Dinámica de reacciones unimoleculares en fase gas: Desviaciones del comportamiento estadístico

The present review summarizes the most relevant results of our research group obtained recently in the field of unimolecular reaction dynamics. The following processes are specifically analyzed: the isomerization, dissociation and elimination in methyl nitrite, the fragmentation reactions of the mercaptomethyl cation, the C-CO dissociation in the acetyl and propionyl radicals, and the decomposition of vinyl fluoride. In all the cases, only state- or energy-selected systems are considered. Special emphasis is paid to the possibility of systems exhibiting non-statistical behavior.

Nano vitrocerâmica de escória de aciaria

The manufacture of glass-ceramics is an alternative route for the commercial use of metallurgical slags. Such types of glass-ceramics may find commercial applications owing to their low cost, good mechanical properties and superior visual aspect. Besides, due to the elimination of that industrial residue from the environment and also due to the possibility of replacement of natural stones such as marbles and granites, the use of slags is an activity with strong ecological appeal. While the use of blast-furnace slags for the production of glass-ceramics is well known, the utilization of steel making slags constitutes a challenge, because these materials possess low concentration of SiO2. In this work a novel composition for producing glasses and glass-ceramics from a steelmaking slag is presented. The crystal nucleation kinetics, the characterization of the resulting microstructures for two different thermal treatments and mechanical properties of the glass-ceramics are discussed. A glass-ceramic having a marble aspect, fine volumetric crystallization, high degree of crystallization and improved mechanical strength was obtained.

Gas-phase ion chemistry of silyl cations obtained from hexamethyldisilazane

The gas-phase ion-molecule reactions of the Me3SiN(H)SiMe2+ ion, obtained by electron ionization from Me3SiN(H)SiMe3, have been studied in a Fourier transform ion cyclotron resonance spectrometer in order to understand the mechanistic details of an important chemical system presently used in film formation. This silyl cation has been observed to undergo addition reactions at electron rich centers to form stable adducts that may undergo further methane elimination in the case of alcohols and amines. The most important feature of these reactions is the fact that a metathesis type reaction can be observed in the presence of H2O, and other hydrogen labile substrates like alcohols, leading to the formation of the corresponding oxygen-containing ion, i.e. Me3SiOSiMe2+. For alcohols (ROH), facile formation of a tertiary product ion, presumably corresponding to an Me3Si-O-Si(Me)=O+-R structure with elimination of an amine reveals the strong tendency of these nitrogen-containing ions to undergo metathesis type reactions with oxygen containing substrates.

Perustutkimus palveluinnovaatioprosessissa rahoitusalalla

Palveluinnovaatioprosessi voidaan jakaa 5 eri vaiheeseen: strategiasidonnaisuus, perustutkimus, suorituskyvyn analysointi, systeemimuutokset sekä kaupallistaminen. Tästä palveluinnovaatioprosessista voidaan johtaa perustutkimusprosessi rahoitusalalle: strategiasidonnaisuus, ideoiden luonti ja karsinta, suorituskyvyn analysointi, differointimahdollisuuksien kartoittaminen ja palveluinnovaation myynti yritysjohdolle sekä osakkaille. Strategiasidonnaisuudella varmistetaan, että yritys pysyy omalla osaamisalueellansa hyödyntämällä omia ydinkompetenssejaan. Perustutkimus osana palveluinnovaatioprosessia selvittää oleellisimmat tiedot markkinatilanteesta sekä toimii ohjaavana että karsivana tekijänä uuden tuotteen jatkotoimenpiteille. Yrityksen kyvykkyyksien mittaaminen perustutkimusta varten on oleellinen vaihe uuden palvelun vaatimien liiketoiminnallisten muutosten määrittämiseksi. Tuotedifferoinnilla voidaan luoda kilpailullista etua tuotteiden puolesta homogeenisilla markkinoilla, joissa kilpailu tapahtuu pääosin hinnoittelussa. Rahoitusalalla tuotedifferointi voi muodostua haastavaksi kuluttajien suhtautuessa konservatiivisesti uusiin tuotteisiin. Makroekonomisten tekijöiden perusteella voidaan päätellä, että suomalaiset kuluttajat ottavat lainaa tulevaisuudessakin. Asuntolaina on ollut lainamarkkinoilla luottokannan kasvun veturina ja tästä syystä uudet asuntolainan kaltaiset tuotteet voisivat olla menestyksekkäitä. Kilpailu asuntolainamarkkinoilla kulminoituu kolmen hallitsevan kilpailijan ympärille: Osuuspankki, Sampo Pankki ja Nordea. Asuntolainan kaltainen käänteinen asuntolaina voisi olla menestys markkinoilla, jos sitä pystyttäisiin differoimaan kylliksi. Markkinapotentiaali pelkälle käänteiselle asuntolainalle on tällä hetkellä liian alhainen. GE Money Finland ei myöskään pysty tarjoamaan tuotetta yhtä kilpailulliseen hintaan kuin kilpailijansa. GE Money Finlandin tulisi edellä mainituista syistä johtuen pyrkiä differoimaan käänteisen asuntolainan kaltaista tuotettaan Heloc, jotta se menestyisi markkinoilla.

Dependência das vias de dissociação unimolecular com a energia interna da molécula de éter dimetílico

Internal energy dependence of the competitive unimolecular dissociation channels of dimethyl ether were studied with the statistical RRKM formalism. The C-O and C-H fission reactions and the 1,2-H and 1,3-H shifts, and 1,1-H2 and 1,3-H2 molecular eliminations are discussed as a function of energy dependence of k a(E*), the microcanonical rate constant for production of transition states. C-O fission is the dominant process while reaction channels involving C-H fission, 1,1-H2 and 1,3-H2 elimination and production of MeOH should be competitive at energies around 400 kJ mol-1. The less favorable process is the channel of CH4 formation.

O uso do forno de microondas na síntese orgânica em fase sólida

Solid-phase organic synthesis (SPOS) has been considered the main strategy for the construction of combinatorial libraries, because its simplicity leads to faster synthetic procedures. In addition to that, a series of reports in the specialized literature show great advantages in the use of microwave activation, when compared to classical heating, for instance: shorter reaction times, in some cases from several hours to a few minutes, increase of selectivity and product yields, energy economy and reduction and/or elimination of solvent. This review describes the use of microwave ovens/reactors in solid phase organic synthesis, describing the advantages, equipment and reactions using both techniques.

Automated flow-injection method for cadmium determination with pre-concentration and reagent preparation on-line

The spectrophotometric determination of Cd(II) using a flow injection system provided with a solid-phase reactor for cadmium preconcentration and on-line reagent preparation, is described. It is based on the formation of a dithizone-Cd complex in basic medium. The calibration curve is linear between 6 and 300 µg L-1 Cd(II), with a detection limit of 5.4 µg L-1, an RSD of 3.7% (10 replicates in duplicate) and a sample frequency of 11.4 h-1. The proposed method was satisfactorily applied to the determination of Cd(II) in surface, well and drinking waters.

Effect of Seasonal Dynamics on Queen Densities of the Argentine Ant (Linepithema Humile) in an Invaded Natural Area of the NE Iberian Peninsula

The annual elimination of large numbers of Argentine ant queens near the advance front of an invasion could be a useful tool for weakening the species’ dispersion and, therefore, limiting its establishment in non-invaded areas. However, before carrying out trials to test the effectiveness of this method it would be essential to have sufficient knowledge of the effect of seasonal dynamics acting on the queens’ densities of the species in order to determine the most favourable period of the year to act. We analyzed the seasonal densities and nest dynamics of Argentine ant queens in an invaded Mediterranean natural ecosystem. We observed that the queens’ density varied depending on the season of the year and that this variation was mainly due to the seasonal dynamics of nest aggregations in winter and ant dispersions in summer. The greatest densities per litre of nest soil were observed in winter (December to March, approximately) and the lowest densities were observed in summer ( June to July). This information is essential for improving current knowledge of the Argentine ant’s biology and developing control methods based on the elimination of queens in invaded natural areas

Fotoquímica de alfa,alfa-dimetilvalerofenona adsorvida em celulose microcristalina

Irradiation of a,a-dimethylvalerophenone (1) adsorbed on microcrystalline cellulose employing methanol as the solvent shows a Norrish Type II/Type I ratio of 1.0±0.1. In solution, values of 2.3±0.3 in benzene and 8.7±2.0 in terc-butanol were obtained. The cyclization/elimination ratio for the Norrish Type II reaction of 1 shows values of 1.2±0.3 in cellulose, 17.9±2.7 in benzene and 3.2±03 in terc-butanol. When samples of 1/microcrystalline cellulose were prepared employing n-hexane, the Type II/Type I (29.5±2.9) and the cycl/elim (113.3±12.1) ratios were dramatically modified. These results demonstrate the difference in the behavior of 1 when entrapped in the cellulose chains or adsorbed on the cellulose surface.

Eliminating Software Failures - A Literature Survey

Software faults are expensive and cause serious damage, particularly if discovered late or not at all. Some software faults tend to be hidden. One goal of the thesis is to figure out the status quo in the field of software fault elimination since there are no recent surveys of the whole area. Basis for a structural framework is proposed for this unstructured field, paying attention to compatibility and how to find studies. Bug elimination means are surveyed, including bug knowhow, defect prevention and prediction, analysis, testing, and fault tolerance. The most common research issues for each area are identified and discussed, along with issues that do not get enough attention. Recommendations are presented for software developers, researchers, and teachers. Only the main lines of research are figured out. The main emphasis is on technical aspects. The survey was done by performing searches in IEEE, ACM, Elsevier, and Inspect databases. In addition, a systematic search was done for a few well-known related journals from recent time intervals. Some other journals, some conference proceedings and a few books, reports, and Internet articles have been investigated, too. The following problems were found and solutions for them discussed. Quality assurance is testing only is a common misunderstanding, and many checks are done and some methods applied only in the late testing phase. Many types of static review are almost forgotten even though they reveal faults that are hard to be detected by other means. Other forgotten areas are knowledge of bugs, knowing continuously repeated bugs, and lightweight means to increase reliability. Compatibility between studies is not always good, which also makes documents harder to understand. Some means, methods, and problems are considered method- or domain-specific when they are not. The field lacks cross-field research.

Uma proposta para o ensino da Química Analítica Qualitativa

In recent years, because of the need for a more flexible curriculum established by the Curriculum Guidelines of the National Brazilian Education (law 9394/96), the pedagogical project of the Chemistry course of FFCLRP/USP has undergone alterations, amongst them the gradual reduction of the hours devoted to the discipline Qualitative Analytical Chemistry. In this context, this discipline has been carefully analyzed and reorganized in order to allow the elimination of redundancies and the introduction of activities considered important for the professional formation of both chemists and chemistry teachers. In this work, we will discuss the main strategies adopted in this reorganization with the objective of making the teaching/learning process more dynamic and efficient.

Blocking and unblocking in a navigation task

Rodrigo, Chamizo, McLaren, & Mackintosh (1997) demonstrated the blocking effect in a navigational task using a swimming pool: rats initially trained to use three landmarks (ABC) to find an invisible platform learned less about a fourth landmark (X) added later than did rats trained from the outset with these four landmarks (ABCX). The aim of the experiment reported here was to demonstrate unblocking using a similar procedure as in the previous work. Three groups of rats were initially trained to find an invisible platfom in the presence of three landmarks: ABC for the Blocking and Unblocking groups and LMN for the Control group. Then, all animals were trained to find the platform in the presence of four landmarks, ABCX. In this second training, unlike animals in the Blocking group to which only a new landmark (X) was added in comparison to the first training, the animals in the Unblocking group also had a change in the platform position. In the Control group, both the four landmarks and the platform position were totally new at the beginning of this second training. As in Rodrigo et al. (1997) a blocking effect was found: rats in the Blocking group learned less with respect to the added landmark (X) than did animals in the Control group. However, rats in the Unblocking group learned about the added landmark (X) as well as did animals in the Control group. The results are interpreted as an unblocking effect due to a change in the platform position between the two phases of training, similarly to what is normal in classical conditioning experiments, in which a change in the conditions of reinforcement between the two training phases of a blocking design produce an attenuation or elimination of this effect. These results are explained within an error-correcting connectionist account of spatial navigation (McLaren, 2002).

Importância do metabolismo no planejamento de fármacos

It is widely recognized that pharmacokinetic optimization needs to be addressed early in drug discovery to reduce the high failure rate in bringing drugs to market. Poor absorption, too short duration of action due to high elimination rate, or the presence of active metabolites are examples of properties that can potentially lead to unsuccessful clinical programmes. Here I describe a brief overview of advantages and molecular strategies for improving metabolic and pharmacokinetic properties applied to the discovery of fluconazol, beta-blockers, ritonavir and ezetimibe and to the development of the prodrugs enalapril and bambuterol.

IAS 39 -standardin mukainen suojauslaskenta ja rahavirran suojaus suomalaisissa pörssiyhtiöissä

Tutkielman tavoitteena oli tutkia IAS 39 -standardin mukaista suojauslaskentaa ja rahavirran suojauksen soveltamista neljässä suomalaisessa pörssiyhtiössä kolmelta eri toimialalta. Tutkielman perusteella suojauslaskennan soveltamisessa ei havaittu suuria eroavaisuuksia eri toimialojen yhtiöiden välillä. Tutkielmassa päädyttiin johtopäätökseen, että suojauslaskennan soveltamiseen vaikuttaa enemminkin yhtiön liikevaihdon suuruus ja liiketoiminnan laajuus kuin esimerkiksi toimialan luonne. Suojauslaskennan mahdollistama tuloksen volatiliteetin tasaaminen on ensisijainen ja suurin hyöty. Tuloksiin kohdistunut huomio on nykypäivänä kasvanut, ja myös sen vuoksi tuloksen muutosten eliminointi ja suojauslaskenta on yhtiöiden mukaan tärkeää. Soveltamista harkittaessa prosessia tarkastellaan monesta eri näkökulmasta. Nykyisellä taloustilanteella on ollut vaikutuksia yhtiöiden liiketoimintaan ja suojauksiin, mutta suojauslaskentaan vain välillisesti.

Sistemes logístics de codificació i identificació, i perspectives de futur

Comptar amb sistemes sofisticats de gestió o programes ERP (Enterprise Resource Planning) no és suficient per a les organitzacions. Per a què aquests recursos donin resultats adequats i actualitzats, la informació d’entrada ha de llegir-se de forma automàtica, per aconseguir estalviar en recursos, eliminació d’errors i assegurar el compliment de la qualitat. Per aquest motiu és important comptar amb eines i serveis d’identificació automàtica i col•lecció de dades. Els principals objectius a assolir (a partir de la introducció al lector de la importància dels sistemes logístics d’identificació en un entorn global d’alta competitivitat), són conèixer i comprendre el funcionament de les tres principals tecnologies existents al mercat (codis de barres lineals, codis de barres bidimensionals i sistemes RFID), veure en quin estat d’implantació es troba cadascuna i les seves principals aplicacions. Un cop realitzat aquest primer estudi es pretén comparar les tres tecnologies per o poder obtenir perspectives de futur en l’àmbit de l’autoidentificació. A partir de la situació actual i de les necessitats de les empreses, juntament amb el meravellós món que sembla obrir la tecnologia RFID (Radio Frequency Identification), la principal conclusió a la que s’arribarà és que malgrat les limitacions tècniques dels codis de barres lineals, aquests es troben completament integrats a tota la cadena logística gràcies a l’estandarització i la utilització d’un llenguatge comú, sota el nom de simbologies GTIN (Global Trade Item Number), durant tota la cadena de subministres que garanteixen total traçabilitat dels productes gràcies en part a la gestió de les bases de dades i del flux d’informació. La tecnologia RFUD amb l’EPC (Electronic Product Code) supera aquestes limitacions, convertint-se en el màxim candidat per a substituir els limitats codis de barres. Tot i això, RFID, amb l’EPC, no serà un adequat identificador logístic fins que es superin importants barreres, com són la falta d’estandarització i l’elevat cost d’implantació.