Properties of the correlated electronic states of pyrene and hydrogenated pyrene

Approximate calculations are reported on pyrene within the PPP model Hamiltonian using a novel restricted CI scheme which employs both molecular orbital and valence bond techniques. Also reported are detailed full CI results of the PPP model on 2,7-dihydropyrene obtained using the valence bond method. Spectral studies, charge and spin density calculations in ground and excited states, and ring current calculations in the ground state of the molecules are presented. In pyrene, the calculated excitation energies are in good agreement with experiment. The closed structure pi-conjugated molecule pyrene appears to show smaller distortions from the ground state geometry compared with the open structure pi-conjugated molecule 2,7-dihydropyrene. The ground state equilibrium structure of 2,7-dihydropyrene can be viewed as two hexatriene molecules connected by a vinyl crosslink, as is evident from bond order and ring current calculations. This is consistent with the only Kekule resonant structure possible for this molecule.

Evolution of electronic structure with dimensionality in divalent nickelates

We investigate the evolution of electronic structure with dimensionality (d) of Ni-O-Ni connectivity in divalent nickelates, NiO (3-d), La2NiO4, Pr2NiO4 (2-d), Y2BaNiO5 (1-d) and Lu2BaNi5 (0-d), by analyzing the valence band and the Ni 2p core-level photoemission spectra in conjunction with detailed many-body calculations including full multiplet interactions. Experimental results exhibit a reduction in the intensity of correlation-induced satellite features with decreasing dimensionality. The calculations based on the cluster model, but evaluating both Ni 3d and O 2p related photoemission processes on the same footing, provide a consistent description of both valence-band and core-level spectra in terms of various interaction strengths. While the correlation-induced satellite features in NiO is dominated by poorly screened d(8) states as described in the existing literature, we find that the satellite features in the nickelates with lower dimensional Ni-O-Ni connectivity are in fact dominated by the over-screened d(10)L(2) states. It is found that the changing electronic structure with the dimensionality is primarily driven by two factors: (i) a suppression of the nonlocal contribution to screening; and (ii) a systematic decrease of the charge-transfer energy Delta driven by changes in the Madelung potential. [S0163-1829(99)09619-8].

Synthesis based on cyclohexadienes. Part 25. Total synthesis of (+/-)-allo-cedrol (khusiol)

The first stereoselective total synthesis of (+/-)-allo-cedrol 20, an enantiomer of khusiol and a complex sesquiterpene having a novel tricyclo[5.2.2.0(1,5)]undecane framework, is reported from 8-methoxytricyclo[6.2.2.0(1,6)]dodec-6-en-9-one 6c. The methodology involves preparation of 9-methoxytricyclo[7.2.1.0(1,6)]dodec-6-en-8-one 12 from 6c and its conversion through the compounds 8-benzyloxy-7,7-dimethyl-9-methoxytricyclo[7.2.1.0(1,6)]dodec-5-ene 38, 7-benzyloxy-8-methoxy-2,6,6-trimethyltricyclo[6.2.1.0(1,5)]undecane 48 into 8-methoxy-2,6,6-trimethyltricyclo[6.2.1.0(1,5)]undecan-7-one 49. Wittig reaction of 49 affords the olefin 50 which has been smoothly rearranged into khusione 51. Metal-ammonia reduction of khusione under specific conditions affords (+/-)-allo-cedrol. Thus, bridgehead substitution of a methoxy group by a methyl group is the key reaction in this synthesis. In an alternative strategy, attempted conversion of 8-methoxy-2-methyltricyclo[6.2.1.0(1,5)]undec-5-en-7-one 16 into khusione 37 results in an inseparable mixture of the isomers. A notable observation in this synthesis is the unusual formation of a gamma-alkylated product 27 during Woodward methylation of 16.

Synthesis, reactivity and structural characterisation of bicyclic tetraphosphapentazanes

The diphenoxy bicyclic tetraphosphapentazane derivatives (EtN)(5)P-4(OPh)(2) 2 and its monoxide (EtN)(5)P-4(O)(OPh)(2) 3 have been prepared. Both 2 and 3 exist as a mixture of two isomers. One isomer of (EtN)(5)P-4(O)(OPh)(2) 3a has been isolated and its reaction with tetrachloro-1,2-benzoquinone yielded (EtN)(5)P-4(O)(OPh)(2)(O2C6Cl4) 5 in which the junction phosphorus atom becomes five-co-ordinated. Treatment of 2 or 3a with [Mo(CO)(4)(nbd)] (nbd = norbornadiene, bicyclo[2.2.1]hepta-2,5-diene), on the other hand, yielded the chelate complex [Mo(CO)(4){(EtN)(5)P-4(O)(n)(OPh)(2)}] (n = 0 or 1; 6 or 7) in which the peripheral phosphorus atoms are bonded to the metal. The structures of 3a and 5-7 have been confirmed by single-crystal X-ray diffraction studies. The two P3N3 rings in 3a and 5 adopt twist/twist and irregular/twist conformations respectively; the phenoxy substituents occupy the 'pseudo axial' positions. However, an ideal chair conformation is observed for the P3N3 rings in 6 and 7 with the phenoxy substituents taking up the 'pseudo equatorial' positions. The NMR spectroscopic data for the compounds are discussed.

Electronic structure studies and photocatalytic properties of cubic Bi1.5ZnNb1.5O7

The photocatalytic ability of cubic Bi1.5ZnNb1.5O7 (BZN) pyrochlore for the decolorization of an acid orange 7 (AO7) azo dye in aqueous solution under ultraviolet (UV) irradiation has been investigated for the first time. BZN catalyst powders prepared using low temperature sol-gel and higher temperature solid-state methods have been evaluated and their reaction rates have been compared.The experimental band gap energy has been estimated from the optical absorption edge and has been used as reference for theoretical calculations. The electronic band structure of BZN has been investigated using first-principles density functional theory (DFT) calculations for random, completely and partially ordered solid solutions of Zn cations in both the A and B sites of the pyrochlore structure.The nature of the orbitals in the valence band (VB) and the conduction band (CB) has been identified and the theoretical band gap energy has been discussed in terms of the DFT model approximations.

The equilibrium geometry and electronic structure of Bi nanolines on clean and hydrogenated Si(001) surfaces

The equilibrium geometry, electronic structure and energetic stability of Bi nanolines on clean and hydrogenated Si(001) surfaces have been examined by means of ab initio total energy calculations and scanning tunnelling microscopy. For the Bi nanolines on a clean Si surface the two most plausible structural models, the Miki or M model (Miki et al 1999 Phys. Rev. B 59 14868) and the Haiku or H model (Owen et al 2002 Phys. Rev. Lett. 88 226104), have been examined in detail. The results of the total energy calculations support the stability of the H model over the M model, in agreement with previous theoretical results. For Bi nanolines on the hydrogenated Si(001) surface, we find that an atomic configuration derived from the H model is also more stable than an atomic configuration derived from the M model. However, the energetically less stable (M) model exhibits better agreement with experimental measurements for equilibrium geometry. The electronic structures of the H and M models are very similar. Both models exhibit a semiconducting character, with the highest occupied Bi-derived bands lying at ~0.5 eV below the valence band maximum. Simulated and experimental STM images confirm that at a low negative bias the Bi lines exhibit an 'antiwire' property for both structural models.

Resistance Noise in Electrically Biased Bilayer Graphene

We demonstrate that the low-frequency resistance uctuations, or noise, in bilayer graphene is strongly connected to its band structure, and displays a minimum when the gap between the conduction and valence band is zero. Using double-gated bilayer graphene devices we have tuned the zero gap and charge neutrality points independently, which oers a versatile mechanism to investigate the low-energy band structure, charge localization and screening properties of bilayer graphene.

Resistance Noise in Electrically Biased Bilayer Graphene

We demonstrate that the low-frequency resistance fluctuations, or noise, in bilayer graphene are strongly connected to its band structure and display a minimum when the gap between the conduction and valence band is zero. Using double-gated bilayer graphene devices we have tuned the zero gap and charge neutrality points independently, which offers a versatile mechanism to investigate the low-energy band structure, charge localization, and screening properties of bilayer graphene.

Synthesis and characterisation of heterometallic molecular triangles using ambidentate linker: self-selection of a single linkage isomer

The coordination driven self-assembly of discrete molecular triangles from a non-symmetric ambidentate linker 5-pyrimidinecarboxylate (5-pmc) and Pd(II)/Pt(II) based 90◦ acceptors is presented. Despite the possibility of formation of a mixture of isomeric macrocycles (linkage isomers) due to different connectivity of the ambidentate linker, formation of a single and symmetrical linkage somer in both the cases is an interesting observation. Moreover, the reported macrocycles represent the first example of discrete metallamacrocycles of bridging 5-pmc. While solution composition in both the cases was characterised by multinuclear NMR study and electrospray ionization mass spectrometry (ESI-MS), the identity of the assemblies in the solid state was established by X-ray single crystals structure analysis. Variable temperature NMR study clearly ruled out the formation of any other macrocycles by [4 + 4] or [2 + 2] self-assembly of the reacting components.

Study of electron states of solids by techniques of electron spectroscopy

Studies of valence bands and core levels of solids by photoelectron spectroscopy are described at length. Satellite phenomena in the core level spectra have been discussed in some detail and it has been pointed out that the intensity of satellites appearing next to metal and ligand core levels critically depends on the metal-ligand overlap. Use of photoelectron spectroscopy in investigating metal-insulator transitions and spin-state transitions in solids is examined. It is shown that relative intensities of metal Auger lines in transition metal oxides and other systems provide valuable information on the valence bands. Occurrence of interatomic Auger transitions in competition with intraatomic transitions is discussed. Applications of electron energy loss spectroscopy and other techniques of electron spectroscopy in the study of gas-solid interactions are briefly presented.

Infrared Spectra and Conformation of N-Acetylthiourea

Infrared spectra of N-acetylthiourea (ATU) and its N,N,N′-trideuterated compound have been examined in the range 4000–50 cm−1. A complete vibrational assignment with a normal coordinate treatment based on a Urey-Bradley type intramolecular potential function supplemented with valence force function for the out of plane and torsional modes is proposed and the feature of the thioureido vibrations explained. A molecular orbital study by the CNDO/2 method of ATU and its oxygen analog is undertaken and the results are analyzed for a comparative study of the molecular electronic structure and conformation.

Dependence of metal Auger intensity ratios on the effective charge on metal atoms

Metal Auger line intensity ratios were shown by Rao and others to be directly related to the occupancy of valence states. It is now shown that these intensity ratios are more generally related to the effective charge on the metal atom. The Auger intensity ratios are also directly proportional to valence band intensities of metals. Correlations of the intensity ratios with Auger parameters have also been examined.

Characterization of Ion-Exchange Fibers for Controlled Drug Delivery

Increasing attention has been focused on methods that deliver pharmacologically active compounds (e.g. drugs, peptides and proteins) in a controlled fashion, so that constant, sustained, site-specific or pulsatile action can be attained. Ion-exchange resins have been widely studied in medical and pharmaceutical applications, including controlled drug delivery, leading to commercialisation of some resin based formulations. Ion-exchangers provide an efficient means to adjust and control drug delivery, as the electrostatic interactions enable precise control of the ion-exchange process and, thus, a more uniform and accurate control of drug release compared to systems that are based only on physical interactions. Unlike the resins, only few studies have been reported on ion-exchange fibers in drug delivery. However, the ion-exchange fibers have many advantageous properties compared to the conventional ion-exchange resins, such as more efficient compound loading into and release from the ion-exchanger, easier incorporation of drug-sized compounds, enhanced control of the ion-exchange process, better mechanical, chemical and thermal stability, and good formulation properties, which make the fibers attractive materials for controlled drug delivery systems. In this study, the factors affecting the nature and strength of the binding/loading of drug-sized model compounds into the ion-exchange fibers was evaluated comprehensively and, moreover, the controllability of subsequent drug release/delivery from the fibers was assessed by modifying the conditions of external solutions. Also the feasibility of ion-exchange fibers for simultaneous delivery of two drugs in combination was studied by dual loading. Donnan theory and theoretical modelling were applied to gain mechanistic understanding on these factors. The experimental results imply that incorporation of model compounds into the ion-exchange fibers was attained mainly as a result of ionic bonding, with additional contribution of non-specific interactions. Increasing the ion-exchange capacity of the fiber or decreasing the valence of loaded compounds increased the molar loading, while more efficient release of the compounds was observed consistently at conditions where the valence or concentration of the extracting counter-ion was increased. Donnan theory was capable of fully interpreting the ion-exchange equilibria and the theoretical modelling supported precisely the experimental observations. The physico-chemical characteristics (lipophilicity, hydrogen bonding ability) of the model compounds and the framework of the fibrous ion-exchanger influenced the affinity of the drugs towards the fibers and may, thus, affect both drug loading and release. It was concluded that precisely controlled drug delivery may be tailored for each compound, in particularly, by choosing a suitable ion-exchange fiber and optimizing the delivery system to take into account the external conditions, also when delivering two drugs simultaneously.

Upregulation and Functionality of Neuronal Nicotinic Acetylcholine Receptors

Cigarette smoking is, in developed countries, the leading cause of premature death. In tobacco smoke, the main addictive compound is nicotine, which in the brain binds to neuronal nicotinic acetylcholine receptors (neuronal nAChRs). These have been implicated in addiction, but also in several neurological disorders including Alzheimer's and Parkinson's diseases, Tourette's syndrome, attention-deficit hyperactivity disorder (ADHD), schizophrenia, pain, depression, and autosomal-dominant noctural frontal lobe epilepsy; all of which makes nAChRs an intriguing target of study. Chronic treatment with nicotine leads to an increase in the number of nAChRs (upregulation) in the brain and changes their functionality. Changes in the properties of nAChRs are likely to occur in smokers as well, since they are exposed to nicotine for long periods of time. Several nAChR subtypes likely play a role in the formation of nicotine addiction by participating in the release of dopamine in the striatum. The aim of this study was to clarify at cellular level the changes in nAChR characteristics resulting from chronic nicotine treatment. SH-SY5Y cells, endogenously several nAChR-expressing, and SH-EP1-h-alfa7 cells, transfected with the alfa 7 nAChR subunit gene were treated chronically with nicotine. The localisation of alfa 7 and beta2 subunits was studied with confocal and electron microscopy. Functionality of nAChRs was studied with calcium fluorometry. Effects of long-term treatment with opioid compounds on nAChRs were studied by means of ligand binding. Confocal microscopy showed that in SH-SY5Y cells, alfa7 and beta2 subunits formed clusters, unlike the case in SH-EP1-h alfa7 cells, where alfa7 nAChRs were distributed more diffusely. The majority of nAChR subunits localised on endoplasmic reticulum (ER). The isomers of methadone acted as agonists at alfa7 nAChRs. Acute morphine challenge also stimulated nAChRs. Chronic treatment with methadone or morphine led to an increased number of nAChRs. In animal studies, mice received nicotine for 7 weeks. Electron microscopical analysis of the localisation of nAChRs showed in the striatum that alfa7 and beta2 nAChR subunits localised synaptically, extrasynaptically, and intracellularly, with the majority localising extrasynaptically. Chronic nicotine treatment caused an increase in the number of nAChR subunits at all studied locations. These results suggest that the alfa7 nAChR and beta2 subunit-containing nAChRs respond to chronic nicotine treatment differently. This may indicate that the functional balance of various nAChR subtypes in control of the release of dopamine is altered as a result of chronic nicotine treatment. Compounds binding both to opioid and nACh receptors may be of clinical importance.

Studies of phosphazenes. Part 15. Chloro(phenoxy)cyclotetraphosphazenes, N4P4Cl8-n(OPh)n

The reaction of N4P4Cl8(1) with sodium phenoxide (or phenol in the presence of triethylamine) has been studied under a variety of experimental conditions. The chloro(phenoxy)-derivatives, N4P4Cl8-n(OPh)n[n= 1 or 2 (mixture of four non-geminal isomers), 3(mixture of non-geminal isomers), 4(mixture of isomers), 5(mixture of isomers), 6(mixture of four non-geminal isomers), or 8], have been isolated by column chromatography over silica gel. Attempts to separate geometric isomers were unsuccessful. Structural elucidation of the products is based on the 31P n.m.r. data for the chloro-precursors and 1H and 31P n.m.r. spectra of the dimethylamino- and/or methoxy-derivatives. The chlorine-replacement pattern is discussed.