyrone 3 generates apparently the same lithium trienediolate, which affords ω-hydroxy acids 9 on reaction with ketones 7. Hydroxy acids 9 are easily dehydrated to octatrienoic acids 5, which are structurally related to retinoic acid. Similarly, sorbic acid 1 leads to nor-retinoic acid analogs 6.
Selective and Sensitive Chromogenic Detection of Cyanide and HCN in Solution and in Gas Phase
Two triphenylmethane based chemodosimeters for selective and chromogenic sensing of cyanide anions in aqueous environments and of hydrogen cyanide in gas phase were prepared and studied.
A Sensitive Nanosensor for the In Situ Detection of the Cannibal Drug.
[EN] A bio-inspired nanodevice for the selective and sensitive fluorogenic detection of 3,4- methylenedioxypyrovalerone (MDPV), usually known as Cannibal drug, is reported. The sensing nanodevice is based on mesoporous silica nanoparticles (MSNs), loaded with a fluorescent reporter (rhodamine B) and functionalized on their external surface with a dopamine derivative (3), which specifically interacts with the recombinant human dopamine transporter (DAT), capping the pores. In the presence of MDPV, DAT detaches from the MSNs consequently causing rhodamine B release and allowing drug detection. The nanosensor shows a detection limit of 5.2 µM and it is able to detect the MDPV drug both in sali…
ChemInform Abstract: Iodine Oxidative Coupling of Diene- and Triene-Diolates of Unsaturated Carboxylic Acids.
Abstract Oxidative Coupling of the dianions of unsaturated carboxylic acids 1 , and 4 with iodine, which provides a convenient and facile preparation of γ,γ and e,e-dicarboxylic acids 2 and 5, apparently occurs through SET substitution of intermediate iodo-carboxylates.
ChemInform Abstract: Enediolates and Dienediolates of Carboxylic Acids in Synthesis. Synthesis of β,γ-Epoxyacids from α-Chloroketones.
Abstract Lithium dienolates of saturated or α,β-unsaturated acids react with α-chloroketones provide a convenient method for preparation of highly sustituted β,γ-epoxyacids. These highly reactive compounds lead in most cases to variable ammounts of the corresponding β-lactones and allylic alcohols.
Structure and Conformational Studies of Aza-Crown 8-Amino-BODIPY Derivatives: Influence of Steric Hindrance on Their Photophysical Properties
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.
3,3′-Disubstitued 2,2′-Bipyridines as Carboxylate Receptors: Conformational Regulation of the Bipyridine Moiety
Two bipyridine derivatives were synthesized and characterized, and their ability to act as sensors for carboxylates was evaluated by UV/Vis and fluorescence studies. The influence of the substituents of the thiourea groups on the stoichiometry of the resulting dicarboxylate complexes was established. Conformational changes in the bipyridine moiety under different conditions were evaluated.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Solid–liquid extraction of ω-amino acids using ditopic receptors
Abstract 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%.
A new fluorescent "turn-on" chemodosimeter for the detection of hydrogen sulfide in water and living cells
[EN] A new fluorescent turn-on probe for the selective detection of hydrogen sulfide in water and living cells based on a 8-hydroxyquinoline fluorophore functionalized with a 2,6-dinitrophenyl ether moiety has been developed.
A Chemosensor Bearing Sulfonyl Azide Moieties for Selective Chromo-Fluorogenic Hydrogen Sulfide Recognition in Aqueous Media and in Living Cells
A simple chemodosimeter based on a sulfonyl azide dye (1-Az), which displayed a highly selective response toward hydrogen sulfide anion in mixed aqueous media, was synthesised and characterised. Addition of hydrogen sulfide to acetonitrile/HEPES 1:1 solutions of 1-Az induced a clear colour change from red-orange to yellow, which was easily detected by the naked eye, and by an enhancement in the emission intensity. Other common anions, thiol-containing biomolecules and oxidants did not induce any noticeable colour or fluorescence modulation in the probe. The chemodosimeter also showed a good sensitivity, with limits of detection of 11.91 and 0.63 μM by using UV/Vis or fluorescence measuremen…
An Efficient Synthesis of γ-Aminoacids and Attempts to Drive Its Enantioselectivity
Addition of carboxylic acid dianions to bromoacetonitrile lead, in good yields,to the corresponding gamma-cyanoacids, which on hydrogenation yielded gamma-amino acids. This two step methodology improves upon previously described results. Poor e.e's resultedfrom our attempts to drive the enantioselectivity of this transformation by chiral amide induction.
Amidase-responsive controlled release of antitumoral drug into intracellular media using gluconamide-capped mesoporous silica nanoparticles
MCM-41 silica nanoparticles were used as inorganic scaffolding to prepare a nanoscopic-capped hybrid material S1, which was able to release an entrapped cargo in the presence of certain enzymes, whereas in the absence of enzymes, a zero release system was obtained. S1 was prepared by loading nanoparticles with Safranine O dye and was then capped with a gluconamide derivative. In the absence of enzymes, the release of the dye from the aqueous suspensions of S1 was inhibited as a result of the steric hindrance imposed by the bulky gluconamide derivative, the polymerized gluconamide layer and the formation of a dense hydrogen-bonded network around the pore outlets. Upon the addition of amidase…
Chromo-fluorogenic BODIPY-complexes for selective detection of V-type nerve agent surrogates
Two new Eu3+ and Au3+ BODIPY-complexes capable of chromofluorogenically detecting micromolar concentrations of V-type nerve agent surrogates by a simple displacement assay are described
Selective chromo-fluorogenic detection of trivalent cations in aqueous environments using a dehydration reaction
[EN] Trivalent cations (Al3+, Fe3+, Cr3+, As3+, In3+ and Ga3+) induced a dehydration reaction of a chemodosimeter in water that is coupled with colour and emission changes.
Unusual Regioselectivity in the Opening of Epoxides by Carboxylic Acid Enediolates
Addition of carboxylic acid dianions appears to be a potential alternative to the use of aluminium enolates for nucleophilic ring opening of epoxides. These conditions require the use of a sub-stoichiometric amount of amine (10% mol) for dianion generation and the previous activation of the epoxide with LiCl. Yields are good, with high regioselectivity, but the use of styrene oxide led, unexpectedly, to a mixture resulting from the attack on both the primary and secondary carbon atoms. Generally, a low diastereoselectivity is seen on attack at the primary center, however only one diastereoisomer was obtained from attack to the secondary carbon of the styrene oxide.
Halogen-containing BODIPY derivatives for photodynamic therapy
Abstract Two iodinated (1 and 2) and two brominated (3 and 4) BODIPY-based photosensitizers are prepared and characterized using slightly modified synthetic procedures previously described. 1–4 present intense absorption bands in the 510–540 nm interval and very weak emissions due to the presence of halogen atoms in their structure. Irradiation of aqueous solutions of 1–4 with visible light (wavelength > 475 nm) induce the generation of singlet oxygen with quantum yields of ca. 0.62–0.66 for the photosensitizers containing iodine atoms (1 and 2) and of ca. 0.16–0.21 for the brominated counterparts (3 and 4). In vitro studies carried out with HeLa, SCC-13 and HaCaT cell lines and the four ph…
Off–on BODIPY-based chemosensors for selective detection of Al3+ and Cr3+versus Fe3+ in aqueous media
[EN] Two new off-on BODIPY-based chemosensors that are highly sensitive for trivalent cations in aqueous solutions are described. Compound 2 exhibits selective sensing of Al3+ and Cr3+ versus Fe3+ through two different channels (UV-vis and fluorescence).
Dyes That Bear Thiazolylazo Groups as Chromogenic Chemosensors for Metal Cations
A family of dyes (L 1-L 6) that contain a thiazolylazo group as signalling subunit and several macrocyclic cavities with different ring sizes and type and number of heteroatoms as binding sites has been synthesized and characterized. Solutions of L 1-L 6 in acetonitrile show broad and structureless absorption bands in the 554-577 nm range with typicalmolar absorption coefficients that range from 20000 to 32000 M -1 cm -1. A detailed protonation study was carried out with solutions of L 1, L 2 and L 5 in acetonitrile. Addition of one equivalent of protons to L 1 and L 2 resulted in the development of a new band at 425 and 370 nm, respectively, which was ascribed to protonation in the aniline…
Aryl carbinols as nerve agent probes. Influence of the conjugation on the sensing properties
Two new aryl carbinols (1 and 3) have been synthesised and characterised and their ability as OFF-ON probes for the chromogenic detection of the nerve agent simulant in acetonitrile has been tested. In addition compound 2 has been also studied. The carbinols suffered a phosphorylation reaction followed by an elimination process giving rise to the corresponding carbocations. This transformation of the carbinol into the carbocation is responsible for a significant color change. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012.
Selective chromo-fluorogenic detection of DFP (a Sarin and Soman mimic) and DCNP (a Tabun mimic) with a unique probe based on a boron dipyrromethene (BODIPY) dye.
[EN] A novel colorimetric probe (P4) for the selective differential detection of DFP (a Sarin and Soman mimic) and DCNP (a Tabun mimic) was prepared. Probe P4 contains three reactive sites; i.e. (i) a nucleophilic phenol group able to undergo phosphorylation with nerve gases, (ii) a carbonyl group as a reactive site for cyanide; and (iii) a triisopropylsilyl (TIPS) protecting group that is known to react with fluoride. The reaction of P4 with DCNP in acetonitrile resulted in both the phosphorylation of the phenoxy group and the release of cyanide, which was able to react with the carbonyl group of P4 to produce a colour modulation from pink to orange. In contrast, phosphorylation of P4 with…
An Au(iii)–amino alcohol complex for degradation of organophosphorus pesticides
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.
Selective opening of nanoscopic capped mesoporous inorganic materials with nerve agent simulants; an application to design chromo-fluorogenic probes.
A hybrid nanoscopic capped mesoporous material, that is selectively opened in the presence of nerve agent simulants, has been prepared and used as a probe for the chromo-fluorogenic detection of these chemicals. © 2011 The Royal Society of Chemistry.
Syntheses of dopaminergic 1-cyclohexylmethyl-7,8-dioxygenated tetrahydroisoquinolines by selective heterogeneous tandem hydrogenation
Abstract We describe the preparation in a ‘one-pot’ sequence 1-cyclohexylmethyl 7,8-dioxygenated tetrahydroisoquinoline, substituted and unsubstituted in the C ring by application of the Photo–Fries transposition, followed by a tandem reduction–cyclization and further reduction. Indeed, we have accomplished for the first time regioselective hydrogenation of the benzylic ring of the tetrahydroisoquinoline systems. All 1-cyclohexylmethyl THIQ synthesized were able to displace D2 dopamine receptor from its specific binding site in rat striatal membranes, while the N-methylated derivatives showed also affinity for D1 dopamine receptors.
Chiral cyclohexane based fluorescent chemosensors for enantiomeric discrimination of aspartate
Some new chiral cyclohexyl based fluorescent anion receptors have been synthesized and their absolute configuration has been determined by using circular dichroism (CD). Complexation experiments have been carried out with several dicarboxylates, and stoichiometries and complexation constants for the corresponding complexes have been determined. The chiral discrimination ability of these ligands for chiral dicarboxylates has been studied and the best results have been obtained with TMA aspartate.
Boolean operations mediated by an ion-pair receptor of a multi-readout molecular logic gate
A heteroditopic BODIPY dye that performs all basic Boolean operations with a cation (K+) and an anion (F-) as inputs and absorption, transmission and fluorescence as outputs is described. The molecular logic gate can also act as a digital comparator between the inputs.
Design of enzyme-mediated controlled release systems based on silica mesoporous supports capped with ester-glycol groups
[EN] An ethylene glycol-capped hybrid material for the controlled release of molecules in the presence of esterase enzyme has been prepared. The final organic-inorganic hybrid solid S1 was synthesized by a two-step procedure. In the first step, the pores of an inorganic MCM-41 support (in the form of nanoparticles) were loaded with [Ru(bipy) 3]Cl 2 complex, and then, in the second step, the pore outlets were functionalized with ester glycol moieties that acted as molecular caps. In the absence of an enzyme, release of the complex from aqueous suspensions of S1 at pH 8.0 is inhibited due to the steric hindrance imposed by the bulky ester glycol moieties. Upon addition of esterase enzyme, del…
Measurement of day and night neutrino energy spectra at SNO and constraints on neutrino mixing parameters
The Sudbury Neutrino Observatory (SNO) has measured day and night solar neutrino energy spectra and rates. For charged current events, assuming an undistorted $^8$B spectrum, the night minus day rate is $14.0% \pm 6.3% ^{+1.5}_{-1.4}%$ of the average rate. If the total flux of active neutrinos is additionally constrained to have no asymmetry, the $\nu_e$ asymmetry is found to be $7.0% \pm 4.9% ^{+1.3}_{-1.2}%$. A global solar neutrino analysis in terms of matter-enhanced oscillations of two active flavors strongly favors the Large Mixing Angle (LMA) solution.
Polyazapodands Derived from Biphenyl. Study of their Behaviour as Conformationally Regulated Fluorescent Sensors
Eight new polyazapodands containing a 4,4′-substituted biphenyl moiety have been synthesised. Four (7, 8, 9 and 11) are functionalised on positions 4 and 4′ with a nitro group and four (1, 2, 3 and 10) with a dimethylamino substituent. Comparison of the emission behaviour of 1, 2, 3 with that of the reference compounds 10 and tetramthylbenzidine, clearly suggests that a modification in the dihedral angle between the biphenyl rings is an important factor in determining the fluorescent response of the molecule. The fluorescence is pH dependent, due to the formation of intramolecular hydrogen bonds between protonated aliphatic nitrogens and a carbonyl oxygen, which influences the aforementione…
Influence of Cation Size on the Fluorescent Properties of Bis-coronand Biphenyl-derived Complexes
A new bis-coronand derived from biphenyl has been prepared and its complexing and sensing properties for alkaline, alkaline-earth and transition cations have been studied. Open and clamp complexes are formed depending on the cation size and complex stoichiometry. Both types of geometries can be distinguished due to their different fluorescent behaviour. Zn2+ gives rise to 1:1 and 1:2 complexes with a similar geometry.
Influence of side chain characteristics on the aggregation-induced emission (AIE) properties of tetrasubstituted tetraphenylethylene (TPE)
[EN] Five new tetraphenylethylene (TPE) derivatives were synthesised and their aggregation-induced emission (AIE) was evaluated in mixtures of THF/water and MeOH/water. The influence of regiochemistry and length of the chains in the substituents on emissive properties was studied.
Reaction of lithium enediolates with perfluoroketene dithioacetals. Synthesis of α-trifluoromethyl γ-dicarboxylic acid derivatives
The reaction of perfluoroketene dithioacetals with dianions of carboxylic acids proceeds through the substitution of the vinylic fluoride. The preparative value of this reaction depends strongly on the reaction and work-up conditions, the optimisation of which led to use LDA as a base and multiple extraction techniques. The overall process may be considered as a formal synthesis of α-trifluoromethyl γ-dicarboxylic acid derivatives.
Dienediolates of Unsaturated Carboxylic Acids in Synthesis. Tandem Michael Diechmann Synthesis of Substituted 2-Cyclohexenones
Abstract 3,5-Disubstituted 2-Cyclohexenones are prepared by tandem Michael-Dieckmann addition of lithium dienediolates of dimethylacrylic and β-methylcinnamic acids to lithium carboxylates of unsaturated carboxylic acids.
Synthesis of a New pH-Dependent Ligand: Conformational and Complexation Studies
A new macrocyclic ligand, 3, which exhibits pH-induced conformational changes, has been prepared. This ligand consists of a crown ether derived from a trans-anti-trans 1,2,4,5-tetrasubstituted cyclohexane. Due to the stereochemistry of the substituents on the carbocyclic ring, two different low-energy conformations of the crown ether are possible. Ligand 3 has been studied in solution by 1H NMR spectroscopy at different values of pH and temperature, showing that the conformation of the crown ether, and thus its complexing ability, is strongly pH-dependent. The solid-state structure of the ligand has been determined by X-ray diffraction.
Fluorogenic detection of Tetryl and TNT explosives using nanoscopic-capped mesoporous hybrid materials
[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.
A new strategy for the synthesis of highly functionalised fluorinated compounds by reaction of lithium dianions of carboxylic acids with perfluoroketene dithioacetals
The reaction of perfluoroketene dithioacetal with lithium dienediolates of carboxylic acids proceeds at the ω position probably through an addition to the π system followed by elimination of the vinylic fluoride. The preparative value of this reaction depends strongly on the reaction and work-up conditions. The overall process lead to highly functionalised synthons containing a trifluoromethyl group.
Chromogenic and fluorogenic reagents for chemical warfare nerve agents' detection
The ease of production, the extreme toxicity of organophosphorus-containing nerve agents, and their facile use in terrorism attacks underscores the need to develop accurate systems to detect these chemicals. Among different technologies we review here recent advances in the design of chromo-fluorogenic methods for the specific detection of nerve agents. Optical sensing (especially colorimetric detection) requires usually low-cost and widely used instrumentation and offers the possibility of so-called “naked eye detection”. Recent reported examples suggest that the application of chromo-fluorogenic supramolecular concepts for the chromogenic or fluorogenic sensing of nerve agents might be an…
Biphenyl derivatives containing trimethylsilyl benzyl ether or oxime groups as probes for NO2 detection
[EN] Four probes based in the use of a biphenyl moiety and functionalized with trimethylsilyl benzyl ether (P1 and P3) and oxime (P2 and P4) groups have been prepared and tested as optical probes for the detection of NO2. Reaction of NO2 with acetonitrile solutions of P2-P4 resulted in the formation of aldehydes 7 and 8 with a concomitant redshift of the absorption bands. Probe P2 displayed a bathochromic shift of 45 nm upon reaction with NO2 and was able to detect this poisonous gas at concentrations as low as 0.02 ppm. P2 was highly selective against NO2 and other gases (i.e. NO, CO2, H2S, SO2) and vapours of organic solvents (i.e. acetone, hexane, chloroform, acetonitrile or toluene) had…
Sensing and discrimination of cyanide and hydrogen sulfide using an 8-alkenyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene derivative
8-(2-Phenylethenyl)BODIPY has been shown to be an appropriate chromo-fluorogenic probe for cyanide in H2O. Good selectivity and LOD values below the allowed cyanide concentration in drinking water were attained. Cyanide can be discriminated from hydrogen sulphide by an oxidation process with hydrogen peroxide.
Measuring the impact of regional export promotion: The Spanish case
This article estimates the effect of Spanish regional trade agencies abroad on exports using the gravity model. The results indicate that regional agencies increase trade. The estimated impact seems to be larger than that of Spanish embassies and consulates. Moreover, a dis- aggregated analysis shows that this effect is not evenly distributed across Spanish regions. JEL classification: F14, R12
ChemInform Abstract: New Conditions for the Generation of Dianions of Carboxylic Acids.
Abstract Lithium carboxylic acid enediolates are generated efficiently using lithium amides prepared from thienyllithium or butyllithium and either diethylamine, piperazine, N,N′-dibenzylethylenediamine, N-benzylpiperazine or 1,3,3-trimethyl-6-azabicyclo[3.2.1]octane, even in catalytic amounts.
5,5′-Bis-vanillin derivatives as discriminating sensors for trivalent cations
[EN] Several bis-vanillin derivatives containing semicarbazone moieties have been prepared and used in discriminating trivalent cations. The prepared probes are readily obtained and they are usually highly crystalline. Depending on the ligand and the studied cations, quenching, enhancement or no changes in the fluorescence spectrum were observed. Using a series of the prepared ligands allows distinguishing between Fe3+, Cr3+ and Al3+. Detection limits and selectivity in front of divalent cations have been evaluated. (C) 2015 Elsevier Ltd. All rights reserved.
Chromogenic Detection of Aqueous Formaldehyde Using Functionalized Silica Nanoparticles
Silica nanoparticles functionalized with thiol reactive units and bulky polar polyamines were used for the selective colorimetric detection of formaldehyde. The reaction of thiols groups in the nanoparticles surface with a squaraine dye resulted in loss of the pi-conjugation of the chromophores, and the subsequent bleaching of the solution. However, when formaldehyde was present in the suspension, the thiol-squaraine reaction was inhibited and a chromogenic response was observed. A selective response to formaldehyde was observed only when the thiol and polyamine groups were anchored to the silica surface. The observed selective response was ascribed to the fact that bulky polyamines generat…
Assessing the Enlargement and Deepening of the European Union
This paper estimates a theoreticallymotivated gravity model to examine the effect of the European Union (EU) on trade and whet her the order of entry has affected the trade performance of member countries. Additionally, we analyse the impact of the diffe rent phases of EU integration on trade. The results show that both original countries and successive enlargements boost intra-b loc trade. Moreover, the results suggest that the deepening in the integration process has led to more trade creation among members. Finally, only the latter ph ase of the European integration process (the single currency) has increased trade with non-members.
Discrimination of nerve gases mimics and other organophosphorous derivatives in gas phase using a colorimetric probe array.
A colorimetric array for the chromogenic discrimination of organophosphorous derivatives in gas phase has been developed. The array allows us to classify the nerve agent simulants DFP, DCP and DCNP.
Biphenylthioureas as organocatalysts for electrochemical reductions
Abstract Thioureas are able to act as organocatalysts in the electrochemical reduction of aromatic carboxylates.
New conditions for the generation of dianions of carboxylic acids
Abstract Lithium carboxylic acid enediolates are generated efficiently using lithium amides prepared from thienyllithium or butyllithium and either diethylamine, piperazine, N,N′-dibenzylethylenediamine, N-benzylpiperazine or 1,3,3-trimethyl-6-azabicyclo[3.2.1]octane, even in catalytic amounts.
Polyenolates of Unsaturated Carboxylic Acids in Synthesis. Synthesis of Unsaturated α-Amino Acids and β-Hydrazing Acids
Abstract Regioselective reaction of lithium diene-and triene-diolates 1 and 2 with O-diphenylphosphinyl hydroxylamine affords unsaturated α-amino acids 3 and 4. Addition to DEAD leads selectively to γ-hydrazino unsaturated acids 5 and 6.
Enantioselective α-alkylation of unsaturated carboxylic acids using a chiral lithium amide
Abstract The regio- and stereochemistry of the alkylation of dienediolates from unsaturated carboxylic acids with benzylic halides, which often results in mixtures of isomers, can be controlled by means of changes in the lithium amide, allowing the α-regioisomer to be obtained as the major diastereoisomer. In addition, when chiral amines are used, moderate enantiomeric excesses can be attained.
NO2-controlled cargo delivery from gated silica mesoporous nanoparticles
[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.
Towards the design of organocatalysts for nerve agents remediation: The case of the active hydrolysis of DCNP (a Tabun mimic) catalyzed by simple amine-containing derivatives
We report herein a study of the hydrolysis of Tabun mimic DCNP in the presence of different amines, aminoalcohols and glycols as potential suitable organocatalysts for DCNP degradation. Experiments were performed in CD3CN in the presence of 5% D2O, which is a suitable solvent mixture to follow the DCNP hydrolysis. These studies allowed the definition of different DCNP depletion paths, resulting in the formation of diethylphosphoric acid, tetraethylpyrophosphate and phosphoramide species as final products. Without organocatalysts, DCNP hydrolysis occurred mainly via an autocatalysis path. Addition of tertiary amines in sub-stoichiometric amounts largely enhanced DCNP depletion whereas non-te…
pH-Dependent ligands as carriers in transport experiments
Abstract Conformationally pH-regulated ligands have been used as carriers in transport experiments. The experiments were carried out through bulky membranes and the pH at the source phase and at the receiving phase were modified to study the ability of ligands to act as pH-regulated carriers. The influence of pH on transport efficiency seems to be related to its influence on conformational equilibrium. X-ray determination of one precursor compound has been useful for determining the stereochemistry of one of the carriers. To cite this article: A.M. Costero et al., C. R. Chimie 7 (2004).
ChemInform Abstract: Lithium Enediolates and Dienediolates of Carboxylic Acids in Synthesis: Alkylation with Secondary Halides.
Abstract High yields in the alkylation of dianions of α,β-unsaturated carboxylic acids with secondary halides can be obtained despite elimination reactions occurring. α-Regioselectivity for the alkylation of but-2-enoic acids ( 1–4 ) is seldom obtained. Although double bond stereoselectivity is higher than 99% for γ-alkylated products, stereoselectivity is rather poor for most of the α-alkylated products.
Synthesis of Dienedioic and Tetraenedioic Acids by Oxidative Coupling of Unsaturated Carboxylic Acid Dienediolates by 1,2-Diiodoethane
Abstract Acyclic and cyclic unsaturated carboxylic acids 1 to 4 are most easily converted to unsaturated dicarboxylic acids 5 to 8 by oxidative coupling of their diene- or triene-diolates by 1,2-diiodoethane. This procedure improves formerly reported oxidations by iodine or silver salts.
New approach to condensed pyrid-2-ones
We wish to report a simple procedure for the preparation of 5-substituted-thienopyridin-7-ones and 7-substituted-1,6-naphthyridin-5(6H)-ones, in good yields, from the dianions of 3-methylthiophene-2-carboxylic and 2-methylnicotinic acids on treatment with nitriles. Brun Sanchez, Eva Maria, Eva.M.Brun@uv.es ; Gil Grau, Salvador, Salvador.Gil@uv.es ; Parra Alvarez, Margarita, Margarita.Parra@uv.es
Reactivity difference between diphosgene and phosgene in reaction with (2,3-anti)-3-amino-1,2-diols
In reactions of (2,3-anti)-3-amino-1,2-diols with diphosgene and phosgene and their conversion into 1,3-oxazolidin-2-ones, some differences in the stereochemistry of the reactions have been found with these two reagents. The reactions with phosgene afforded the expected cis-oxazolidinones, and in the reaction with diphosgene under the same reaction conditions, the trans-oxazolidinones were also obtained.
Optical chemosensors and reagents to detect explosives
[EN] This critical review is focused on examples reported from 1947 to 2010 related to the design of chromo-fluorogenic chemosensors and reagents for explosives (141 references). © 2012 The Royal Society of Chemistry.
13C NMR studies of dianions of unsaturated carboxylic acids
Abstract 13C NMR Spectra of the dianions Li2-n resulting from double deprotonation of unsaturated carboxylic acids 1 to 6 by lithium dialkylamides, are examined. Higher field resonance for C2 than for C4 atoms are observed, which reveal higher elctron density at C2 than at C4, in agreement with the kinetic α-regioselectivity exhibited by these dianions on reaction with electrophiles.
Silver ion oxidative coupling of diene and triene-diolates of unsaturated carboxylic acids. A facile synthesis of octa- and dodeca-dienedioic acids
Abstract Polyunsaterated dicarboxylic acids 3 and 5 are very easily prepared by oxidative coupling of lithium diene- and triene-diolates 1 and 2 with silver nitrate.
Azide and sulfonylazide functionalized fluorophores for the selective and sensitive detection of hydrogen sulfide
[EN] Three fluorescent probes (1–3) for the selective and sensitive detection of hydrogen sulfide have been synthesized and characterized. Probe 1 is a coumarin derivative functionalized with an azide moiety whereas 2 contain the azide reactive group into a naphthalene fluorophore backbone. Probe 3 is composed also by a naphthalene fluorophore but, in this case, functionalized with a sulfonylazide reactive moiety. Probes 1 and 3 are non-fluorescent whereas 2 is weakly emissive in HEPES (10 mM, pH 7.4)–DMSO 99:1 (v/v). The emission behavior of the three probes was tested against selected anions, bio-thiols and oxidant molecules. Of all the chemical species tested, only HS− is able to induce …
A new chromo-fluorogenic probe based on BODIPY for NO2 detection in air
[EN] A novel colorimetric probe for the selective and sensitive detection of NO2 in solution and in air based on a BODIPY core containing an oxime group has been prepared.
Towards the potential use of (1)H NMR spectroscopy in urine samples for prostate cancer detection
A simple method based in multivariate analysis of 1H NMR spectra profiles of urine samples can be used to detect patients with prostate cancer.
Relationship between ligand conformations and complexation properties in ditopic biphenyl thioureas
Four new homoditopic biphenyl thiourea derivatives have been prepared to be used in carboxylate sensing. Experiments carried out with these ligands have demonstrated that the conformation of the free ligand has a strong influence on both complex stoichiometry and geometry. High equilibrium constants were obtained in DMSO.
A New Environmentally-Friendly Colorimetric Probe for Formaldehyde Gas Detection under Real Conditions
[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.
Concentration depending fluorescence of 8-(di-(2-picolyl)) aminoBODIPY in solution
[EN] An 8-dipicolylBODIPY derivative has been prepared and its photophysical properties evaluated under different conditions. Two different structures, hemicyanine and cyanine, are observed (depending on the solvent or the solution concentration). The hemicyanine form is not emissive whereas the cyanine form is fluorescent. This behavior is related with the planarity degree of the BODIPY core. The X-ray structure of the compound is reported and it shows that in solid state the hemicyanine form is present. The hemicyanine form seems to be stabilized by aggregation and is the main compound in concentrated solutions whereas the cyanine form is present in diluted solutions that are photochemica…
Novel examples of the N-methyl effect on cyclisations of N-Boc derivatives of amino alcohols. A theoretical study
New examples of the N-methyl effect on the cyclisation of N-tert-butoxycarbonyl derivatives of amino alcohols are reported. Ab initio studies for the displacement step with formation of the five-membered heterocycle indicate that the increase of the nucleophile character of the carbonyl oxygen of the carbamate group with the N-methyl substitution is responsible for the acceleration of the cyclisation step.
Bis(crown ethers) derived from biphenyl: extraction and electrochemical properties
Abstract Ligands derived from 4,4′-dinitrobiphenyl containing azacrown cavities in the 2,2′ position have been used in extraction and transport experiments. Control experiments with a system containing only one complexing cavity have demonstrated that the capability of forming a sandwich-type complex in the aforementioned ligand not only increases extraction but also the transport across a liquid membrane. Extraction studies have also shown that the complex present in the membrane has a 1:1 stoichiometry with regard to both ligands. Electrochemical studies have also been carried out. The ligand containing two complexing cavities is capable of giving rise to a 2:1 complex under electrochemic…
Perfluoroketene dithioacetals and perfluorodithiocarboxylic acid derivatives: Versatile tools for organofluorine synthesis
Perfluoroketene dithioacetals are simple and versatile compounds that can be transformed into a large variety of trifluoromethyl derivatives, in particular aza- and thiaheterocycles, perhalodithiocrotonic esters, and fluorinated dithiol thiones. These unsaturated perfluorodithioesters and analogs give interesting polar cycloaddition reactions whose mechanism is strongly influenced by the fluorine substitution. This substitution plays an important role in the reactivity of saturated perfluorodithiocarboxylic acids as well. Except for the carbophilic addition of allyl Grignard reagents to perfluorocarboxamides, a domino thiophilic addition-fluoride elimination was the main reaction process. I…
Heteroditopic chemosensor to detect γ-hydroxybutyric acid (GHB) in soft drinks and alcoholic beverages.
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 …
CCDC 1819378: Experimental Crystal Structure Determination
Related Article: Mónica Gorbe, Ana M. Costero, Félix Sancenón, Ramón Martínez-Máñez, Rafael Ballesteros-Cillero, Luis. E. Ochando, Katherine Chulvi, Raúl Gotor, Salvador Gil|2019|Dyes Pigm.|160|198|doi:10.1016/j.dyepig.2018.08.007
CCDC 1549738: Experimental Crystal Structure Determination
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CCDC 966420: Experimental Crystal Structure Determination
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CCDC 1549735: Experimental Crystal Structure Determination
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CCDC 1549736: Experimental Crystal Structure Determination
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CCDC 1549739: Experimental Crystal Structure Determination
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CCDC 1819380: Experimental Crystal Structure Determination
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CCDC 1549737: Experimental Crystal Structure Determination
Related Article: Ana M. Costero, María L. Betancourt-Mendiola, Pablo Gaviña, Luis E. Ochando, Salvador Gil, Katherine Chulvi and Eduardo Peña-Cabrera|2017|Eur.J.Org.Chem.|2017|6283|doi:10.1002/ejoc.201701016
CCDC 1819379: Experimental Crystal Structure Determination
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CCDC 1549734: Experimental Crystal Structure Determination
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CCDC 1819381: Experimental Crystal Structure Determination
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