Atrane complexes chemistry as a tool for obtaining trimodal UVM-7-like porous silica

Abstract

The use of atrane complexes as hydrolytic precursors enables the homogeneous incorporation of manganese (25 ≤ Si/Mn ≤ 48) throughout the porous walls of the nanoparticles of a surfactant-templated bimodal mesoporous silica (UVM-7). The subsequent leaching of the manganese nanodomains allows adding controlled microporosity to the host silica framework. The resulting final silica material presents three pore systems structured at different length scales: interparticle textural-type macroporosity (ca. 43.2 nm), ordered intraparticle mesoporosity (ca. 2.63 nm; after template removal), and well-dispersed microporosity (< 2 nm; as consequence of the lixiviation of the Mn-rich domains). The good dispersion of the guest element (Mn) in the silica intermediate provided by the atrane route is responsible for the disordered but regular microporosity achieved.     

Study of the Reaction 2-(p-Nitrophenyl)Ethyl Bromide + OH(-) in Sulfobetaine Aqueous Micellar Solutions in the Presence and Absence of Added Salts

The reaction of dehydrobromination of 2-(p-nitrophenyl)ethyl bromide with hydroxide ions has been studied in aqueous micellar solutions of N-tetradecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate, SB3-14. The kinetic effects of added salts (NaF, NaCl, NaBr, and NaNO(3)) on the reaction rate in SB3-14 aqueous micellar solutions have also been studied. They were rationalized by considering the binding of the anions, which come from the salt, to the sulfobetaine micelles and their competition with the reactive hydroxide ions for the micellar surface. The equilibrium binding constant of the 2-(p-nitrophenyl)ethyl bromide to the sulfobetaine micelles was estimated by recording the changes in the spectra of the organic substrate when the SB3-14 concentration in the micellar medium changed. This value was in agreement with that obtained from fitting of kinetic data. The second-order rate constant in the micellar pseudophase revealed that the reaction is faster in SB3-14 micelles than in water. This acceleration seems independent of the presence of added salts and can be explained by considering that SB3-14 micelles favor reactions in which charge is delocalized in the transition state. Copyright 2001 Academic Press.     

Solution 1H NMR characterization of axial interactions of the proximal and distal His in the cyanomet complexes of the isolated chains and the 65 kDa intact tetramer of human hemoglobin A.

Solution 1H NMR has been used to investigate the axial bonding of the proximal His and the hydrogen-bonding of the distal His to the bound ligand in the isolated chains as well as the subunits of intact, tetrameric, cyanomet human hemoglobin A. The complete proximal His, including all ring protons necessary to monitor bonding in each subunit, could be definitively assigned by 1D/2D methods despite the large size (approximately 65 kDa) and severe relaxation (to T(1) approximately 3 ms, line width approximately 1.5 kHz) of two of the protons. The complete distal His E7 ring was assigned in the alpha-chain and alpha-subunit of HbA, and the dipolar shifts and relaxation were analyzed to reveal a disposition intermediate between the positions adopted in HbCO and HbO2 that is optimal for forming a hydrogen bond with bound cyanide. The lability of the alpha-subunit His E7 NepsilonH is found to be similar to that in sperm whale cyanomet myoglobin. The orientation of the distal His E7 in the beta-subunit is found to be consistent with that seen in either HbCO or HbO2. While the His E7 labile NepsilonH proton signal could not be detected in either the beta-chain or subunit, it is concluded that this more likely reflects increased lability over that of the alpha-subunit, and not the absence of a hydrogen bond to the bound ligand. Analysis of the heme mean methyl hyperfine shift, which has been shown to be very sensitive to the presence of distal hydrogen bonds to bound cyanide (Nguyen, B. D.; Xia, Z.; Cutruzzolá, F.; Travaglini Allocatelli, C.; Brancaccio, A.; Brunori, M.; La Mar, G. N. J. Biol. Chem. 2000, 275, 742-751), directly supports the presence of a distal His E7 hydrogen bond to cyanide in the beta-chain and beta-subunit which is weaker than the same hydrogen bond in the alpha-subunit. The potential for the proximal His hyperfine shifts in serving as indicators of axial strain in the allosteric transition of HbA is discussed.     

Solution NMR determination of the seating(s) of meso-nitro-etioheme-1 in myoglobin: implications for steric constraints to meso position access in heme degradation by coupled oxidation

The highly stereoselective cleavage of hemin in myoglobin by coupled oxidation has been attributed to steric barriers that leave more space near the alpha- than the other meso-positions. The steric barriers near meso positions in myoglobin have been investigated by establishing the thermodynamics and dynamics of possible seatings in the pocket of horse myoglobin of a four-fold symmetric etioheme I modified with a bulky nitro group at a single meso position. The cyanomet complex of this reconstituted myoglobin exhibits three sets of (1)H NMR resonances that are linked dynamically and occur in approximate populations ratios of 0.82:0.10:0.08. Two dimensional (1)H NMR has been used to assign the hemin and heme pocket resonances in the major isomer in solution and to determine that the hemin is oriented with the nitro group at the canonical gamma-meso position of native hemin. The dominance of this isomer is attributed to the solvent exposure of this portion of the hemin which stabilizes the highly polar nitro group. Using a combination of magnetization transfer among methyl groups of the three isomers due to "hopping" of the hemin about its normal, the assigned resonances of an isoelectronic, bis-cyano complex of meso-nitro-etioheme I, and the known essentially constant rhombic perturbation of heme pocket sites on the hyperfine shifts of heme methyl (Kolczak, U.; Hauksson, J. B.; Davis, N. L.; Pande, U.; de Ropp, J. S.; Langry, K. C.; Smith, K. M.; LaMar, G. N. J. Am. Chem. Soc. 1999, 121, 835-843); the two minor isomers are shown to place their bulky nitro group at the canonical delta-meso (8%) and alpha-meso positions (10%). The comparable population of the isomers with nitro groups at the hydrophobic alpha- and delta-meso positions dictates that, while the static crystal structure finds more room near the alpha-meso position, the deformation at minimal energetic expense near the alpha- and delta-meso positions is comparable. These results argue that factors other than simple steric influences control the selectivity of the ring cleavage in myoglobin.     

Bis(2,4,6-trifluorophenyl) derivatives of palladium(II)

Summary The organopalladium(II) complexes: Pd(2,4,6-C₆F₃H₂)₂L₂ [L=triphenylphosphine(PPh₃), methyldiphenylphosphine(PPh₂Me), dimethylphenylphosphine-(PPhMe₂) or pyridine(py); L₂=1,2-bis(diphenylphosphino)ethane(dpe), 2,2-bipyridine(bipy), 1, 10-phenanthroline(phen) or ethylenediamine(en)] have been prepared by addition of the appropriate compound to the THF-dioxane solution resulting from the arylation of potassium tetrachloropalladate(II) with (2,4,6-C₆F₃H₂)MgBr. The i.r. data suggest that the py and PPhMe₂ compounds are thecis-isomers, whereas the PPh₃ and PPh₂Me compounds have thetrans configuration.¹H- and¹⁹F-n.m.r. data for the compounds are reported.     

Synthetic hosts for molecular recognition of ureas

Four hosts (7-10) containing 2,6-bisamidopyridine- and 2,5-bisamidopyrrole-bearing pyridyl or 1,8-naphthyridyl groups have been prepared and their structures studied by a combination of multinuclear NMR spectroscopy and X-ray crystallography. Their behavior in molecular recognition of urea derivatives, including (+)-biotin methyl ester, has been approached by molecular modeling (Monte Carlo conformational search, AMBER force field). The minimum energy values for the complexes are correlated with the experimental binding energies determined by means of (1)H NMR titrations.     

Ferrocene-based heteroditopic receptors displaying high selectivity toward lead and mercury metal cations through different channels

The synthesis and electrochemical, optical, and ion-sensing properties of ferrocene-imidazophenazine dyads are presented. Dyad 4 behaves as a highly selective chemosensor molecule for Pb(2+) cations in CH(3)-CN/H(2)O (9:1). The emission spectrum (λ(exc) = 317 nm) undergoes an important chelation-enhanced fluorescence effect (CHEF = 47) in the presence of Pb(2+) cations, a new low-energy band appeared at 502 nm, in its UV/vis spectrun, and the oxidation redox peak is anodically shifted (ΔE(1/2) = 230 mV). The presence of Hg(2+) cations also induced a perturbation of the redox potencial although in less extension than those found with Pb(2+) cations. Dyad 7, bearing two fused pyridine rings, has shown its ability for sensing Hg(2+) cations selectively through three channels: electrochemical, optical, and fluorescent; the oxidation redox peak is anodically shifted (ΔE(1/2) = 200 mV), a new low-energy band of the absorption spectrum appeared at 485 nm, and the emission spectrum (λ(exc) = 340 nm) is red-shifted by 32 nm accompanied by a remarkable chelation-enhanced fluorescent effect (CHEF = 165). Linear sweep voltammetry revealed that Cu(2+) cations induced oxidation of the ferrocene unit in both dyads. (1)H NMR studies have been carried out to obtain information about the molecular sites which are involved in the binding process.     

Basicity of bisperhalophenyl aurates toward closed-shell metal ions: metallophilicity and additional interactions

The interaction of bisperhalophenyl aurates [AuR₂]^? (R?=?C₆F₅, C₆F₃Cl₂, and C₆Cl₅) with the closed-shell Ag⁺, Cu⁺, and Tl⁺ ions has been studied theoretically and compared with the experimentally known X-ray diffraction crystal structures. Initially, the aurates have been fully optimized at MP2 level of theory in a D _2h symmetry. The analysis of the basicity of the three aurates [AuR₂]^? (R?=?C₆F₅, C₆F₃Cl₂ and C₆Cl₅) against Ag⁺ ions in a C _2v symmetry has been calculated in point-by-point bsse-corrected interaction energy analysis at HF and MP2 levels of theory. Taking into account the experimental observation of additional interactions between the heterometals and C _ipso atoms at the perhalophenyl rings or halogen atoms at the ortho position of the perhalophenyl rings, dinuclear models of the type [AuR₂]^?···Ag⁺ (R?=?C₆Cl₅, and C₆F₅); [AuR₂]^?···Cu⁺ (R?=?C₆F₅, and C₆Cl₅) and [AuR₂]^?···Tl⁺ (R?=?C₆F₅, and C₆Cl₅) with a C _2v , C ₂ , and C _s symmetries have been optimized at DFT-B3LYP level. The interaction energies have been computed through bsse-corrected single point HF and MP2 calculations. The energy stabilization provided and the heterometal preference have been analyzed and compared with the experimental results.     

Enthalpies of sublimation of ferrocene and nickelocene measured by calorimetry and the method of Langmuir

A quick and accurate methodology that is based on Langmuir’s equation and that is developed by utilising a DSC7 device is proposed for the measurement of the enthalpies of sublimation of substances characterised by vapour pressures of approximately 1.0 Pa at room temperature. The procedure was applied to ferrocene and nickelocene; the accuracy and uncertainty associated with the experimental results show that the reliability of the developed indirect method is comparable to the direct calorimetric measurements also performed in this work. Furthermore, the melting data and crystal-phase heat capacities for both metallocenes were calorimetrically measured, whereas the gas-phase heat capacity for each metallic bis(cyclopentadienyl) was theoretically estimated by DFT calculations.