Silvano Geremia

Silvano Geremia
  • PhD
  • Professor at University of Trieste

About

278
Publications
20,726
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8,006
Citations
Current institution
University of Trieste
Current position
  • Professor
Additional affiliations
November 1996 - present
University of Trieste
Position
  • Head of Department

Publications

Publications (278)
Article
Full-text available
In this study, we report the design and development of a stable fluorescent probe that is selectively localized in the cytosol of Hela cells. We designed two probes, 1 and 2, with D‐π‐A (carbazole (Cbz)‐vinyl‐naphthalimide (NPI)) and A‐π‐D‐π‐A (NPI‐vinyl‐Cbz‐vinyl‐NPI) architecture, respectively. Probes 1 and 2 exhibit broad photoluminescence (PL)...
Preprint
Full-text available
Poly(methyl methacrylate) (PMMA) matrix has been extensively explored for decades to achieve efficient room-temperature phosphorescence in blue-to-red regions from dispersed chromophores. Isolated chromophores at low-weight concentrations in the polymer matrix eliminate the inter-chromophore interactions. However, the impact of the polymer matrix o...
Article
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We recently introduced calix[n]naphth[m]arenes as a novel class of deep-cavity hybrid macrocycles constituted by phenol (n) and naphthalene (m) units. In this study, we report the synthesis, conformational analysis, spectroscopic properties, and solid-state structures of calix[4]naphth[4]arene (C4N4) and its permethylated analog (C4N4-Me), thereby...
Article
Full-text available
The diterpene cafestol represents the most potent cholesterol-elevating compound known in the human diet, being responsible for more than 80% of the effect of coffee on serum lipids, with a mechanism still not fully clarified. In the present study, the interaction of cafestol and 16-O-methylcafestol with the stabilized ligand-binding domain (LBD) o...
Article
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This paper investigates pseudo-polymorphism in 2-pyridylmethoxy derivatives of p-tert-butylcalix[4]arene (PyC4), p-tert-butyldihomooxa-calix[4]arenes (PyHOC4), and p-tert-butylhexahomotrioxacalix[3]arenes (PyHO3C3), presenting 11 crystal structures with 15 crystallographically independent molecules. The macrocycle of PyC4 is smaller and less flexib...
Preprint
Full-text available
This paper investigates pseudo-polymorphism in 2-pyridylmethoxy derivatives of p-tert-butylcalix[4]arene (PyC4), p-tert-butyldihomooxa-calix[4]arenes (PyHOC4), and p-tert-butylhexahomotrioxacalix[3]arenes (PyHO3C3), presenting 11 crystal structures with 15 crystallographically independent molecules. The macrocycle of PyC4 is smaller and less flexib...
Article
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A novel octaurea-calix[4]tube (UC4T) has been synthesized in three steps from the original Beer's p-tert-butylcalix[4]tube ionophore. In a polar solvent (DMSO-d6), UC4T rapidly interconverts between two identical conformations with C2v symmetry for the two calix[4]arene subunits. However, in a less polar solvent mixture (CDCl3/DMSO-d6, 98 : 2), UC4...
Article
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Herein, we report the design, synthesis, structure, and electrochemical study of doubly βC−B−N fused Ni(II) porphyrins (1‐trans, 1‐cis, 2‐trans, and 2‐cis). These compounds have been synthesized from A2B2 type dipyridyl Ni(II) porphyrins (Ar=Ph for 1 a; Ar=C6F5 for 2 a) via Lewis base‐directed electrophilic aromatic borylation reactions. The soluti...
Article
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The direct macrocyclization to prism[5]arenes of 2,6-dialkoxynaphthalenes with branched and bulky alkyl groups has been obtained in good yields in the presence of 1,4-dihexyl-DABCO template. These novel prism[5]arenes exhibit typical...
Article
Full-text available
Novel Resorcin[4]arene-based, octacationic Quaternary Ammonium Compounds (ResQAC R ) were obtained by linking tetraalkylammonium groups on the macrocycle wider rim to give multivalent multi-QACs. Their structures were elucidated through 1D and 2D...
Article
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The Front Cover shows images of buds and blossomed waterlilies. As the sun favours the blossoming of the waterlilies, a molecular recognition event triggers a conformational change of the isopropoxy-prism[6]arene from a closed to open structure. Cover design by Rocco Del Regno, Carmine Gaeta and Silvano Geremia.
Preprint
Full-text available
The divergent supramolecular behavior of a series of tripeptide stereoisomers was elucidated through spectroscopic, microscopic, crystallographic and computational techniques. Only two epimers were able to effectively self-organize into amphipathic structures, leading to supramolecular hydrogels or crystals, respectively. Despite the similarity bet...
Article
Full-text available
In this work, the direct macrocyclization of a prism[6]arene macrocycle bearing branched alkyl chains on the rims is reported. Isopropoxyprism[6]arene adopts in solution and in the solid state a cuboid D2‐conformation in which four isopropyl groups are folded inside the cavity, to give C−H⋅⋅⋅π interactions and filling the internal void. The conform...
Article
Here, we present the crystal structure of the synthetic peptide KE1, which contains four K-coil heptads separated in the middle by the QFLMLMF heptad. The structure determination reveals the presence of a canonical parallel three stranded coiled coil. The geometric characteristics of this structure are compared with other coiled coils with the same...
Article
Full-text available
Vitamin B12, also known as the anti-pernicious anemia factor, is an essential micronutrient totally dependent on dietary sources that is commonly integrated with food supplements. Four vitamin B12 forms—cyanocobalamin, hydroxocobalamin, 5′-deoxyadenosylcobalamin, and methylcobalamin—are currently used for supplementation and, here, we provide an ov...
Article
Full-text available
The confused‐prism[5]arene macrocycle (c‐PrS[5]Me) shows conformational adaptive behavior in the presence of ammonium guests. Upon guest inclusion, the 1,4‐bridged naphthalene flap reverses its planar chirality from pS to pR (with reference to the pS(pR)4 enantiomer). Stereoselective directional threading is also observed in the presence of directi...
Article
Chloroquine (CQ) is a first-choice drug against malaria and autoimmune diseases. It has been co-administered with zinc against SARS-CoV-2 and soon dismissed because of safety issues. The structural features of Zn-CQ complexes and the effect of CQ on zinc distribution in cells are poorly known. In this study, state-of-the-art computations combined w...
Preprint
Chloroquine (CQ) is a first-choice drug against malaria and autoimmune diseases. It may act as a zinc ionophore. In this study, state-of-the-art computations and experiments were leveraged to solve the structure of the Zn chloride-CQ complex in solution and in solid state. The integration of different techniques (NMR, ESI-MS, X-ray absorption and d...
Preprint
Chloroquine (CQ) is a first-choice drug against malaria and autoimmune diseases. It may act as a zinc ionophore. In this study, state-of-the-art computations and experiments were leveraged to solve the structure of the Zn chloride-CQ complex in solution and in solid state. The integration of different techniques (NMR, ESI-MS, X-ray absorption and d...
Article
Full-text available
Inclusion of polymethine cyanine dyes in the cavity of macrocyclic receptors is an effective strategy to alter their absorption and emission behavior in aqueous solution. In this paper, the effect of the host‐guest interaction between cucurbit[8]uril (CB[8]) and a model trimethine indocyanine (Cy3) on dye spectral properties and aggregation in wate...
Article
Full-text available
Monopropargyloxy-tripropoxy-calix[4]arene 1 was subjected to a propargyl Claisen rearrangement to give unusual calix[3]arene[1]chromene and homocalix[3]arene[1]benzofuran macrocycles. Quantum mechanical density functional theory calculations indicated that an initial [3,3] sigmatropic reaction affords a highly reactive allene intermediate, stabiliz...
Article
The two isomers 4,4´-dihydroxydiphenyl sulphone and 2,4´-dihydroxydiphenyl sulphone (bisphenol S, BPS) form inclusion complexes with β-CD in solution, in the gas phase, and in the solid state. The complexes 4,4´-BPS@β-CD and 2,4´-BPS@β-CD were studied in solution by 1D and 2D NMR experiments. Calorimetric investigation by ITC evidenced that the β-C...
Article
Full-text available
Cone-shaped calix[4]arene-tetrol 3 has the ability to form open structures due to the presence of four OH groups at the upper rim, which allows the construction of H-bonded supramolecular organic frameworks (SOFs). In the presence of water, SOF-1 is formed, which contains hydrophilic channels (mean diameter of 8.5 Å) contoured by the p-phenolic OH...
Article
The conformational changes of the homooxa adamantyl ketones 1 and 2, as well as of the calix[4]arene analogue derivative 3, all in the cone conformation, upon Pb²⁺ complexation were investigated by ¹H, ¹³C, ²⁰⁷Pb NMR and proton spin-lattice relaxation times (T1) experiments. The X-ray crystal structures of ketones 1 and 3 were determined. The inclu...
Article
Full-text available
Ethyl- and propyl-prism[6]arenes are obtained in high yields and in short reaction times independent of the nature and size of the solvent in the cyclization of 2,6-dialkoxynaphthalene by paraformaldehyde. PrS[6]Et or PrS[6]nPr adopt, both in solution and in the solid state, a folded cuboid-shaped conformation, in which four inward oriented alkyl c...
Article
Full-text available
The host–guest inclusion complexes of cucurbiturils with alkyl viologen have interesting architectures, chemical properties, and potential applications in sensors and nanotechnology. A highly hydrated triclinic crystal of cucurbit[8]uril (CB[8]) complexed by methyl hexadecyl viologen (MVC16) is characterized by the unprecedented coexistence in the...
Article
Full-text available
Direct O-alkylation of p-tert-butyldihomooxacalix[4]arene (1) with N-(bromopropyl)- or N-(bromoethyl)phthalimides and K2CO3 in acetonitrile was conducted under conventional heating (reflux) and using microwave irradiation and ball milling methodologies. The reactions afforded mono- and mainly distal di-substituted derivatives in the cone conformati...
Article
Full-text available
Viologens are among the most studied guests for cucurbit[8]uril (CB[8]) and their complexation is usually driven by bipyridyl core inclusion inside the cavity to maximize both hydrophobic and cation‐dipole interactions. The presence of alkyl substituents on the guest alters this complexation mode, switching to aliphatic chain inclusion in U‐folded...
Article
There is considerable interest in dynamic materials featuring modular components with nano-scale dimensions and controlled responsiveness to external stimuli. Supramolecular polymers are a class of materials that fulfil all these conditions well. Here, we present a family of host–guest supramolecular polymers that combine the outstanding complexing...
Article
Full-text available
Diphenylalanine is an amyloidogenic building block that can form a versatile array of supramolecular materials. Its shortcomings, however, include the uncontrolled hierarchical assembly into microtubes of heterogeneous size distribution and well-known cytotoxicity. This study rationalized heterochirality as a successful strategy to address both of...
Article
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The chiral (R)-10-hydroxystearic acid ((R)-10-HSA) is a positional homologue of both (R)-12-HSA and (R)-9-HSA with the OH group in an intermediate position. While (R)-12-HSA is one of the best-known low-molecular-weight organogelators, (R)-9-HSA is not, but it forms crystals in several solvents. With the aim to gain information on the structural ro...
Article
Full-text available
Fluorescent dihomooxacalix[4]arene-based receptors 5a–5c, bearing two naphthyl(thio)ureido groups at the lower rim via a butyl spacer, were synthesised and obtained in the cone conformation in solution. The X-ray crystal structures of 1,3- (5a) and 3,4-dinaphthylurea (5b) derivatives are reported. Their binding properties towards several anions of...
Article
Amino acid stereoconfiguration has been shown to play a key role in the self-assembly of unprotected tripeptides into hydrogels under physiological conditions. Dramatic changes were noted for hydrophobic sequences based on the diphenylalanine motif from the formation of amorphous aggregates in the case of homochiral peptides to nanostructured and s...
Article
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Calix[6]arenes bearing adamantyl groups at the exo-rim form pseudorotaxanes with dialkylammonium axles paired to the weakly coordinating ([B(ArF)4]- anion. The exo-adamantyl groups give rise to a more efficient threading with respect to the exo-tert-butyl ones leading to apparent association constants more than one order of magnitude higher. This i...
Article
Full-text available
We here explore the soluble Human Leukocyte Antigen-G (sHLA-G) expression level as clinical biomarker in metastatic colorectal cancer (mCRC). To this aim the sHLA-G protein was measured in plasma samples of 40 patients with mCRC treated with the FOLFIRI (irinotecan (CPT-11) plus 5-fluorouracil (5-FU) and leucovorin (LV)) regimen. The results sugges...
Article
Di-nuclear Cu2(II,II) cores stabilized by the N3O-donor set of HL1=(2-{[[di(2-pyridyl)methyl](methyl)amino] methyl}phenol), HL2=2-({[di(2-pyridyl)methyl]amino}methyl) phenol) and HL3=2-({[di(2-pyridyl)methyl]amino}methyl)-4-nitrophenol, display a unique Superoxide Dismutase (SOD) combined with Catalase (CAT)-like activity in water, at neutral pH. T...
Article
Full-text available
Hexahomotrioxacalix[3]arene‐based receptors (phenylurea 4a, phenylthiourea 4b and tert‐butylurea 4c) were synthesised and obtained in the partial cone conformation in solution. Phenylurea 4a was also obtained in the cone conformation and its X‐ray crystal structure is reported. Their binding properties towards several anions of different geometries...
Article
Full-text available
The design and synthesis of a novel tert-butyl-calix[4]arene functionalized at 1, 3 positions of the lower rim with two terminal 2-hydroxybenzeledene-thiosemicarbazone moieties is reported. The new ligand with multi-dentate chelating properties was fully characterized by several techniques: ESI-Mass spectroscopy, FT-IR, 1 H-NMR, and single crystal...
Article
Full-text available
The novel title macrocycles, based on methylene-bridged 1,5-naphthalene units, have been obtained by template effect in a thermodynamically controlled synthesis. In details, the prism[5]arene 1 or the prism[6]arene 3 was selectively taken away from the equilibrium mixture by using the complemen-tary ammonium-templating agent. When only the solvent...
Article
Sulfonato-calix[n]arenes (sclxn) are promising tools to generate crystalline protein frameworks. We report, for the first time, a lower rim functionalised octa-anionic calix[4]arene (sclx4mc) in complex with proteins. Two crystal structures of sclx4mc bound to yeast or horse heart cytochrome c (cytc) are described. Highly porous honeycomb or tubula...
Article
Full-text available
Two bidentate dihomooxacalix[4]arene receptors bearing phenylurea moieties substituted with electron-withdrawing groups at the lower rim via a butyl spacer (CF3-Phurea 5b and NO2 Phurea 5c) were obtained in the cone conformation in solution, as shown by NMR. The X-ray crystal structure of 5b is reported. The binding affinity of these receptors towa...
Article
Full-text available
A four component system consisting of two water-soluble calix[5]arenes ( 1 and 2 ) with differently substituted upper-rims and two α,ω-alkanediyldiammonium ions of different lengths ( NC8N and NC10N ) was found to assemble...
Article
Full-text available
In this study, we synthesized a new thiosemicarbazide-functionalized calix[4]arene L and its Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺ transition metal complexes. For characterization several techniques were employed: Fourier-transform infrared (FT-IR), ¹H nuclear magnetic resonance (NMR), ¹³C-NMR, ¹⁵N-NMR, correlation spectroscopy (COZY), nuclear Overhauser enha...
Article
Calix[6]arenes disubstituted at the methylene bridges, which are stable in the cone or 1,2,3-alternate conformation, form pseudorotaxanes with dialkylammonium axles. The cone-wheel based pseudorotaxanes are 10-100 times more stable than those obtained with the native conformationally-mobile calix[6]arene wheel, as a consequence of their higher degr...
Article
We report here the synthesis of two [8]cycloparaphenylenes ([8]CPP) derivatives, 1 and 2, bearing a mono-substituted benzene moiety. The presence of the substituent implies a planar chirality for the mono-substituted [8]CPP 1 and 2, whose configuration is here described by applying the chirality descriptors pR and pS. Experimental evidence of this...
Article
In this paper, we report the synthesis, structural characterization, and solvatochromic properties of a N-linked p-pyridiniumcalix[4]arenediol derivative 1. In the solid state, 1 forms a dimeric assembly stabilized by a network of weak H-bonding interactions involving acetonitrile solvent molecules. In solution, 1 shows a peculiar negative solvatoc...
Article
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The preparation and characterisation of a novel three‐dimensional organic material consisting of porphyrin arrays on carbon nanotubes embedded in an organogel is reported. Firstly, the porphyrin array was prepared through metal‐ligand coordination of a ditopic ligand (1,2‐bis(4‐pyridyl)ethane) and two bis‐Zn(II) porphyrins, linked through a pyrene...
Article
Full-text available
Crystallization of tetraphosphonate cavitand Tiiii[H, CH3, CH3] in the presence of positively charged amino acids, namely arginine, lysine, or histidine, afforded host-guest complex structures. The X-ray structure determination revealed that in all three structures, the fully protonated form of the amino acid is ditopically complexed by two tetraph...
Article
Full-text available
Pillar[5]arene-decorated quartz slides for the direct detection of linear amines and diamines are now available.
Article
Tetraureido‐dihomooxacalix[4]arenes (tert‐butyl 4a and phenyl 4b) were synthesised and obtained in a partial cone conformation in solution and in the solid state, as confirmed by NMR and X‐ray diffraction studies. Their complexation ability towards halides, pseudo‐halides and oxoanions was assessed by 1H NMR and UV‐Vis titrations. Structural and en...
Article
Praziquantel is the only available drug to treat Schistosomiasis. However, its utilization is limited by many drawbacks, including the high therapeutic dose needed, resulting in large tablets and capsules difficult to be swallowed, especially from pediatric patients. In this study, an alternative option to overcome these disadvantages is proposed:...
Article
The properties of two inherently chiral cavitands in enantioselective recognition of N-methyl-leucine was studied in solution, through ¹H and ³¹P NMR experiments, and in the solid state, through co-crystallisation experiments. The inherent chirality of the receptors was obtained through the desymmetrization of the rigid concave cavity by introducin...
Article
A new series of supramolecular assemblies was obtained through the interaction of 3-pyridylmethyl-calixarenes and copper or zinc ions. Here, we report the characterization of the complexes formed both in solution and at the solid state. The results offer appealing insights on how the steric crowding of the lower rim and different coordination modes...
Article
A novel FeL/Fe₂L₂ manifold, with HL= 2-{[[di(2-pyridyl)methyl] (methyl)amino]methyl}phenol, has been prepared in gram scale (>50% yield) and characterized in solution and solid state. The monomer/dimer interconversion is controlled in aqueous phase, upon varying the pH conditions. The electrocatalytic hydrogen evolving reaction (HER) occurs through...
Article
Three novel tetra(thio)ureido dihomooxacalix[4]arene anion receptors (phenylurea 4a, phenylthiourea 4b and tert-butylurea 4c) were synthesised and obtained in the cone conformation in solution, as shown by NMR studies. The X-ray crystal structure of 4c is reported. The host-guest properties of these receptors toward several anions were investigated...
Article
The supramolecular organization in the solid state of five novel gamma-hydroxybutenolides is described. The functionalities on their framework drive the construction of the crystalline packing through weak non-covalent forces such as H-bonds, CH-pi, pi-pi and CH....O interactions. Gamma-butenolides bearing an unsubstituted aromatic or heteroaromati...
Article
The reaction of cis-blocked, square-planar MII complexes with tetratopic N-donor ligands is known to give metallasupramolecular assemblies of the formula M2nLn. These assemblies typically adopt barrel-like structures, with the ligands paneling the sides of the barrels. However, alternative structures are possible, as demonstrated by the recent disc...
Article
Full-text available
A new inherently chiral cavitand is described, in which the desymmetrization of the rigid concave cavity is achieved by introducing three different bridging groups at the upper rim, namely two inward P=O groups, one inward P=S moiety and one methylene bridge in the AABC mode. The racemic mixture of cR and cS enantiomers is resolved by semi-preparat...
Article
The simple tetraminocalix[4]arene 1, bearing weak H-bond donor NH2 groups, is a highly efficient organocatalyst for the Vinylogous Mukaiyama Aldol Reaction (VMAR) of 2-(trimethylsilyloxy)furan 5 with ?-ketoesters 6a-l under "on-water conditions", thanks to the hydrophobic amplification of weak interactions. The catalytic efficiency of calixarene ca...
Article
The coupling of a polycationic Mn(III)-porphyrin, with a dinuclear Mn2(II,II)L2 core (HL = 2-{[[di(2-pyridyl)methyl](methyl)amino]methyl}phenol), results in a dual Superoxide Dismutase (SOD) and Catalase (CAT) functional analogue, Mn2L2Pⁿ⁺, enabling a detoxification cascade of the superoxide anion and hydrogen peroxide into benign H2O and O2. The S...
Article
The phenomenon of polymorphism is of great relevance in pharmaceutics, since different polymorphs have different physico-chemical properties, e.g. solubility, hence, bioavailability. Coupling diffractometric and spectroscopic experiments with thermodynamic analysis and computational work opens to a methodological approach which provides information...
Article
Full-text available
Protease inhibitors are key components in the chemotherapy of HIV infection. However, the appearance of viral mutants routinely compromises their clinical efficacy, creating a constant need for new and more potent inhibitors. Recently, a new class of epoxide-based inhibitors of HIV-1 protease was investigated and the configuration of the epoxide ca...
Article
Protease inhibitors are key components in the chemotherapy of HIV infection. However, the appearance of viral mutants routinely compromises their clinical efficacy, creating a constant need for new and more potent inhibitors. Recently, a new class of epoxide-based inhibitors of HIV-1 protease was investigated and the configuration of the epoxide ca...
Article
The first example of a resorcin[6]arene cavitand in which sulfate bridges are introduced between the OH groups is here reported. In addition to their structural role, sulfate bridges behave as functional supramolecular interacting groups thus favoring the complexation of suitable organic ammonium guests.
Article
Large (Mw > 10 kDa) heterometallic coordination cages with gyrobifastigium-like geometry are obtained by using metalloligands with sterically demanding FeII clathrochelate cores and four divergent pyridyl groups. Upon reaction with cis-blocked PtII and PdII complexes, MII8L4 cages are formed. The gyrobifastigium geometry of these cages is in contra...
Article
The synthesis of the first examples of calix[4]arene-based Fischer carbene complexes is reported here. Fischer carbene complex 2 is the key intermediate to reach uracil-like derivatives 3 and 4. X-ray and NMR studies revealed that the uracyl-like synthon gives rise to a supramolecular dimer. The organometallic calixarene complexes showed a promisin...
Article
The biogenic tetraamines, spermine and norspermine, are efficiently encapsulated in the solid state by two molecules of carboxylcalix[5]arene, by means of a highly regioselective proton-transfer followed by bis-endo-cavity inclusion, providing overall-neutral complexes with a 70-72% packing coefficient, despite the modest affinity shown in solution...
Article
Full-text available
The two-domain protein PduO, involved in 1,2-propanediol utilization in the pathogenic Gram-negative bacterium Salmonella enterica is an ATP:Cob(I)alamin adenosyltransferase, but this is a function of the N-terminal domain alone. The role of its C-terminal domain (PduOC) is, however, unknown. In this study, comparative growth assays with a set of S...
Article
We report on the eligibility of tetraphosphonate resorcinarene cavitands for the molecular recognition of amino acids. We determined the crystal structure of thirteen complexes of the tetraphosphonate cavitand Tiiii[H, CH3, CH3] with amino acids. 1H and 31P NMR experiments and ITC analysis were performed to probe the binding between cavitand Tiiii[...
Article
The synthesis of the larger resorcin[5 and 6]arene macrocycles [5]OMe and [6]OMe has been obtained by a Lewis acid-catalyzed condensation of 1,3-dimethoxy-2-methylbenzene with paraformaldehyde in o-dichlorobenzene as the solvent. The methoxy-resorcin[5 and 6]arenes were quantitatively demethylated by treatment with BBr3 to obtain the corresponding...
Article
Molecular recognition of C60 fullerene by two cavitands, bearing four and three quinoxaline walls, is reported here. Fluorescence titrations show the recognition ability of the receptors with high binding constant values. The formation of a stable 1:1 supramolecular complex was also confirmed by DOSY, EI-MS and X-ray analysis. The crystal structure...
Article
Two novel triptycene quinoxaline cavitands (DiTriptyQxCav and MonoTriptyQxCav) have been designed, synthesized, and applied in the supramolecular detection of benzene, toluene, ethylbenzene, and xylenes (BTEX) in air. The complexation properties of the two cavitands towards aromatics in the solid state are strengthened by the presence of the tripty...
Article
The octaanionic 5,11,17,23-tetrasulfonato-25,26,27,28-tetrakis(hydroxycarbonylmethoxy)-calix[4]arene (cone conformation) (C4TsTc) was investigated as a sensor for the biogenic tetracationic polyamine, spermine .(H4Spe4+). Fluorescence titration experiments of the water-soluble calixarene with spermine showed the formation of the 2:1 and 1:1 calixar...
Article
The solid state structures of a resorcin[6]arene macrocycle crystallized in two different forms are here reported. In both instances, the molecule adopts a pinched cone conformation very similar to that of p-tert-butylcalix[6]arene. In one case, the resorcin[6]arene macrocycle self-assembles in a molecular capsule able to host toluene and ethyl ace...
Article
Polyoxomolybdate-based organic−inorganic hybrid architectures were synthesised and characterised by X-ray crystallography. The supramolecular assemblies present rows of metallic clusters H-bonded by ammonium cations, with a 1:2 molybdate/ammonium ratio. The organic moieties of the ammonium cations establish hydrophobic contact among them such as va...
Article
A combined XRD and 1H NMR study revealed that two molecules of tetrakis-(tert-butyloxycarbonylmethoxy)-calix[5]arene carboxylic acid are able to efficiently encapsulate α,ω-diaminoalkanes of suitable length as a result of proton-transfer-mediated recognition. In the case of 1,10-diaminodecane and 1,11-diaminoundecane, rim-to-rim attractive van der...
Article
An easily accessible polyoxomolybdate-calix[4]arene hybrid 1 has been synthesized and applied as a heterogeneous catalyst in the sulfoxidation of thioethers to sulfoxides and to sulfones under strictly stoichiometric amounts of 30% H2O2 in CH3CN as the solvent. This study represents the first promising example of successful employment of calixarene...
Article
Using our previously reported maps of the electrostatic surface of horse heart ferri- and ferro-cyt c, comparisons were made between the complementary electrostatic surfaces of three cyt c peroxidase-cyt c complexes and the photosynthetic reaction center-cyt c complex, considering both iron oxidation states. The results obtained were consistent wit...
Article
Full-text available
Ion-pair recognition/complexation of monoamine neurotransmitter and trace amine hydrochlorides takes place –with outstanding efficiency and selectivity– within the π-rich cavity and the pocket formed at the lower rim by the two ureido moieties of tailor-made dihomooxacalixarene receptors 1 and 2. The solid-state structure of 1 is also reported.
Article
The reaction of [Co-III(4,4'dmsalen)(CH2Cl)(S)], where 4,4'dmsalen = 4,4'-dimethylsalen and S = solvent, with pyridine led to the formation of [Co-III(4,4'dmsalen)(CH(2)py)(Cl)], containing a nonstabilized pyridinium ylide as axial ligand. The complex has been unambiguously characterized by single-crystal X-ray diffraction analysis. Time-resolved H...
Article
Negatively charged gemini guests in the presence of a tetracationic host trigger the formation of self-assembling structures at physiological pH in water generating entities of the HG and H2G type (H = host and G = guest). ITC measurements show that the gemini guests are included via concerted electrostatic and hydrophobic interactions and that the...
Article
An original method to evaluate the occupancy factors of ligands based on the direct treatment of the diffraction intensities obtained from isomorphous single crystals grown in the presence of binary mixtures of competitive ligands is presented. This method was developed and first applied to evaluate the affinity of a tetraphosphonate cavitand recep...
Article
Functionalization of the lower rim of p-tert-butyldihomooxacalix[4]arene with two (thio)ureido moieties provided new diurea (n-propyl 5a, tert-butyl 5b and phenyl 5c) and dithiourea (phenyl 5d) derivatives, all in the cone conformation, as shown by NMR studies. The X-ray crystal structure of 5c is reported. The binding ability of these neutral rece...
Article
A new pseudopeptide epoxide inhibitor, designed for irreversible binding to HIV protease (HIV-PR), has been synthesized and characterized in solution and in the solid state. However, the crystal structure of the complex obtained by inhibitor-enzyme cocrystallization revealed that a minor isomer, with inverted configuration of the epoxide carbons, h...

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