Your browser doesn't support javascript.
loading
Show: 20 | 50 | 100
Results 1 - 20 de 23
Filter
Add more filters










Publication year range
1.
Nanomaterials (Basel) ; 8(10)2018 Oct 11.
Article in English | MEDLINE | ID: mdl-30314278

ABSTRACT

Mesostructured layered silicas have been prepared through a surfactant-assisted procedure using neutral alkylamines as templates and starting from atrane complexes as hydrolytic inorganic precursors. By adjusting the synthetic parameters, this kinetically controlled reproducible one-pot method allows for obtaining both pure and functionalized (inorganic or organically) lamellar silica frameworks. These are easily deconstructed and built up again, which provides a simple way for expanding the interlamellar space. The materials present high dispersibility, which results in stable colloidal suspensions.

2.
Chempluschem ; 80(6): 1014-1028, 2015 Jun.
Article in English | MEDLINE | ID: mdl-31973264

ABSTRACT

Nanoparticulate bimodal porous silica-based materials have been prepared through a surfactant-assisted procedure by using a simple template and starting from inexpensive sodium silicate as silicon source. Different procedural variables, such as pH or the nature and concentration of the surfactant, have been explored to optimize the preparative protocol, which allows, in turn, improved understanding of the formation process. The final bulk materials (called UVM-10 or M-UVM-10) are formed by pseudomorphic transformation of fresh silica-based xerogels under mild basic conditions. The UVM-10 architecture is constructed from small mesoporous nanoparticles, the aggregation of which generates a disordered secondary 3 D pore system (large-meso/macropores) defined by interparticle voids. Modulation of the intraparticle mesopore size is achieved by using surfactants with variable tail lengths, while maintaining the same head group. Textural porosity has been handled independently by hydrothermally modifying the particle size of the reactive silica-based xerogel. By simply adding metal alkoxides to the initial reaction mixture, the preparative protocol allows for functionalizing the silica walls by incorporating relatively high proportions of homogeneously dispersed heteroelements, such as Al and Ti.

3.
Dalton Trans ; 42(31): 11194-204, 2013 Aug 21.
Article in English | MEDLINE | ID: mdl-23807542

ABSTRACT

The new receptor 3,7,11,15,19,23-hexaaza-1(2,6)-pyridinacyclotetracosaphane (L1) containing a complete sequence of propylenic chains has been synthesised. The acid-base behaviour and Cu²âº and Zn²âº coordination have been analysed by potentiometric measurements in 0.15 M NaClO4 for L1 and for the related compounds 3,7,11,14,18,22-hexaaza-1(2,6)-pyridinacyclotricosaphane (L2), 3,7,10,13,16,20-hexaaza-1(2,6)-pyridinacycloheneicosaphane (L3) and 3,7,10,12,15,19-hexaaza-1(2,6)-pyridinacycloicosaphane (L4). The crystal structure of [(CuH4L2)(H2O)(ClO4)](ClO4)5·3H2O shows an interesting combination of a metal ion coordinated by the pyridine nitrogen atom and the adjacent amine groups of the chain, and a perchlorate anion sitting at the middle of the site defined by the remaining four protonated ammonium groups of L1. Paramagnetic NMR data suggest that imidazole coordinates to the Cu²âº ions as a bridging ligand in a wide pH range. SOD activity for Cu²âº-Cu²âº and Cu²âº-Zn²âº complexes with L1-L4 have been measured by NBT assays at pH 7.4, obtaining some of the lowest values so far reported for SOD mimics. SOD activity has also been checked by chemiluminescence assays using polymorphonuclear leukocytes (PMNLs).


Subject(s)
Biomimetic Materials/metabolism , Coordination Complexes/chemistry , Copper/chemistry , Pyridines/chemistry , Zinc/chemistry , Antioxidants/chemistry , Antioxidants/metabolism , Biomimetic Materials/chemistry , Crystallography, X-Ray , Humans , Leukocytes, Mononuclear/enzymology , Luminescent Measurements , Molecular Conformation , Superoxide Dismutase/chemistry , Superoxide Dismutase/metabolism
4.
J Mol Model ; 18(7): 3301-10, 2012 Jul.
Article in English | MEDLINE | ID: mdl-22252834

ABSTRACT

Quantum chemical calculations using density functional theory have been carried out to investigate two chemical pathways for the last step of the hydrolysis of tetraethylorthosilicate (TEOS) in basic catalyzed environment. The two models that are introduced in this study depend on the number of water molecules involved at the base catalyzed hydrolysis. Solution equilibrium geometries of the molecules involved in the transition states, reactants and product complexes of the two chemical pathways were fully optimized at B3LYP level of theory with the standard 6-31+G(d) basis set, modeling solvent effects using a polarizable continuum solvation model (PCM). Both models predict relative low activation energies. However, the model with two water molecules seems to be more adequate to describe the basic hydrolysis. A natural bond orbital (NBO) analysis seems to show that the proton transfer from water to ethoxy group would occur through a large hyperconjugative interaction, LP(O) → σ*(O-H), which is related to the nonbonding oxygen lone pair orbital from ethoxy group with the vicinal σ*(O-H) anti bonding orbital O-H of a water molecule.


Subject(s)
Models, Theoretical , Silanes/chemistry , Silicon Dioxide/chemistry , Catalysis , Hydrolysis , Solvents/chemistry , Water/chemistry
5.
J Org Chem ; 76(20): 8223-31, 2011 Oct 21.
Article in English | MEDLINE | ID: mdl-21910468

ABSTRACT

By using an improved synthetic method reported earlier, the cyclic stannoxanes obtained from RN-diethanolamine (R = Me, Bu) and dibutyltin oxide have been reacted with 1H-pyrazole-3,5-dicarbonyl dichloride to afford 26-membered diaza tetraester crowns (1, R = Me; 3, R = Bu) and 39-membered triaza hexaester crowns (2, R = Me; 4, R = Bu). The new structures were identified from their analytical and spectroscopic ((1)H and (13)C NMR, FAB-MS, and/or ESI-MS) data. Both diaza tetraester crowns (1 and 3), containing two 1H-pyrazole units, self-assemble into dimeric species through the formation of four hydrogen bonds involving the two NH pyrazole groups and the two tertiary amine groups of both crowns, as proved by X-ray crystallography and NMR analysis. Preliminary NMR, ESI-MS, MALDI-TOF-MS, and molecular modeling studies suggest that, in CDCl(3) solution, 1 interacts with ethyleneurea (ETU), affording 1:1, 2:1, and 2:2 1-ETU complexes.


Subject(s)
Crown Compounds/chemistry , Esters/chemistry , Molecular Probes/chemistry , Pyrazoles/chemistry , Amines/chemistry , Chloroform/chemistry , Crown Compounds/analysis , Crystallography, X-Ray , Cyclization , Deuterium/chemistry , Dimerization , Esters/analysis , Ethanolamines/chemistry , Hydrogen Bonding , Magnetic Resonance Spectroscopy , Models, Molecular , Molecular Probes/analysis , Organotin Compounds/chemistry , Pyrazoles/analysis , Solutions , Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization
6.
Chem Commun (Camb) ; 47(21): 5988-90, 2011 Jun 07.
Article in English | MEDLINE | ID: mdl-21537499

ABSTRACT

Mn(II) complexes of scorpiand-type azamacrocycles constituted by a tretrazapyridinophane core appended with an ethylamino tail including 2- or 4-quinoline functionalities show very appealing in vitro SOD activity. The observed behaviour is related to structural and electrochemical parameters.


Subject(s)
Aza Compounds/chemistry , Coordination Complexes/chemistry , Macrocyclic Compounds/chemistry , Manganese/chemistry , Biomimetic Materials/chemistry , Crystallography, X-Ray , Molecular Conformation , Quinolines/chemistry , Superoxide Dismutase/chemistry , Superoxide Dismutase/metabolism
7.
Inorg Chem ; 49(15): 7016-27, 2010 Aug 02.
Article in English | MEDLINE | ID: mdl-20614930

ABSTRACT

The synthesis of two new ligands constituted of a tris(2-aminoethyl)amine moiety linked to the 2,6 positions of a pyridine spacer through methylene groups in which the hanging arm is further functionalized with a 2-pycolyl (L1) or 3-pycolyl (L2) group is presented. The protonation of L1 and L2 and formation of Cu(2+) complexes have been studied using potentiometric, NMR, X-ray, and kinetic experiments. The results provide new information about the relevance of molecular movements in the chemistry of this kind of so-called scorpiand ligand. The comparison between these two ligands that only differ in the position of the substituent at the arm reveals important differences in both thermodynamic and kinetic properties. The Cu(2+) complex with L1 is several orders of magnitude more stable than that with L2, surely because in the latter case the pyridine nitrogen at the pendant arm is unable to coordinate to the metal ion with the ligand acting as hexadentate, a possibility that occurs in the case of [CuL1](2+), as demonstrated by its crystal structure. Significant differences are also found between both ligands in the kinetic studies of complex formation and decomposition. For L1, those processes occur in a single kinetic step, whereas for L2 they occur with the formation of a detectable reaction intermediate whose structure corresponds to that resulting from the movement typical of scorpiands. Another interesting conclusion derived from kinetic studies on complex formation is that the reactive form of the ligand is H(3)L(3+) for L1 and H(2)L(2+) for L2. DFT calculations are also reported, and they allow a rationalization of the kinetic results relative to the reactive forms of the ligands in the process of complex formation. In addition, they provide a full picture of the mechanistic pathway leading to the formation of the first Cu-N bond, including outer-sphere complexation, water dissociation, and reorganization of the outer-sphere complex.


Subject(s)
Copper/chemistry , Hydrogen/chemistry , Organometallic Compounds/chemistry , Pyridines/chemistry , Crystallography, X-Ray , Hydrogen-Ion Concentration , Kinetics , Ligands , Models, Molecular , Molecular Conformation
8.
Org Biomol Chem ; 7(16): 3212-4, 2009 Aug 21.
Article in English | MEDLINE | ID: mdl-19641775

ABSTRACT

Hydrogen-bonded double-stranded hetero-helices are formed when reacting sodium 3,5-bis(ethoxycarbonyl)pyrazolate with beta-phenethylammonium or homoveratrylammonium chloride, in which one of the strands is defined by the ammonium cations and the other one by the pyrazolate anions.


Subject(s)
Anions/chemistry , Phenethylamines/chemistry , Protein Structure, Secondary , Quaternary Ammonium Compounds/chemistry , Circular Dichroism , Crystallography, X-Ray , Hydrogen Bonding
9.
Chem Commun (Camb) ; (19): 2694-6, 2009 May 21.
Article in English | MEDLINE | ID: mdl-19532924

ABSTRACT

Both bulk and mesoporous silica nanoparticles can be obtained in the form of granular aggregates using chitosan flakes as additive under very soft biomimetic reaction conditions.


Subject(s)
Biomimetics , Nanoparticles/chemistry , Silicon Dioxide/chemistry , Chitosan/chemistry , Microscopy, Electron, Scanning , Microscopy, Electron, Transmission
10.
Inorg Chem ; 47(18): 8267-77, 2008 Sep 15.
Article in English | MEDLINE | ID: mdl-18700753

ABSTRACT

Nanoparticulated bimodal porous silicas (NBSs) with pore systems structured at two length scales (meso- and large-meso-/macropores) have been prepared through a one-pot surfactant-assisted procedure by using a simple template agent and starting from silicon atrane complexes as hydrolytic inorganic precursors. The final bulk materials are constructed by an aggregation of pseudospherical mesoporous primary nanoparticles process, over the course of which the interparticle (textural) large pore system is generated. A fine-tuning of the procedural variables allows not only an adjustment of the processes of nucleation and growth of the primary nanoparticles but also a modulation of their subsequent aggregation. In this way, we achieve good control of the porosity of both the intra- and interparticle pore systems by managing independent variables. We analyze in particular the regulating role played by two physicochemical variables: the critical micelar concentration (cmc) of the surfactant and the dielectric constant of the reaction medium.

11.
Nanotechnology ; 19(22): 225603, 2008 Jun 04.
Article in English | MEDLINE | ID: mdl-21825763

ABSTRACT

Silica-based ZnO-MCM-41 mesoporous nanocomposites with high Zn content (5≤Si/Zn≤50) have been synthesized by a one-pot surfactant-assisted procedure from aqueous solution using a cationic surfactant (CTMABr = cetyltrimethylammonium bromide) as structure-directing agent, and starting from molecular atrane complexes as inorganic hydrolytic precursors. This preparative technique allows optimization of the dispersion of the ZnO nanodomains in the silica walls. The mesoporous nature of the final materials is confirmed by x-ray diffraction (XRD), transmission electron microscopy (TEM) and N(2) adsorption-desorption isotherms. The ZnO-MCM-41 materials show unimodal pore size distributions without blocking of the pore system even for high Zn content. A careful optical spectroscopic study (using x-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and UV-visible spectroscopy) of these materials shows that, irrespective of the Si/Zn ratio, the Zn atoms are organized in well-dispersed, uniform low-defect ZnO nanodomains (radius about 1 nm) and are partially embedded within the silica walls.

12.
Dalton Trans ; (41): 4726-37, 2007 Nov 07.
Article in English | MEDLINE | ID: mdl-17940655

ABSTRACT

The dinuclear Cu2+ and Zn2+ as well as the mixed Cu2+-Zn2+ complexes of a 5,5''-pentaazaterpyridinophane ligand (L) are able to incorporate imidazolate (Im-) as a bridging ligand. The crystal structure of [Cu(2)L(Im)(Br)(H2O)](CF(3)SO(3))(2).3H2O (1) shows one copper coordinated by the three pyridine nitrogens of the terpyridine unit, one nitrogen of the imidazolate bridge (Im-) and one bromide anion occupying the axial position of a distorted square pyramid. The second copper atom is coordinated by the remaining imidazolate nitrogen, the three secondary nitrogens at the centre of the polyamine bridge and one water molecule that occupies the axial position. Magnetic measurements have been performed in the 2.0-300.0 K temperature range. Experimental data could be satisfactorily reproduced by using an isotropic exchange model H = -JS(1)S(2) with J = -52.3 cm(-1) and g = 2.09. Potentiometric studies have provided details of the speciation and stability constants for the mixed Cu2+-L-HIm, Zn2+-L-HIm (HIm = imidazole) and Cu2+-Zn2+-L-HIm systems. The apparent stability constant obtained at pH = 9 for the addition of imidazole to the dinuclear Cu2+ complexes is one of the highest so far reported (log K = 7.5). UV-Vis spectroscopy and paramagnetic NMR data show that imidazole coordinates to the Cu2+ ions as a bridging imidazolate ligand from pH 5 to 10. Electrochemical reduction of the Cu2+-Zn2+-L complex occurs in two successive one-electron per copper ion quasi-reversible steps. The formal potential of the Cu2+-Zn2+-L/Cu+-Zn2+-L couple is close to that of SOD. The IC50 values measured at pH 7.8 by means of the nitro blue tetrazolium method show significant SOD activity for the dinuclear Cu2+ complexes (IC50 = 2.5 microM) and moderate activity for the Cu2+-Zn2+ mixed systems (IC50 = 30 microM).


Subject(s)
Copper/chemistry , Imidazoles/chemistry , Macrocyclic Compounds/chemistry , Organometallic Compounds/chemistry , Pyridines/chemistry , Zinc/chemistry , Aza Compounds/chemistry , Crystallography, X-Ray , Electrochemistry , Enzyme Activation , Hydrogen-Ion Concentration , Ligands , Magnetic Resonance Spectroscopy/methods , Magnetics , Models, Molecular , Molecular Structure , Solutions/chemistry , Superoxide Dismutase/chemistry , Temperature
13.
Inorg Chem ; 46(14): 5707-19, 2007 Jul 09.
Article in English | MEDLINE | ID: mdl-17555313

ABSTRACT

Two aza scorpionand-like macrocycles (L2 and L3) have been prepared. L2 consists of a tren amine with two of its arms cyclizized with a 2,6-bis(bromomethyl)pyridine. In L3, the remaining pendant arm has been further functionalized with a fluorophoric naphthalene group. X-ray data on the compounds [H(L3)]ClO4.H2O (1) and [H3(L3)](H2PO4)3.H2O (2) as well as solution studies (pH-metry, UV-vis, and fluorescence data) show the movement of the pendant arm as a result of the protonation degree of the macrocycles and of the formation of intramolecular hydrogen bonds. X-ray data on the complexes [Cu(L2)](ClO4)2]2.H2O (3) and [Cu(L3)](ClO4)2 (4) and solution studies on Cu2+ coordination show the implication of the nitrogen of the arm in the binding to the metal ion. Kinetic studies on the decomposition and formation of the Cu2+ complexes provide additional information about the pH-dependent molecular reorganizations. Moreover, the obtained information suggests that the kinetics of the tail on/off process is essentially independent of the lability of the metal center.


Subject(s)
Copper/chemistry , Hydrogen/chemistry , Ions/chemistry , Hydrogen-Ion Concentration , Kinetics , Ligands , Models, Molecular , Molecular Structure , Phosphorus Acids/chemistry , Potentiometry , Water/chemistry , X-Ray Diffraction
14.
Inorg Chem ; 45(9): 3803-15, 2006 May 01.
Article in English | MEDLINE | ID: mdl-16634617

ABSTRACT

The synthesis of the terpyridinophane-type polyamine 2,6,9,12,16-pentaaza[17]-(5,5' ')-cyclo-(2,2':6',2' ')-terpyridinophane heptahydrobromide tetrahydrate (L.7HBr.4H2O) is described. L presents six protonation constants with values in the range 9.21-3.27 logarithmic units. L interacts with Cu2+ and Zn2+ forming in both cases, neutral, protonated, and hydroxylated mono- and binuclear complexes whose constants have been calculated by potentiometry in 0.15 M NaClO4 at 298.1 K. The crystal structures of the compounds [Cu(HL-carb)(H2O)](ClO4)3.2H2O (1) and [Cu2(H2L)(CO3)]2(ClO4)8.9H2O (2) have been solved by X-ray diffraction. In 1, the metal center presents square pyramidal geometry. The base of the pyramid is formed by the three nitrogen atoms of pyridine and one oxygen atom of a CO2 group which is forming a carbamate bond with the central nitrogen atom of the polyamine chain. The axial position is occupied by a water molecule. In 2, one Cu2+ is bound by the three pyridine nitrogens and the other one by the three central nitrogen atoms of the polyamine chain. The square planar coordination geometry is completed by a carbonate group taken up from the atmosphere that behaves as a bridging mu,mu'-ligand between the two centers. The pH-metric titrations on the ternary Cu2+-L-carbonate and Zn2+-L-carbonate systems show the extensive formation of adduct species which above pH 6 are formed quantitatively in solution. The stoichiometries of the main species formed in solution at pH = 6.8 agree with those found in the crystalline compounds. CO2 uptake by the Zn2+ and Cu2+ 1:1 complexes in aqueous solution has also been followed by recording the variations in the band at ca. 300 nm. The formation of the Zn2+ carbamate moiety has been evidenced by 13C NMR and ESI spectroscopy.


Subject(s)
Carbon Dioxide/chemistry , Copper/chemistry , Organometallic Compounds/chemical synthesis , Polyamines/chemical synthesis , Zinc/chemistry , Crystallography, X-Ray , Electrochemistry , Hydrogen-Ion Concentration , Molecular Structure , Organometallic Compounds/chemistry , Plants/metabolism , Polyamines/chemistry , Spectrum Analysis
15.
Inorg Chem ; 44(21): 7503-10, 2005 Oct 17.
Article in English | MEDLINE | ID: mdl-16212376

ABSTRACT

Three crystal structures of a ditopic cyclophane ligand (L) in which two 1,5,8,12-tetraamine molecules have been attached through methylene spacers to the ortho positions of a benzene ring are reported. The first one (1) corresponds to the tetraprotonated free macrocycle (H4L4+) having two tetrachlorozincate(II) counteranions (C24H54O2N8Cl8Zn2, a = 9.1890(2) A, b = 14.0120(3) A, c = 15.3180(3) A, alpha = 89.2320(7) degrees , beta = 82.0740(6) degrees , gamma = 83.017(1) degrees , Z = 2.00, triclinic, P); the second one (2) is of a binuclear Cu2+ complex having coordinated chloride anions and perchlorate counteranions (C24H58O14N8Cl4Cu2 a = 9.9380(2) A, b = 30.2470(6) A, c = 53.143(1) A, orthorhombic, F2dd, Z = 18), and the third one (3) corresponds to an analogous Zn2+ complex that has been crystallized using triflate as counteranion (C26H(51.2)O(6.6)N8Cl2F6S2Zn2 a = 8.472(5) A, b = 9.310(5), c = 13.745(5) A, alpha = 84.262(5) degrees , beta = 77.490(5) degrees , gamma = 73.557(5) degrees , triclinic, P, Z = 2). The analysis of the crystallographic data clearly shows that the conformation of the macrocycle and, in consequence, the overall architecture of the crystals are controlled by the anions present in the moiety, pi-pi-stacking associations, and hydrogen bonding interactions. The protonation and stability constants for the formation of the Cu2+ and Zn2+ complexes in aqueous solution have been determined potentiometrically in 0.15 mol dm(-3) NaClO4 at 298.1 K. Intramolecular hydrogen bonding defines the protonation behavior of the compound. Positive cooperativity is observed in the formation of the Cu2+ complexes.

16.
J Am Chem Soc ; 126(28): 8612-3, 2004 Jul 21.
Article in English | MEDLINE | ID: mdl-15250688

ABSTRACT

An ionically controlled nanoscopic molecular gate has been developed by using functionalized mesoporous materials. The system shows that control of mass transport at nanometric scale can be achieved by using suitable rigid solids and pH-active molecules. The design principle suggests new perspectives in the search of ionically tuned tailored materials and devices with a fine control of mass transport for new applications in fields such as drug delivery, selective removal of toxic species, sensing, or catalysis.

17.
J Am Chem Soc ; 126(16): 5082-3, 2004 Apr 28.
Article in English | MEDLINE | ID: mdl-15099087

ABSTRACT

CO2 is fixed by a Cu2+ complex of a macrocyclic terpyridinophane ligand forming a carbamate group. Several features of the structure mimic the enzyme rubisco.

18.
Chem Commun (Camb) ; (12): 1448-9, 2003 Jun 21.
Article in English | MEDLINE | ID: mdl-12841285

ABSTRACT

Silica-based materials with hierarchical pore systems at three different length scales (small mesopores-large mesopores-macropores) have been prepared through a nanotectonic approach by using mesoporous nanoparticles as building blocks; the resulting materials present a highly accessible foam-like architecture and can be prepared as large monoliths.

19.
Chem Commun (Camb) ; (4): 330-1, 2002 Feb 21.
Article in English | MEDLINE | ID: mdl-12120059

ABSTRACT

Porous pure and doped silicas with pore sizes at two length scales (meso/macroporous) have been prepared and shaped both as powders and monoliths through a one-pot surfactant assisted procedure by using a simple template agent and starting from atrane complexes as inorganic precursors.

20.
Chem Commun (Camb) ; (9): 936-7, 2002 May 07.
Article in English | MEDLINE | ID: mdl-12123056

ABSTRACT

The crystal structure of the complex [Cu4(H-2L)2(H2O)2(ClO4)2](ClO4)(2).2H2O where L is a new pyrazole ligand containing 1,5-diaminopentane spacers represents a new form of obtaining metal ion-induced inorganic-organic cages.

SELECTION OF CITATIONS
SEARCH DETAIL
...