Structural aspects of semantic-directed clusters

Knowledge-based clusters are studied from the structural point of view. Generalized descriptions for such clusters are stated and illustrated. Peculiarities of certain knowledge-based cluster configurations are highlighted. The adequacy of the connectives logical and (“and”) logical or (“exclusive-or”) in describing such clusters is justified. The definition of “concept” is elaborated from the clustering point of view and used to establish the equivalence between, descriptions of clusters and concepts. The order-independence of semantic-directed clustering approach is established formally based on axiomatic considerations.

Aspects of tautomerism. Part 16. Influence of the y-keto function on the reactions of sulphonic acids

Reaction of sodium 2-formylbenzenesulphonate (1) with thionyl chloride or phosphorous pentachloride gives a mixture of pseudo (2) and normal (3) sulphonyl chlorides. Whereas ammonium 2-carboxybenzenesulphonate (6) gives only the normal sulphonyl chloride (7) on reaction with thionyl chloride, a mixture of normal (7) and pseudo (8) isomers are formed on reaction with phosphorous pentachloride. Sodium 2-benzoylbenzenesulphonate (15), on the other hand, gives the corresponding normal sulphonyl chloride (16) on reaction with both of the reagents mentioned above. Based on these observations it is concluded that γ-keto sulphonic acids are amenable to the influence of γ-carbonyl group as in the case of γ-keto carboxylic acids but to a lesser extent. © 1989 Indian Academy of Sciences.

Synthesis and structural aspects of quasicrystals in Mg-Al-Ag system: Mg4Al6Ag

The existence of an icosahedral phase in Mg−Al−Ag is better understood on a crystallographic basis rather than on a quantum structural diagram basis. The quasicrystalline structure is delineated in terms of quasiperiodic arrangement of Pauling triacontahedra, which can be identified in the equilibrium structure. Subtle differences in the electron diffraction patterns have been recorded compared to the ideal quasicrystalline pattern. The misalignment of spots and distortions are better attributed to higher order rational approximate structure than anisotropic phason strain. Ares of diffuse intensity have been related to the ordering among the atoms in the clusters.

Chemical Aspects of the Synergistic Hypergolic Ignition in Hybrid Systems with N2O4 as Oxidizer

Synergistic hypergolic ignition with nitrogen tetroxide ( N2O4) as oxidizer has been observed in hybrid systems comprising of a mixture of magnesium and Schiff bases as fuels. The ignition delays (IDs) measured using a modified device, have been compared with those of magnesium-Schiff base-WFNA systems under identical conditions. The ID has been found to vary with the nature of the substitution in both the benzene rings. A linear relationship emerges when the ignition delays are plotted against the Hammett substitution constants (σ). The preignition products of the reaction of N2O4 with magnesium and benzylidineaniline have been analysed to be Mg(NO3)2, benzenediazonium salt and benzaldehyde. Based on the preignition products isolated, a probable reaction mechanism has been proposed. The previously proposed preignition mechanism for the Schiff base-magnesium-WFNA system has been further supported from the present ignition delay data.

Structural aspects of high-temperature cuprate superconductors

High-temperature superconductivity constitutes the most sensational discovery of recent times. Since these new superconductors are complex metal oxides, chemistry has had a big role to play in the investigations. For the first time, stoichiometry, structure, bonding, and such chemical factors have formed central themes in superconductivity, an area traditionally dominated by physicists. These oxide superconductors have given a big boost to solid-state chemistry.

A study of geotechnical properties of Cochin Marine Clays

Most of the Greater Cochin area, which is undergoing rapid industrialisation, consists of extremely soft marine clay calling for expensive deep foundations. This paper presents a study on the physical properties and engeering characteristics of Cochin marine clays. These marine clays are characterised by high Atterberg limits and natural water contents. They are moderately sensitive with liquidity indices ranging over 0.46 to 0.87.The grain size distribution shows almost equal fractions of clay and silt size with sand content varying around 20%. Use of a dispersing agent in carrying out grain size distribution test plays an important role. The fabric of these clays had been identified as flocculant. The pore water has low salinity which results in marginal changes in properties on washing.Consolidation test results showed a preconsolidation pressure of up to about 0.5 kg/cm2 with high compression indices. Compression index vs liquid limit yielded a correlation comparable to that of published data. The undisturbed samples have a much larger coefficient of secondary consolidation as a result of flocculant fabric. These clays have very low undrained shear strength.

Only Connect?: Aspects of Intertextuality in Zadie Smith's On Beauty

Tutkielma käsittelee intertekstuaalisuuden eri muotoja Zadie Smithin romaanissa On Beauty (suom. Kauneudesta). Tutkimuksen tarkoitus on osoittaa kuinka oleellisesti intertekstuaalisuuden teoria on vaikuttanut kirjallisuustieteen metodeihin ja postmoderniin kirjallisuuskäsitykseen, sekä käsitellä sen soveltuvuutta nykykirjallisuuden tutkimiseen analysoimalla teorian sisäistä monimuotoisuutta ja ristiriitoja. Tutkimusmateriaalina käytetään Smithin romaanin lisäksi E. M. Forsterin romaania Howards End (suom. Talo jalavan varjossa), johon On Beauty tietoisesti viittaa. Teoreettisena viitekehyksenä tutkielmassa toimii Gérard Genetten teoksessa Palimpsests sekä Roland Barthesin esseessä Tekijän kuolema esille tuodut kirjallisuusteoreettiset käsitykset. Valittu metodologia antaa mahdollisuuden hahmottaa intertekstuaalisuus kahdella eri tavalla: Genetten strukturalistinen lähestymistapa soveltuu teosten välisten viittaussuhteiden tutkimiseen, kun taas Barthesin jälkistrukturalistinen diskurssi auttaa ymmärtämään tekstienvälisyyden osana merkityksen jatkuvaa epävakautta. Tutkielman ensimmäinen osio keskittyy analysoimaan lähiluvun keinoin romaanien On Beauty ja Howards End välistä strukturalistista suhdetta vertailemalla teosten eroja ja yhtäläisyyksiä Genetten intertekstuaalisuusteorian valossa. Vertailussa kiinnetetään erityisesti huomiota teosten juoneen, rakenteeseen, aikaan ja paikkaan, sekä uudelleenkirjoitusten yleiseen tendenssiin päivittää alkuperäistä tarinaa kohdeyleisölle paremmin sopivaksi. Toisessa osiossa tutkimusta esille nousee jälkistrukturalistinen näkemys intertekstuaalisuudesta osana lukijan tuottaman merkityksen tulkinnanvaraisuutta. Osiossa käsitellään Rembrandtin taideteosten roolia Smithin romaanissa ja analysoidaan hahmojen tulkintoja sekä suhtautumista Rembrandtin tuotantoon Barthesin teoreettisten käsitteiden kautta. Keskeiseksi analyysin kohteeksi nousee lukija sekä lukijan tuottamat tulkinnat ja niiden merkitys Smithin romaanin tematiikassa. Tutkielmassa osoitetaan kuinka intertekstuaalisuus ei ole niin yksinkertainen termi kuin sen laaja käyttö niin kirjallisuustieteessä kuin mediassakin antaa ymmärtää, sekä selvitetään intertekstuaalisuuden teorian kehitystä 60-luvulta nykypäivään. Vaikka strukturalistisessa muodossa käsite soveltuu etenkin kahden toisiinsa kytkeytyneen teoksen tutkimiseen, vertaileva analyysi kuitenkin osoittaa, että On Beauty ei ole pelkkä uudelleenkirjoitus, vaan romaanin tulkintaan tarvitaan myös jälkistrukturalistisen dekonstruktion käsitteitä, jotta laajemmat tekstuaalisuuden verkostot aukeavat lukijalle. Romaanissa esiintyvä taitelijakuva myös osoittaa, että Smith itse on hyvin tietoinen kirjallisuusteoreettisesta keskustelusta.

Dental identification and aspects of medico-legal investigations of the Finnish victims of the Sumatra-Andaman earthquake on 26 December 2004

Tsunami waves of the Sumatra-Andaman earthquake on 26 December 2004 claimed approximately 230 000 lives and started the biggest identification operation in Interpol's history. The aim of this study was to resolve methods of the identification and results received. The viewpoint is mainly that of forensic odontology, but also includes other means of identification and results of the medico-legal examination performed in Finland. Of the 5395 victims in Thailand, approximately 2 400 were foreigners from 36 nations including 177 Finnish nationals. Additionally, a Finnish woman perished in Sri Lanka and a severely injured man after the evacuation in a hospital. The final numbers of missing persons and dead bodies registered in the Information Management Centre in Phuket,Thailand, were 3 574 ante-mortem (AM) and 3 681 post-mortem (PM) files. The number of identifications by December 2006 was 3 271 or 89% of the victims registered. Of Finnish victims, 172 have been identified in Thailand and 163 repatriated to Finland. One adult and four children are still missing. For AM data, a list of Finnish missing persons including 178 names was published on 30 December 2004. By February 2005 all useful dental AM data were available. Five persons on the list living in Finland lacked records. Based on the AM database, for the children under age 18 years (n=60) dental identification could be established for 12 (20%). The estimated number for adults (n=112) was 96 (86%). The final identification rate, based on PM examinations in Finland, was 14 (25%) for children (n= 56) and 98 (90%) for adults (n= 109). The number of Finnish victims identified by dental methods, 112 (68%), was high compared to all examined in Thailand (43%). DNA was applied for 26 Finnish children and for 6 adults, fingerprints for 24 and 7, respectively. In 12 cases two methods were applied. Every victim (n=165) underwent in Finland a medico-legal investigation including an autopsy with sampling specimens for DNA, the toxicological and histological investigation. Digital radiographs and computed tomography were taken of the whole body to verify autopsy findings and bring out changes caused by trauma, autolysis, and sampling for DNA in Thailand. Data for identification purposes were also noted. Submersion was the cause of death for 101 of 109 adults (92.7%), and trauma for 8 (7.3%). Injuries were 33 times contributing factors for submersion and 3 times for trauma-based death. Submersion was the cause of death for 51 (92.7%) children and trauma for 4 (7.3%). Injuries were in 3 cases contributing factors in submersion and once in trauma-based death. The success of the dental identification of Finnish victims is mainly based on careful registration of dental records, and on an education program from 1999 in forensic odontology.

Dietary aspects of cow's milk allergy in young children

Cow s milk allergy (CMA) affects about 2-6% of infants and young children. Environmental factors during early life are suggested to play a role in the development of allergic diseases. One of these factors is likely to be maternal diet during pregnancy and lactation. The association between maternal diet and development of CMA in offspring is not well known, but diet could contain factors that facilitate development of tolerance. After an established food allergy, another issue is gaining tolerance towards an antigen that causes symptoms. The strictness of the elimination depends on the individual level of tolerance. This study aimed at validating a questionnaire used to inquire about food allergies in children, at researching associations between maternal diet during pregnancy and lactation and subsequent development of cow s milk allergy in the offspring, and at evaluating the degree of adherence to a therapeutic elimination diet of children with CMA and factors associated with the adherence and age of recovery. These research questions were addressed in a prospective birth cohort born between 1997 and 2004 at the Tampere and Oulu University Hospitals. Altogether 6753 children of the Diabetes Prediction and Prevention (DIPP) Nutrition cohort were investigated. Questionnaires regarding allergic diseases are often used in studies without validation. High-quality valid tools are therefore needed. Two validation studies were conducted here: one by comparing parentally reported food allergies with information gathered from patient records of 1122 children, and the other one by comparing parentally reported CMA with information in the reimbursement records of special infant formulae in the registers of the Social Insurance Institution for 6753 children. Both of these studies showed that the questionnaire works well and is a valid tool for measuring food allergies in children. In the first validation study, Cohen s kappa values were within 0.71-0.88 for CMA, 0.74-0.82 for cereal allergy, and 0.66-0.86 for any reported food allergy. In the second validation study, the kappa value was 0.79, sensitivity 0.958, and specificity 0.965 for reported and diagnosed CMA. To investigate the associations between maternal diet during pregnancy and lactation and CMA in offspring, 6288 children were studied. Maternal diet during pregnancy (8th month) and lactation (3rd month) was assessed by a validated, 181-item semi-quantitative food frequency questionnaire (FFQ), and as an endpoint register-based information on diagnosed CMA was obtained from the Social Insurance Institution and complemented with parental reports of CMA in their children. The associations between maternal food consumption and CMA in offspring were analyzed by logistic regression comparing the highest and lowest quarters with two middle quarters of consumption and adjusted for several potential confounding factors. High maternal intake of milk products (OR 0.56, 95% CI 0.37-0.86 p = 0.002) was associated with a lower risk of CMA in offspring. When stratified according to maternal allergic rhinitis or asthma, a protective association of high use of milk products with CMA was seen in children of allergy-free mothers (OR 0.30, 95% CI 0.13 - 0.69, p < 0.001), but not in children of allergic mothers. Moreover, low maternal consumption of fish during pregnancy was associated with a higher risk of CMA in children of mothers with allergic rhinitis or asthma (OR 1.47, 95% CI 0.96 - 2.27 for the lowest quarter, p = 0.043). In children of nonallergic mothers, this association was not seen. Maternal diet during lactation was not associated with CMA in offspring, apart from an inverse association between citrus and kiwi fruit consumption and CMA. These results imply that maternal diet during pregnancy may contain factors protective against CMA in offspring, more so than maternal diet during lactation. These results need to be confirmed in other studies before giving recommendations to the public. To evaluate the degree of adherence to a therapeutic elimination diet in children with diagnosed CMA, food records of 267 children were studied. Subsequent food records were examined to assess the age at reintroduction of milk products to the child s diet. Nine of ten families adhered to the elimination diet of the child with extreme accuracy. Older and monosensitized children had more often small amounts of cow s milk protein in their diet (p < 0.001 for both). Adherence to the diet was not related to any other sociodemographic factor studied or to the age at reintroduction of milk products to the diet. Low intakes of vitamin D, calcium, and riboflavin are of concern in children following a cow s milk-free diet. In summary, we found that the questionnaires used in the DIPP study are valid in investigating CMA in young children; that there are associations between maternal diet during pregnancy and lactation and the development of CMA in offspring; and that the therapeutic elimination diet in children with diagnosed CMA is rigorously adhered to.

Aspects of tautomerism. 7. Study of keto participation in alkaline hydrolysis of normal esters of .gamma.-keto acids

Study of the alkaline hydrolysis of a number of variously substituted normal o-benzoylbenzoic esters has been reported. Although carbonyl-assisted hydrolysis is the general rule, in compounds containing strongly electron-donating groups, the ester function is directly attacked. The cause of rate enhancement in carbonyl-assisted hydrolysis and in greater detail the case of 6-substituted derivatives are discussed. It is shown that the carbonyl-assisted hydrolyses are characterized by decreased sensitivity to leaving-group structure. The implications of this result are pointed out.

Mechanistic Aspects of Nucleophilic Substitution at Half-Sandwich Metal Complexes

The hydrolysis reactions of organometallic ruthenium(II) piano-stool complexes of the type Ru-II(eta(6)-cymene)(L)Cl](0/+) (1-5, where L = kappa(1)- or kappa(2)-1,1-bis(diphenylphosphino)methane,1,1bis-(diphenylphosphino)methane oxide, kappa(1)-mercaptobenzothiazole) have been studied using density functional theory at the B3LYP level. In addition to considering a syn attack in an associative fashion, where the nucleophile approaches from the same side as the leaving group, we have explored alternative paths such as an anti attack in an associative manner, where the nucleophile attacks from the opposite side of the leaving group. During the anti attack, an intermediate is formed and there is a coordination mode change of the arene ring from eta(6) to eta(2) along with its rotation. When the intermediate goes to the product, the arene ring slips back from eta(2) to eta(6) coordination. This coordinated movement of the arene ring makes the associative anti attack an accessible pathway for the substitution process. Our calculations predict very similar activation barriers for both syn and anti attacks. In the dissociative path, the rate-determining step is the generation of a coordinatively unsaturated 16-electron ruthenium species. This turns out to be viable once solvent effects are included. The large size of the ancillary ligands on Ru makes the dissociative process as favorable as the associative process. Activation energy calculations reveal that although the dissociative path is favorable for kappa(1) complexes, both dissociative and associative processes can have significant contribution to the hydrolysis reaction in kappa(2) complexes. Once activated by hydrolysis, these complexes react with guanine and adenine bases of DNA. The thermodynamic stabilities of complexes formed with the nucleobases are also presented.