Evolution of the properties of Al(n)N(n) clusters with size

A global optimization of stoichiometric (AlN)(n) clusters (n = 1-25, 30, 35, ..., 95, 100) has been performed using the basin-hopping (BH) method and describing the interactions with simple and yet realistic interatomic potentials. The results for the smaller isomers agree with those of previous electronic structure calculations, thus validating the present scheme. The lowest-energy isomers found can be classified in three different categories according to their structural motifs: (i) small clusters (n = 2-5), with planar ring structures and 2-fold coordination, (ii) medium clusters (n = 6-40), where a competition between stacked rings and globular-like empty cages exists, and (iii) large clusters (n > 40), large enough to mix different elements of the previous stage. All the atoms in small and medium-sized clusters are in the surface, while large clusters start to display interior atoms. Large clusters display a competition between tetrahedral and octahedral-like features: the former lead to a lower energy interior in the cluster, while the latter allow for surface terminations with a lower energy. All of the properties studied present different regimes according to the above classification. It is of particular interest that the local properties of the interior atoms do converge to the bulk limit. The isomers with n = 6 and 12 are specially stable with respect to the gain or loss of AlN molecules.     

Structural, energetic, electronic, bonding, and vibrational properties of Ga3O, Ga3O2, Ga3O3, Ga2O3, and GaO3 clusters

The results of density functional theory based calculations on Ga3O, Ga3O2, Ga3O3, Ga2O3, and GaO3 clusters are reported here. A preference for planar arrangement of the constituent atoms maximizing the ionic interactions is found in the ground state of the clusters considered. The sequential oxidation of the metal-excess clusters increases the binding energy, but the sequential removal of a metal atom from the oxygen-excess clusters decreases the binding energy. The increase in the oxygen to metal ratio in these clusters is accompanied by increase in both electron affinity and ionization potential. The ionization induced structural distortions in the neutral clusters are relatively small, except those for Ga3O2. In anionic (cationic) clusters, the added (ionized) electron is shared by the Ga atoms, except in the case of GaO3. The vibrational frequencies and charge density analysis reveal the importance of the ionic Ga-O bond in stabilizing the gallium oxide clusters considered in this study.     

Organic Surface Modification of TEOS Based Silica Aerogels Synthesized by Co-Precursor and Derivatization Methods

The experimental results on the organic modification of tetraethoxysilane (TEOS) based silica aerogels synthesized by co-precursor and derivatization methods are reported and discussed. In order to obtain silica aerogels with better physicochemical properties in terms of higher hydrophobicity, optical transmission and thermal stability, eight organosilane compounds (hydrophobic reagents) of the type R _n SiX_4–n have been used. The molar ratio of tetraethoxysilane (TEOS), ethanol (EtOH), water (0.001 M oxalic acid catalyst) was kept constant at 1:5:7 respectively. The organically modified silica aerogels were produced by two different methods: (i) Co-precursor method and (ii) Derivatization method. In the former method, the molar ratio of hydrophobic reagent (HR) to TEOS was varied from 0.1 to 0.6. In the later method, derivatization of the wet gels was carried out using 20% hydrophobic reagent in methanol. The merits and demerits of both these methods have been presented. The organic surface modification of the aerogels was confirmed by the Fourier Transform Infrared (FTIR) spectroscopic studies and the contact angle measurements. In the co-precursor method, with the increase in hydrophobic reagent/TEOS molar ratio, the hydrophobicity increases ( = 136°) and the optical transmission decreases (5%), whereas in the derivatization method the optical transmission is very high (T 85%) but the hydrophobicity is low ( = 120°). The thermal stability of the hydrophobic aerogels (the temperature up to which the hydrophobicity is retained) was studied in the temperature range of 25–800°C. The aerogels based on the co-precursor method retained the hydrophobicity up to a temperature as high as 520°C and on the other hand, the derivatized aerogels are hydrophobic only up to a temperature of 285°C. For the first time, TEOS based hydrophobic silica aerogels have been obtained with negligible volume shrinkage using the trimethylethoxysilane (TMES) co-precursor. The aerogels were characterized by Fourier transform infrared spectroscopy (FTIR), optical transmittance, Scanning Electron Microscope (SEM), thermogravimetric (TG) and differential thermal (DT) analyses and the contact angle measurements.     

Inclusion of multi-ring compounds byp-tert-butylcalix[5]arene

The inclusion complex ofp-tert-butylcalix[5]arene with tetralin has been characterized in the solid state by a single crystal X-ray diffraction study and by¹³C CP/MAS NMR experiments. A crystallographic mirror plane bisects the calix[5]arene and contains the tetralin molecule (which is dynamically disordered). The guest penetrates the upper rim of the calixarene and the experimental results indicate the saturated ring is imbedded most deeply.p-tert-Butylcalix[5]arene (tetralin) · 2 EtOH belongs to the monoclinic space group C2/m witha = 22.187(6),b = 15.823(6),c = 18.168(5) Å, = 99.70(2)°, andD _c = 1.09 g cm^–3 forZ = 4. Refinement based on 1652 observed reflections led to a finalR value of 0.081. Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82/82129 (19 pages).     

Fluorinated photosensitizers: synthesis, photophysical, electrochemical, intracellular localization, in vitro photosensitizing efficacy and determination of tumor-uptake by F in vivo NMR spectroscopy

For in vivo NMR studies, starting from pyrroles, a series of fluorinated porphyrins were synthesized by following the MacDonald reaction conditions. Upon reaction with osmium tetroxide, a fluorinated porphyrin containing four trifluoromethyl groups (12 fluorine units) was converted into the related chlorin and bacteriochlorin which exhibited long-wavelength absorptions at 652 and 720 nm, respectively. All compounds produced good singlet oxygen production efficiency. A comparative study of nine porphyrins with and without fluorine substituents indicated no adverse effects of the presence of fluorinated groups in the photophysical properties of the porphyrins, chlorins or bacteriochlorins. The first and second one-electron reduction potentials (vs SCE) of the investigated compounds range between −1.29 and −1.49 V and between −1.66 and −1.84 V in PhCN containing 0.1 M TBAP. UV-visible spectroelectrochemical data suggested the formation of π-anion and π-cation radicals upon the first reduction and first oxidation. The in vivo ¹⁹F MR study of a representative fluorine labeled compound with twelve equivalent fluorines confirmed the presence of the fluorine labeled sensitizer in mouse (C3H/HeJ) implanted with RIF tumors on mouse foot dorsum by inoculating 2×10⁵ cells (the studies were repeated on four tumored mice to confirm the feasibility and reproducibility). All fluorinated compounds were found to be quite effective in vitro. In a comparative intracellular localization study with Rhodamine-123 in RIF tumor cells, the most soluble porphyrin containing two propionic ester side chains was found to localize in mitochondria as well as the related chlorin and bacteriochlorin.     

Ultrasound-assisted rapid and efficient synthesis of propargylamines

Ultrasound was used for the addition of metal acetylides to in situ generated imines to generate propargylamines in good to excellent yields using copper iodide in water at ambient temperature. This process is an efficient alternative to traditional heated reactions. A variety of aldehydes and amines were used for this reaction.     

Kinetics of aquation and base hydrolysis ofcis-(carboxylato) (ethylamine)bis(ethylenediamine)cobalt(III) ions

Summary The aquation ofcis-[Co(en)₂(NH₂Et)O₂CR]²⁺ [R=H or Me] is strongly acid-catalysed and the rate and activation parameters for this process are reported. No significant rate difference is observed in the spontaneous aquation path for the complexes. The acetato complex undergoes acid catalysed aquation at a rate comparable to the of the corresponding formato complex, in contrast with the relative basicities of the coordinated formate and acetate. This result is interpreted in terms of relative solvation effects of the initial and transition states of both complexes.The base hydrolysis of both complexes obeys overall second order kinetics in the 0.05[OH^–]_T 0.35 mol dm^–3 range (I=0.5 mol dm^–3). The formato complex reacts five times faster than its acetato analogue under comparable conditions, which is fully consistent with the dissociative mode of activation of the amido conjugate base involving Co–O bond heterolysis. A substantially large positive value for the activation entropy supports SN₁CB mechanism for base hydrolysis.     

Geometry and electronic structure of Vn(Bz)m complexes

First-principles calculations based on the generalized gradient approximation to the density functional theory are performed to explore the global geometries, ground-state spin multiplicities, relative stabilities, and energetics of neutral and anionic V(n)(Bz)(m) (n=1-3, m=1-4, with n相似文献   

The role of the peripheral benzodiazepine receptor in photodynamic activity of certain pyropheophorbide ether photosensitizers: albumin site II as a surrogate marker for activity

A study has been carried out to define the importance of the peripheral benzodiazepine receptor (PBR) as a binding site for a series of chlorin-type photosensitizers, pyropheophorbide-a ethers, the subject of a previous quantitative structure-activity relationship study by us. The effects of the PBR ligand PK11195 on the photodynamic activity have been determined in vivo for certain members of this series of alkyl-substituted ethers: two of the most active derivatives (hexyl and heptyl), the least active derivative (dodecyl [C12]) and one of intermediate activity (octyl [C8]). The photodynamic therapy (PDT) effect was inhibited by PK11195 for both of the most active derivatives, but no effect on PDT activity was found for the less active C12 or C8 ethers. The inhibitory effects of PK11195 were predicted by the binding of only the active derivatives to the benzodiazepine site on albumin, ie. human serum albumin (HSA)-Site II. Thus, as with certain other types of photosensitizers, it has been demonstrated with this series of pyropheophorbide ethers that in vitro binding to HSA-Site II is a predictor of both optimal in vivo activity and binding to the PBR in vivo.     

Theoretical studies on conformational preferences of modified nucleic acid base N6-(N-glycylcarbonyl) adenine

Conformational preferences of modified nucleic acid base N⁶-(N-glycylcarbonyl) adenine, gc⁶Ade, have been investigated using the quantum chemical PCILO (Perturbative configuration interaction using localized orbitals) method. The multidimensional conformational space has been searched using selected grid points formed by combining various torsion angles that take favored values derived from energy variation with respect to each torsion angle individually. The theoretically predicted most stable, minimum energy conformation of the molecule is such that the substituent on N(6) spreads away from the imidazole moiety of the adenine ring, thus keeping distal orientation. The preferred molecular orientation is stabilized by an intramolecular hydrogen bond from N(11)H of the amino acid to N(1) of the adenine. The carboxylic group of the substituent is trurned away in relation to N(11)H…?N(1) and is perpendicular to the plane through the rest of the molecule The alternative stable conformation corresponding to an 0.8 kcal/mol higher energy has a coplanar carboxylic group turned towards the same side as N(11)H…?N(1) and is exhibited in the crystal structure of the nucleoside derivative, gc⁶A. Energetically, the carboxyl group may change its orientation over a wide range, without much destabilization. This suggests probing by the carboxyl group of the molecular environment in the vicinity of the anticodon in tRNA.