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Purpose – The purpose of this paper is to show the development of Appropriate Adult services in Scotland over the past nine years and considers how this differs from the rest of the UK. Design/methodology/approach – New analysis of existing statistical information is provided to show pattern of demand, type of interview, nature of mental disorder involved and regional differences. Findings – Growth in demand for services is identified for both suspect and witness interviews, with people with learning disabilities most frequently receiving support. There is significant variation in the pattern of referrals across Scotland. Practical implications – The results reflect heightened awareness amongst police officers of the need for Appropriate Adults, but there should be examination of the different types of provision to promote equity of service. Originality/value – This is the first time that these figures have been collated and subject to analysis. They provide comparative information within Scotland that is also of relevance to the rest of the UK.

AIMS AND OBJECTIVES: To explore the experiences and perceptions of close and sexual relationships of people with an intellectual disability. BACKGROUND: Positive interpersonal relationships are beneficial for people with an intellectual disability, acting as a protective barrier against, social stigma and negative outcomes such as physical and mental health problems. The social networks of people with an intellectual disability are, however, often more restricted than those of the general population. There has been very little research exploring the views and experiences of people with an intellectual disability about social and sexual relationships. DESIGN: Exploratory study using a qualitative research design. METHODS: Semi-structured interviews were conducted with 10 (6 male, 4 female) participants. Data were analysed using interpretive phenomenological analysis. RESULTS: 'Touching other people in relationships' was identified as a superordinate theme. The theme was represented by five subthemes: 'Is wrong'; 'Unsafe to talk about'; 'Suggesting is safe'; 'No freedom or fun'; and 'Being touched'. The findings presented are drawn from a larger qualitative study. CONCLUSIONS: The findings highlight the importance of touch and sexual behaviours in the close relationships of participants. Negative perceptions were observed to surround sexual behaviours. Rules and restrictions regarding physical contact were also described. RELEVANCE TO CLINICAL PRACTICE: Disseminating these findings may increase awareness of the importance of physical contact in the close relationships of people with an intellectual disability and promote positive support arrangements.

Background Positive interpersonal relationships have been found to enhance an individual's quality of life. However, people with intellectual disabilities (PWID) often have restricted social networks, and little is known about their views on close social relationships. The study aimed to explore how this group perceives and experiences close relationships. Materials and Methods Ten (6 = men 4 = women) PWID participated. Data were collected using semi-structured interviews, and analysed using interpretive phenomenological analysis. Results The results report on three of five themes drawn from a larger qualitative study: ‘Relationships feeling safe and being useful’; ‘Who's in charge?’ and ‘Struggling for an ordinary life’. Conclusions Close relationships are valued and desired by PWID, but a variety of barriers inhibit their development and maintenance. This includes the failure of others to value, accept and appropriately support the independence and relationships of PWID. Potential ways of addressing these issues are discussed.

The results of ab initio (HF, MP2) and density functional (B3LYP) calculations on a series of γ-oxocarboxylic acids [(Z)-3-acetyl or benzoylacrylic and 2-acetyl or benzoylbenzoic acids] A and their cyclic tautomers B are presented. For the open-chain tautomers, different rotamers were considered. Bulk solvent effects were considered by using the polarised continuum model (PCM) and were found to be essential for a proper description of the ring-chain tautomeric equilibrium. Acetyl derivatives generally prefer the cyclic form, whereas for benzoyl derivatives the preference depends on the nature of the link. Introduction of substituents (methyl, phenyl) at C2 and/or C3 for acrylic acid derivatives substantially shifts the equilibrium towards the cyclic form B.

Ab initio (HF and MP2) and density functional (B3LYP) calculations with different basis sets (6-31G∗, 6-311+G∗∗, 6-311+G(2df,p)) on the various conformers of (Z)-3-formyl-acrylic acid and the corresponding ring-closed tautomer 5-hydroxy-furan-2(5H)-one are performed. At all levels of theory the ring tautomer is predicted to be the most stable one. Inclusion of bulk solvent effects (H2O) by the self-consistent isodensity surface polarized continuum model (SCIPCM) further shifts the ring-chain tautomeric equilibria towards the furanone form. Among the open chain tautomers, the s-cis–s-trans conformation is the most stable.

A novel synthesis of clindamycin from lincomycin using N-chlorosuccinimide and triphenylphosphine is reported. This results in high yields and avoids the use of tetrachloromethane employed in the current manufacturing process. This article has been corrected. Link to the correction 10.2298/JSC0012975E

The infrared absorption bands of the C*O stretching vibration and the 13C NMR chemical shifts were measured for a series of nine substituted 3,4-diphenyl-cyclobut-3-ene-1,2-di-ones in CHCl3, CDCl3, and partially in CCl4. The AM1 charge densities, bond orders, and valence angles were calculated for the optimized geometry. Good to satisfactory mutual correlations were found between the arithmetic means of the wave numbers of symmetric and asymmetric C*O stretching vibrations, Hammettσ constants, rate coefficients, and enthalpies of activation of the base-catalyzed ring fission as well as the AM1 oxygen charge densities and bond orders at the carbonyl groups. The results show that the factors controlling the reactivity of these compounds and the structural and IR spectroscopic properties of the C*O groups must be the same. The correlation between the wave numbers of symmetric and asymmetric C*O stretching vibrations affords a slope of a=1.069 which points to the existence of a strong cross-conjugation effect in the cyclobutenedione ring. The correlation of the wave number separation of the absorption bands of symmetric and asymmetric C*O stretching vibrations (Δv(C*O)) for various cyclic diketones enabled the prediction of the angle γ=83° between the bond vectors of the two carbonyl groups in the cyclobutenedione rings, which is in satisfactory agreement with the value calculated by the semiempirical AM1 method.

Mitochondrial DNA (mtDNA) analysis has proved useful in studies of recent human evolution and the genetic affinities of human groups of different geographical regions. As part of an extensive survey of mtDNA diversity in present-day Pacific populations, we obtained sequence information of the hypervariable mtDNA control region of 452 individuals from various localities in the western Pacific. The mtDNA types fell into three major groups which reflect the settlement history of the area. Interestingly, we detected an extremely rare point mutation at high frequency in the small island of Nguna in the Melanesian archipelago of Vanuatu. Phylogenetic analysis of the mtDNA data indicated that the mutation was present in individuals of separate mtDNA lineages. We propose that the multiple occurrence of a rare mutation event in one isolated locality is highly improbable, and that recombination between different mtDNA types is a more likely explanation for our observation. If correct, this conclusion has important implications for the use of mtDNA in phylogenetic and evolutionary studies.

The rate coefficients for the esterification of a series of oxocarboxylic acids with diazodiphenylmethane have been determined in ethanol or 2-methoxyethanol at 30.0 °C. These and the rates of reaction with model compounds have been used to estimate the equilibrium constants for ring-chain tautomerism for the oxocarboxylic acids.

The rate coefficients for the base-catalysed ring fission of a series of 2-phenyl-3-(2-, 3- or 4-substituted phenyl)cycloprop-2-en-1-ones to give the corresponding (E)-2,3-diphenylacrylic acids have been determined in water at 30.0 °C, as well as for the unsubstituted compound at 40.0, 50.0 and 60.0 °C. The effects of meta- and para-substituents on the rates have been correlated using the Hammett equation to give a reaction constant, ρ, equal to ca 1.2 at 30 °C. For the unsubstituted compound, the activation parameters have been calculated and the kinetic solvent isotope effect has been studied. The effects of ortho-substituents on the rates appear to be mainly polar, rather than steric, in origin. The evidence indicates a mechanistic pathway which proceeds by addition of hydroxide anion to the ketone, which is rate-determining. The adduct suffers ring fission to give the final product via a carbanionic intermediate.

Rate coefficients have been measured for the alkaline hydrolysis of methyl 2-trichloro- and tribromoacetylbenzoate, as well as the alkaline hydrolysis of the corresponding 2-trichloro- and tribromobenzoate anions, in 30% (v/v) dioxane–water at several temperatures. The relative rates of hydrolysis and activation parameters demonstrate relatively rapid hydrolysis via neighbouring group participation by the acyl-carbonyl group in the ester hydrolysis and slower hydrolysis via intramolecular fission of the adducts in the benzoate anion hydrolysis. The pKa values of the corresponding benzoic acids have been measured in water and their ring–chain tautomeric equilibrium constants determined.

Summary The synthesis and study of a novel series of potential prodrugs of aspirin is reported. 2-, 3- and 4-formylphenyl aspirins, as well as a series of 4-substituted 2-formylphenyl aspirins, have been prepared. A study of their alkaline hydrolysis indicates that these compounds act as true prodrugs of aspirin which hydrolyse to aspirin and the formylphenol. The rates of hydrolysis and activation parameters indicate that hydrolysis of the 2-formylphenyl esters employs an intramolecular catalytic route.

(1998). Guest Editorial THE EMERGENCE OF PHYSICAL STRUCTURE FROM INFORMATION THEORY. International Journal of General Systems: Vol. 27, No. 1-3, pp. 1-7.

We discuss the emergence of topology from a consideration of set extensions in General Systems Theory. Boundaries arise in a natural way, separating independent elements or regions of the system. Our aim is a unification of Etter theory, Kron's method of Tearing and Jessel's formulation of Huygens' Principle. This should make explicit the equivalence between the objective, structural, holographic and the subjective, relative definitions of information, sought in Bowden (1994b), reprinted in this Special Issue. It connects the abstract generalisations of Schrodinger's equation and Bom's rule derived in probabilistic Etter theory with the real world of electrical and other physical phenomena in General Physical Systems Theory. This paper can be considered as a continuation of Bowden (1990; 1994a) and as a response to Bowden (1994b), reprinted in this issue. We review the ideas behind Kron's Method of Tearing and Jessel's Principle of Secondary sources (both special cases of the above theory) and their equiv...

Rate coefficients were measured for the base-catalysed hydrolysis of a series of substituted 3-(phenoxy- or thiophenoxymethylene)-(Z)-1(3H)-isobenzfuranones (3-phenoxy- or thiophenoxymethylenephthalides) in 70% (v/v) aqueous dioxane at 30.0 °C, in addition to the carbonyl stretching frequencies in chloroform and tetrachloromethane following deconvolution and band separation, when required. The Hammett reaction constants for the alkaline hydrolysis of the 3-/4-substituted phenoxy and thiophenoxy series are ca 0.75 and 1.10, respectively. These results are related to electrostatic field and resonance effects. Successful correlations between the carbonyl stretching frequencies and substituent constants and the rates of alkaline hydrolysis were found. Computational studies using the semi-empirical AM1 method correctly model both the details of the mechanistic pathway and the substituent effects. © 1998 John Wiley & Sons, Ltd.

The synthesis and study of a novel series of potential prodrugs of indomethacin, ketoprofen, ibuprofen and aspirin are reported. 2-Formylphenyl esters of the NSAIDs, together with two 6-substituted 2-formyl and two 2-acylphenyl aspirins and 4-formylphenyl indomethacin, have been prepared. A study of their alkaline and neutral hydrolysis shows that these compounds, with the exception of 2-acetylphenyl aspirin, act as true prodrugs of the NSAIDs, giving the NSAID and acylphenol. The rates of hydrolysis and activation parameters indicate that the 2-acylphenyl esters employ an intramolecular catalytic route. The 2-formylphenyl esters were more potent as anti-inflammatory agents than the parent compounds in the carragheenan-induced paw oedema test.

The infrared and 13C NMR spectra and the kinetics of alkaline hydrolysis of chromium, tricarbonyl[3-[(η6-aryl)methylene]-Z-1(3H)-isobenzofuranones] have been studied in comparison with those of 3-arylmethylene-Z-1(3H)-isobenzofuranones. The 13C NMR spectroscopy has been found to be the most suitable tool for recognition of the site of complexation in the 3-arylmethylene-Z-1(3H)-isobenzofuranone system. A statistically significant correlation has been found between the arithmetic means of the wave numbers of symmetric and asymmetric stretching vibrations of Cr(CO)3 group and σp constants of the substituents. The large slope of this linear dependence suggests an important role of the mesomeric mechanism in the transmission of electronic effects to the Cr(CO)3 moiety. The strong electron-withdrawing effect of the Cr(CO)3 group causes a significant decrease of the polarity of the phthalide CO bond. The reaction rates of the alkaline hydrolytic ring-opening reaction dramatically increase due to the effect of Cr(CO)3 group. The absorption bands of the carbonyl stretching vibrations are markedly split due to Fermi resonance effect. After mathematical correction for Fermi resonance the wave numbers of the unperturbed fundamental CO stretching vibration and the log k values of alkaline hydrolysis exhibit significant linear correlations mutually, as well as with Hammett σ substituent constants. Charton's transmissive factors γ(PhCr(CO)3) have been determined for tricarbonylchromiumphenyl system using the parameters of the linear correlations. The efficiency of the substituent effect transmission is high in CCl4, because a back-donation effect of the carbonyl ligands and decreases in CHCl3 due to the hydrogen bonding between carbonyl groups and solvent molecules. The preparation of some novel chromium, tricarbonyl[3-[(η6-aryl)methylene]-Z-1(3H)- isobenzofuranones] is described.

The Perkin rearrangement of 3-halocoumarins to benzofuran-2-carboxylic acids, catalysed by base, proceeds in two separate stages. The first stage is a relatively rapid base-catalysed ring fission of the 3-halocoumarins to give (E)-2-halo-3-(2-hydroxyphenyl)acrylic acids. Rate coefficients have been measured for the base-catalysed ring fission of 6-substituted and 4-methyl-3-bromocoumarins and of 3-chlorocoumarin in 70% (v/v) dioxane–water at various temperatures. The second stage is a relatively slow cyclisation process. Rate coefficients have been measured for the cyclisation of the same series of substrates in 70% (v/v) dimethyl sulfoxide–water at various temperatures. The enthalpies and entropies of activation have been evaluated. The Hammett reaction constant for the ring fission at 30.0 °C is 2.34 and for the cyclisation at 60.0 °C is –3.54. The ring fission appears to occur by rate-determining addition of hydroxide anion to the carbonyl group, followed by a relatively rapid ring opening process; while the cyclisation probably proceeds by rate-determining fission of the carbon–halogen bond, following formation of a relatively unstable carbanion intermediate formed by intramolecular nucleophilic attack on the vinyl group by the phenoxide anion.

The design and synthesis of a series of multifunctional metronidazole derivatives are described. The main series are multi-esters having two or more metronidazole groups linked together by aryl or alkyl systems. A second system is two nitro-2-methylimidazole groups joined by a dimethylene link. The third is polymeric 2-(2-methyl-5-nitroimidazol-1-yl)ethyl acrylate. The triester, metronidazole trimesate, is exceptionally active as an antibacterial compound, which appears to be associated with a rigid, three-point attachment.

Ring–chain tautomerism in N-methyl- and N-(substituted phenyl)-2-formylbenzamides, 2-benzoylbenzamides, 8-formyl-1-naphthamides, 8-benzoyl-1-naphthamides and 5-formyl-4-phenanthramides has been investigated by IR and 1H NMR spectroscopy and the measurement of their pKa values in 30% (v/v) dimethyl sulfoxide–water. The tautomeric pair synthesised, i.e. hydroxylactam–acylamide or aminolactone–iminocarboxylic acid, appears to be a function of the method of preparation and/or the basicity of amine used. The cyclic tautomer, i.e. hydroxylactam or aminolactone, is predominant in all cases studied. However, equilibrium constants have been estimated from the pKa values for aminolactone–iminocarboxylic acid tautomerisation in which the effect of the links follow similar trends as found for the corresponding hydroxylactone–acylcarboxylic acid tautomeric systems.

Rate coefficients were measured for the base-catalysed hydrolysis of a series of γ-lactones, i.e. 39 substituted 3-(aryl- and alkylmethylene)-(Z)-1(3H)-isobenzofuranones (3-aryl- and alkylmethylenephthalides) in 70% (v/v) aqueous dioxane at 30·0 °C. A Hammett reaction constant for the 3- or 4-substituted phenyl series is ca 1·5, whereas those for the 2-substituted phenyl and 4-substituted 1-naphthyl series, using para-σ values, are ca 1·0 and 1·9. These results are related to an electrostatic field effect model. A very successful correlation between the rates of alkaline hydrolysis of all 39 phthalides and the carbonyl stretching frequencies in chloroform was found. Substituent effects in widely different environments give linearly related effects on both reactivity and physical properties. Computational studies using the semi-empirical AM1 method correctly modelled both the details of the mechanistic pathway and the substituent effects. © 1997 John Wiley & Sons, Ltd.

The rate coefficients for the rearrangement of substituted (E)-5,5′-diphenylbifuranylidenediones to form the corresponding 3,7-diphenylpyrano[4,3-c]pyran-1,5-diones in ethane-1,2-diol at 30.0 °C, catalysed by sodium acetate, were determined. For the unsubstituted dione, the rate coefficients for there arrangement in various alcohols at 30.0 °C, and for three at 59.8 °C, were measured. The reactions were first order in both substrate and acetate anion. Rate coefficients were also measured for the catalysis of the rearrangement of the unsubstituted dione in ethanol and ethane-1,2-diol at 30.0 °C by a series of sodium meta/para-substituted benzoates. Bronsted-type correlations for the latter give α≈1.2. Substrate substitutent effects on the rates of rearrangement of the diones were not marked. A good correlation was found between the rates of rearrangement of the unsubstituted dione and the solvent effect parameter ET(30). This and other evidence indicated a probable mechanism involving a rapid pre-equilibrium between the substrate diones and the carboxylate anion, followed by the formation of an s-trans-enolate anion. The latter rotates to the s-cis isomer, which then intramolecularly attacks the second lactone ring. The process is then repeated with the product dione resulting from loss of the carboxylate anion. © 1997 John Wiley & Sons, Ltd.

The absorption bands of the C=O Stretching vibrations of a series of thirty-nine substitutedZ-3-methylene phthalides (1a-s, 2a-h, 3a-f, 4a-c, and5a-c) were measured in CHCl3 and CCl4. The two-levelFermi resonance effect on the infrared spectra of the above compounds was investigated after deconvolution and band separation. The wave numbers of the unperturbed fundamental C=O stretching vibrations exhibit excellent linear correlations withHammet's constants of substituents and13C NMR chemical shifts of the C=O group.

Rate coefficients have been measured for the base-catalysed cyclisation of 1,2-diacetylbenzene 1, 1,8-diacetylnaphthalene 2, 4,5-diacetylphenanthrene 3 and 2,2′-diacetylbiphenyl 4 in a range of aqueous dimethyl sulfoxide (DMSO) compositions at 30.0 °C, as well as at 45.0 and 60.0 °C at certain concentrations, containing tetramethylammonium hydroxide. For three of the substrates, 1, 2 and 4, the di-[2H3]acetyl compounds were also studied. Studies of the relative rates, activation parameters, kinetic isotope and solvent isotope effects and correlation of the rates with an acidity function were made to give detailed mechanistic pathways. Thus, 2, 3 and 4 react with rate-determining base-catalysed ionisation to give the enolate anion, followed by relatively rapid intramolecular nucleophilic attack and dehydration to give the corresponding cyclic enones; whereas, 1 reacts by the same pathway but with rate-determining intramolecular nucleophilic attack. An intermolecular base-catalysed aldol reaction was also detected for the product of the intramolecular reaction of 2 at high DMSO contents.

Rate coefficients have been measured for the alkaline hydrolysis of a series of chain (normal) esters, the methyl cis-3-(substituted benzoyl)-2,3-diphenylacrylates, and the corresponding ring (pseudo) esters, the 5-methoxy-5-(substituted phenyl)-3,4-diphenylfuran-2(5H)-ones, in 70% (v/v) dioxane–water at 30 °C. Those for the two parent esters were also measured at 45.0 and 60.0 °C and the enthalpies and entropies of activation have been evaluated. A consideration of relative rates, activation parameters and substituent effects indicates hydrolysis of the chain esters with neighbouring group participation by the keto-carbonyl group. The ring esters demonstrate the high reactivity of the five-membered lactone-like system. The steric effects of the phenyl groups does not switch mechanisms, but only modifies reactivity. The equilibrium constants for ring-chain tautomerism in a series of cis-3-(substituted benzoyl)-2,3-diphenylacrylic acids have been determined by using the observed pKa values in 80% (m/m) 2-methoxyethanol–water together with estimated true pKa (pKTa) values. The equilibrium constants for these acids have been correlated using the Hammett equation to give ρ as ca. 1.3. The results are discussed in terms of steric ‘bulk’ and resonance effects.

The base-catalysed ring fission of a series of substituted 2,2-dihydroxyindane-1,3-diones and phenalene-1,3-dione has been studied in 30% (v/v) dioxane–water. The reaction proceeds in two distinct steps. The first is a relatively fast base-catalysed ring fission to give substituted o-carboxyphenylglyoxals, and the second is a rearrangement of the latter resulting in formation of substituted o-carboxymandelic acids. Rate coefficients for the ring fission of a limited series of substrates have been determined at 25.0 °C. The reaction is first order in the mono-anion of the substrate alone. The Hammett reaction constants, ρ, have been obtained from both the kinetic and product studies. The rate- and product-determining step appears to be an intramolecular nucleophilic attack. The rate coefficients for the rearrangement have been determined for all substrates at 25.0, 35.0 and 45.0 °C. The activation parameters have been calculated. The kinetic solvent isotope, solvent and salt effects have been studied. The effects of the 5-substituted and 5,6-disubstituents on the rates have been correlated using a modified Hammett equation giving a reaction constant, ρ, equal to 3.4 at 25 °C.

The rate coefficients for the base-catalysed ring fission of a series of substituted 3,4-diphenylcyclobut-3-ene-1,2-diones to give the corresponding (Z)-2-oxo-3,4-diphenylbut-3-enoic acids have been determined in 50% (v/v) aqueous dimethyl sulfoxide (DMSO) at 25.0 and 45.0 °C, as well as for a limited series in 70% (v/v) aqueous DMSO. The activation parameters have been calculated. The effect of both mono- and di-substitution of the phenyl groups has been studied and gives a Hammett ρ value of ca. 1.3 in 50% aqueous DMSO at 25.0 °C. The kinetic solvent isotope and solvent effect and enrichment in 18O-enriched water have been studied. The product composition of the reaction of the monosubstituted compounds gave a ρ value of ca. 0.9. All the evidence indicates a mechanistic pathway which proceeds by a rapid, reversible addition of hydroxide anion to the dione, followed by a benzilic acid-type rearrangement to form a 1-hydroxycyclopropene-1-carboxylic acid. The latter then suffers ring fission to give the final product.

Rate coefficients have been measured for the alkaline hydrolysis of 2-formylbenzonitrile 1, N-(2-formyl and -acetylphenyl)acetamides 2, N-(2-formylphenyl)-3-substituted benzamides 3,4-(2-formylbenzoyl)morpholine 4, 3-(4-morpholino)- and -(N-methylanilino)-phthalides 5 and -naphthalides 6 in 70% (v/v) dioxane–water at various temperatures. The enthalpies and entropies of activation have been evaluated. The hydrolysis of the nitrile is second order in base and that of the amides is first order in base. The relative rates of hydrolysis, activation parameters and substituent effects have been used to suggest the mechanisms of the reactions. Intramolecular catalysis by the neighbouring carbonyl group occurs in the alkaline hydrolysis of 1–4. The alkaline hydrolysis of 5 and 6 is rapid due to their lactone structures.

The rate coefficients for the hydrolysis of p-nitrophenyl acetate catalysed by a series of imidazoles, 4,5-diphenylimidazoles, benzimidazoles and perimidines in 30 mol% aqueous dimethyl sulfoxide at 30.0 °C have been measured, as have the pKa values of the catalysts in the same medium. The effect of a 2-(2-carboxyphenyl) substituent in each system has been studied. The pKa values of the imidazolium and related ions show that the 2-carboxylate group increases their acidity by 1.03 to 1.32 pKa units. The same effect on the nucleophilicity of the corresponding imidazole and related compounds gives rise to rate increases of a factor of 1.4 to 3.2. These effects are related to the structure of the imidazoles, indicating the importance of the environment of carboxylate groups.

Semi-empirical molecular orbital (AM1 and PM3) calculations including solvent effects by the SCRF model on the mechanism of the addition of nucleophiles to unsaturated five- and six-membered bislactones of the Pechmann dye type indicate a similar mechanism for both systems. The rate-determining step appears to be the addition of a second nucleophile to the enol of the ring-opened monolactone. The five-membered lactones are found to be more reactive than their six-membered analogues. Electron donor substituents (p-Me, p-MeO) increase and acceptor substituents (p-Cl, m-NO2) decrease the activation energy.

We review foundational aspects of Kron's Method of Tearing including Roth and Amari's derivation of Tearing using Homology Theory or Algebraic Topology and Bowden's proposal that Huygens' Principle is sufficient to justify the method. Some of the questions asked in [Bowden 1990a] are answered, in particular with respect to the limitations of Huygens' Principle and the relationship between Huygens' Principle and Homology Theory. It is proposed that multilevel, hierarchical system decomposition would be a good approach to Engineering analysis. A time and storage efficient algorithm for the direct solution of hierarchically decomposed linear continuous systems with a topology is described. We make some comments on the optimal level of tearing. It is shown that the approach is valid for any simply or multiply connected discrete system and that information is transmitted between the subsystems by a holographic process. It is this that gives rise to its efficiency. The paradigm proposed is similar to Bohm's hol...

Issues relating to the assessment of people with a learning disability who commit sexual offences are presented. The particular difficulties in working with this client group are highlighted. A core structure for assessment of an individual is provided consisting of background, functional analysis, personal history, knowledge, skills, arousal, cognition's and mental state.

Studies on the title compound have established that, although it could be oxidised with a concomitant change in its visible spectrum, this process is not reversible. This is discussed in the light of the crystal structure which is also reported in this paper. The title compound crystallises in the monoclinic space group P21/n, a= 27.033(6)A, b= 4.988(2)A, c= 5.372(2)A, β= 94.59(2)°. The molecules have close intermolecular contacts along stacks packing in the c direction. The packing is compared to that found in two other Pechmann dyes.

Researchers suggest that people with an intellectual disability (ID) undertake less physical activity than the general population and many rely, to some extent, on others to help them to access activities. The Theory of Planned Behaviour (TPB) model was previously found to significantly predict the intention of care staff to facilitate a healthy diet in those they supported. The present study examined whether the TPB was useful in predicting the intentions of 78 Scottish care staff to support people with ID to engage in physical activity. Regression analyses indicated that perceived behavioural control was the most significant predictor of both care staff intention to facilitate physical activity and reported physical activity levels of the people they supported. Attitudes significantly predicted care staff intention to support physical activity, but this intention was not itself significantly predictive of reported activity levels. Increasing carers’ sense of control over their ability to support clients’ physical activity may be more effective in increasing physical activity than changing their attitudes towards promoting activity.

The equilibrium constants. Ke, for ring–chain tautomerism in a series of substituted benzil-2-carboxylic and 2-phenylacetylbenzoic acids, as well as for the methyl esters of the latter series, have been determined by IR and NMR spectroscopic methods. The observed pKa values, which have been measured for solutions in 80%(w/w) 2-methoxyethanol–water, have been corrected for the tautomeric equilibria to give the true pKa(pKaT). The effects of substitution on both log Ke and pKa, values have been assessed by means of the Hammett equation. The results are discussed.

1,2-Dicarbonyl compounds can undergo base-catalysed reactions in three ways: rearrangement of the benzil–benzilic acid type, fission of the carbon–carbonyl carbon bond and fission of the carbonyl carbon–carbonyl carbon bond. The requirements for the observation of the variant reaction types are discussed both for open-chain and for ring systems in terms of electronic and stereochemical factors. Copyright © 2001 John Wiley & Sons, Ltd.

o-Phthalaldehyde, as well as the α,α′-dideuterio isomer, has been shown to undergo a Cannizzaro reaction in water containing base, while partially hydrated and ionised. The reaction of the monoanion of the hydrate is intramolecular and of the first order in the monoanion of the hydrate, and either first or zero order in the base. The rate coefficients have been measured at several temperatures and activation parameters evaluated. The kinetic isotope effect, kH/kD, for the first and second order processes were found to be ca. 1.9 and 1.8, respectively. The alkaline hydrolysis of the corresponding lactone, phthalide, has also been studied under the same conditions. The evidence for the intramolecular Cannizzaro reaction indicates a mechanistic pathway involving rate-determining hydride transfer from the chain tautomers of both monoanion and dianion of the hydrate.

Rate coefficients for the base-catalysed detritiation of 4,4′,4″-trinitro-,4,4′-dinitro- and 4-nitrotriphenyl-methanes in dimethyl sulphoxide have been measured at 25.0 °C. The bases are a series of secondary aliphatic amines and tetramethylguanidine and of benzoate anions. For 4,4′-dinitrophenylmethane and piperidine, the rate coefficients for detritiation at 55.0 °C and, for α-[2H1]-4,4′-dinitrotriphenylmethane and piperidine, dedeuteriation at 25.0 °C were also measured. The kinetic isotope effect and activation parameters indicate the rate-determining step to be the ionisation process. Bronsted coefficients, β, have been calculated using the known or previously measured pKa values of the conjugate acids of the bases in dimethyl sulphoxide. The β values for both carbon acids are significantly greater for the benzoate anion than for the nitrogen base catalysis, and those for the dinitro-carbon acid are less than those for the trinitro-acid. No reactivity-selectivity relationship exists. This behaviour is discussed in relation to Marcus and related theories.

The rate-coefficients for the alkaline hydrolysis of 3-methyl-5-methylidene- and 3,5-dimethyl-thiazolidine-2,4-diones in water at 25.0 °C have been measured. The reaction of the 5-methylidene substrate is first order in both substrate and hydroxide ion. The reaction of the 5-methyl substrate is two-phase. The first and more rapid reaction of this substrate is 1.4 times faster than the only observed reaction of the former substrate. The second reaction is the hydrolysis of an intermediate, which is first order in substrate and has two components, one first and the other second order in hydroxide ion. The rate coefficients for the addition of a series of thiols to the 5-methylidene substrate in water at pH 7.40 have been measured. A Bronsted coefficient of ca. 0.37 has been found. The detailed reaction pathway and relation to Marcus and related theories are discussed.

The rate coefficients for the alkaline hydrolysis of a series of N-methyl, N-phenyl and bicyclo lactams, penicillins and N-alkyl-N-methylacetamides in water or in aqueous dimethyl sulphoxide have been measured at several temperatures. The reactions were first order in both substrates and base. The reactivities are related to the structures of the substrates, especially N-substitution, ring size and fused ring effects. The reactivities, as well as the activation parameters, kinetic solvent and solvent isotope effects, are used to suggest the detailed mechanisms. All the β-lactams appear to react with rate-determining addition of hydroxide anion; while the N-alkyl γ- and δ-lactams and N-alkyl-N-methylacetamides have rate-determining ring fission of the tetrahedral adduct, assisted by water-catalysis. The reactivity of penicillin in alkaline hydrolysis has been analysed by the studies of model compounds. These show that the increased reactivity of the penicillin β-lactam ring arises from the direct action of the fused ring structure and the acylamino side-chain.

Phenanthrene-4,5-dicarbaldehyde has been shown to form a bridged (cyclic) hydrate in aqueous solution, as a cis–trans mixture. The rate coefficients for the uncatalysed hydration has been measured at two temperatures and the activation parameters evaluated. The dialdehyde, as well as the α,α′-dideuterio isomer, has been shown to undergo a Cannizzaro reaction in 70%(v/v) dioxane-water. The reaction has been shown to be intramolecular and of the second order, i.e. first order in the monoanion of the hydrate and in base. The rate coefficients have been measured at several temperatures and activation parameters evaluated. The kinetic isotope effect, kH/kD, was found to be ca. 1.7 and the kinetic solvent isotope effect, kH2O/kD2O, ca. 0.59. The alkaline hydrolysis of the corresponding lactone of 5-(hydroxymethyl)phenanthrene-4-carboxylic acid was studied under the same conditions. As an intermediate in the intramolecular Cannizzaro reaction, the lactone can be excluded as it cannot be detected directly under conditions where it is relatively long-lived. The evidence for the Cannizzaro reaction indicates a mechanistic pathway involving rate-determining hydride transfer from the chain tautomer of the dianion of the hydrate.

The alkaline hydrolyses of aseriesof substituted (E)-5,5′-diphenylbifuranylidenediones and 3,7-diphenylpyranq[4,3-c]pyran-1,5-diones have been shown to proceed by biphasic pathways. In both cases, a very rapid primary reaction gives hydrolysis of one lactone ring. This is followed by a less rapid secondary reaction giving hydrolysis of the second ring and identical products from both systems. Rate coefficients for the secondary reactions have been measured in 70%(v/v) dioxane–water at 30.0 °C and, for the parent substrates, at 49.0 °C. The enthalpies and entropies of activation have been evaluated. The effects of substitution have been assessed by means of the Hammett equation. Reaction pathways are suggested and the reactivity is related to the ring size.