Pitkäketjuisten keteenien valmistusreaktiot ja kinetiikka.

Tämän diplomityön tarkoituksena oli tutkia pitkäketjuisten rasvahappokloridien ja alkyyliketeenidimeerien (AKD) valmistusreaktioiden kinetiikkaa. Työn tavoitteena oli saada mittaustuloksia, joiden perusteella voitaisiin kehittää reaktioille kineettinen kineettinen malli ja suorittaa valmistusprosessien alustava optimointi. Teoreettisessa osassa on selvitetty rasvahappokloridien ja alkyyliketeenidimeerien (AKD) eri valmistustapoja. Lisäksi on perehdytty tarkemmin rasvahappokloridien dehydrohalogenointireaktioiden reaktiomekanismeihin ja valmistusprosessin problematiikkaan. Kokeellisessa osassa tutkittiin rasvahappokloridien valmistusta klooraamalla öljyhappoa 30 mol-% fosforitrikloridiylimäärällä lämpötiloissa 45, 50 ja 55OC. Alkyyliketeenidimeerien valmistusta tutkittiin dehydrohalogenoimalla palmitiini- ja öljyhappokloridia 0-30 mol-% trietyyliamiiniylimäärällä inertissä liuottimessa, lämpötiloissa 45 ja 50OC. Reaktiot toteutettiin puolipanosreaktiona, joissa reaktioastiassa olevaan reagenssin ja liuottimen seokseen lisättiin lähtöaine tasaisena massavirtana. Reaktioiden etenemistä seurattiin FT-IR- ja GC-analyysien avulla. Kalorimetrisilla kokeilla tutkittiin öljyhappokloridin dimeroitumisreaktion reaktiolämmön muodostumista ja UV-VIS-analyyseillä seurattiin öljyhappokloridin vanhenemista. Öljyhappokloridin valmistusreaktiolle saatiin hyvä kineettinen malli. Kineettisen mallin puutteena voidaan pitää sitä, ettei kokeissa saatu tietoa mahdollisten sivutuotteiden muodostumisesta. Sovitusohjelmalla saatiin sovitettua estimaatit reaktionopeusvakioille lämpötiloissa 45, 50 ja 55OC. Happokloridien dimeroitumisreaktioiden kineettisen mallin sopivuudelle saatiin suhteellisen hyvä kuva Kuten öljyhappokloridin tapauksessa, myöskään AKD:n valmistusreaktioissa syntynyt sivutuotteita, joten niiden osuutta oletettuun kineettiseen malliin ei tunneta. Sovitusohjelmalla saatiin sovitettua estimaatit reaktionopeusvakioille lämpötiloissa 45 ja 50OC.

Automatic Segmentation of the Eye in 3D Magnetic Resonance Imaging: A Novel Statistical Shape Model for Treatment Planning of Retinoblastoma.

PURPOSE: Proper delineation of ocular anatomy in 3-dimensional (3D) imaging is a big challenge, particularly when developing treatment plans for ocular diseases. Magnetic resonance imaging (MRI) is presently used in clinical practice for diagnosis confirmation and treatment planning for treatment of retinoblastoma in infants, where it serves as a source of information, complementary to the fundus or ultrasonographic imaging. Here we present a framework to fully automatically segment the eye anatomy for MRI based on 3D active shape models (ASM), and we validate the results and present a proof of concept to automatically segment pathological eyes. METHODS AND MATERIALS: Manual and automatic segmentation were performed in 24 images of healthy children's eyes (3.29 ± 2.15 years of age). Imaging was performed using a 3-T MRI scanner. The ASM consists of the lens, the vitreous humor, the sclera, and the cornea. The model was fitted by first automatically detecting the position of the eye center, the lens, and the optic nerve, and then aligning the model and fitting it to the patient. We validated our segmentation method by using a leave-one-out cross-validation. The segmentation results were evaluated by measuring the overlap, using the Dice similarity coefficient (DSC) and the mean distance error. RESULTS: We obtained a DSC of 94.90 ± 2.12% for the sclera and the cornea, 94.72 ± 1.89% for the vitreous humor, and 85.16 ± 4.91% for the lens. The mean distance error was 0.26 ± 0.09 mm. The entire process took 14 seconds on average per eye. CONCLUSION: We provide a reliable and accurate tool that enables clinicians to automatically segment the sclera, the cornea, the vitreous humor, and the lens, using MRI. We additionally present a proof of concept for fully automatically segmenting eye pathology. This tool reduces the time needed for eye shape delineation and thus can help clinicians when planning eye treatment and confirming the extent of the tumor.

Influence of heart motion on cardiac output estimation by means of electrical impedance tomography: a case study.

Electrical impedance tomography (EIT) is a non-invasive imaging technique that can measure cardiac-related intra-thoracic impedance changes. EIT-based cardiac output estimation relies on the assumption that the amplitude of the impedance change in the ventricular region is representative of stroke volume (SV). However, other factors such as heart motion can significantly affect this ventricular impedance change. In the present case study, a magnetic resonance imaging-based dynamic bio-impedance model fitting the morphology of a single male subject was built. Simulations were performed to evaluate the contribution of heart motion and its influence on EIT-based SV estimation. Myocardial deformation was found to be the main contributor to the ventricular impedance change (56%). However, motion-induced impedance changes showed a strong correlation (r = 0.978) with left ventricular volume. We explained this by the quasi-incompressibility of blood and myocardium. As a result, EIT achieved excellent accuracy in estimating a wide range of simulated SV values (error distribution of 0.57 ± 2.19 ml (1.02 ± 2.62%) and correlation of r = 0.996 after a two-point calibration was applied to convert impedance values to millilitres). As the model was based on one single subject, the strong correlation found between motion-induced changes and ventricular volume remains to be verified in larger datasets.

Ympäristöjärjestelmien kehittäminen rakennustuotealan yrityksen Keski-Euroopan toimipaikoissa

Tämän diplomityön tavoitteena oli antaa kehittämisehdotuksia, joilla voidaan parantaa rakennustuotealan yrityksen ympäristöjärjestelmien kustannustehokkuutta sekä ympäristöpolitiikkaan liittyvän jatkuvan parantamisen yhtenäistä toteutumista eri toimipaikoilla. Lähtökohtana olivat havainnot siitä, että melko pienissä toimipaikoissa laatu- ja ympäristöasiat kattavan toimintajärjestelmän rakentaminen ja ylläpitäminen vie paljon resursseja. Lisäksi selvitettiin uuden ISO 14001-standardiehdotuksen mahdollisia vaikutuksia käytössä oleviin ympäristöjärjestelmiin. Tutkimusmenetelminä käytettiin eri sertifiointielimille tehtyä haastattelua, toimipaikkojen ympäristövastaaville lähetettyä kyselyä, verkkosivuille kohdistettua kilpailijaseurantaa sekä selvitystä uuden ISO 14001- standardiehdotuksen muutoksista. Eri toimipaikkojen ympäristöjärjestelmien yhdistäminen saman sertifikaatin alle oli kaikkien sertifiointielinten edustajien mielestä hyvä tapa vähentää järjestelmien ulkoisesta valvonnasta aiheutuvia kustannuksia ja parantaa järjestelmien tehokkuutta. Ulkoisten kustannusten aleneminen on noin yksikolmasosa, joka syntyy ensinnäkin sertifikaattimaksujen alenemista ja toisaalta sertifiointipäivien vähenemisestä. Sertifikaattimaksut alenevat, koska yhdistetyssä järjestelmässä sertifikaatteja on vähemmän, ja sertifiointipäivien määrä vähenee, koska yhdistetyn järjestelmän ulkoisessa valvonnassa käytetään otanta -periaatetta. Kilpailijaseurannan osalta havaittiin, että yrityksen verkkosivuilla kerrottiin kilpailijoita paremmin ympäristö- sekä laatujärjestelmistä. Kehitettävää on eri maiden verkkosivujen yhtenäisyydessä ja ympäristö- ja laatupolitiikan esittämisessä. Nämä politiikat tulee olla esillä, koska järjestelmästandardit edellyttävät politiikkojen julkisuutta. Ympäristövastaaville tehdyn kyselyn perusteella havaittiin, että tällä hetkellä toimipaikoilla käytössä olevissa ympäristäjärjestelmissä on eroavuuksia. Syynä tähän on muun muassa järjestelmien eri-ikäisyys, maiden toimipaikkojen erilainen lainsäädäntö sekä erilaiset resurssit. Kehittämistä on erityisesti ympäristönnäkökohtien tunnistamisessa ja merkittävien ympäristönäkökohtien valinnassa, ympäristöjärjestelmän tavoitteissa ja päämäärissä sekä käytettävissä indikaattoreissa. Näiden osalta tulee lisätä koulutusta ja ohjeistusta. Uuden ISO 14001 -standardin muutoksia tarkasteltaessa havaittiin, ettei se aiheuta suuria muutostarpeita nykyisiin ympäristöjärjestelmiin. Standardin suurimmat muutokset ovat tulleet tekstin rakenteeseen, joka on nyt selkeälukuista ja yhteensopivampaa ISO 9001 laatuhallintastandardin kanssa. Standardi painottaa entistä standardia enemmän tuotteista aiheutuvia ympäristönäkökohtia, mutta on muistettava, että sen vaikutukset nykyisiin ympäristöjärjestelmiin tiedetään vasta, kun sitä aletaan tulkita. Tulosten perusteella päädyttiin siihen, että ympäristöjärjestelmien yhdistäminen saman sertifikaatin alle on tehokkain tapa parantaa kustannustehokkuutta sekä parantaa ympäristöpolitiikkaan liittyvää jatkuvaa parantamista. Ulkoisten kustannusten aleminen ei ole tärkein syy järjestelmien yhdistämiseen, koska yhdistämisen alkuvaiheessa se aiheuttaa sisäisten kustannusten lisääntymistä. Jatkossa yhdistämisestä voidaan odottaa myös sisäisten kustannusten säästöjä, koska yhdistäminen vähentää päällekkäistä työtä. Yrityksen ympäristöpolitiikan mukaiseen jatkuvaan parantamiseen järjestelmien yhdistäminen vaikuttaa positiivisesti usealla tavalla, ja tätä voidaan pitää kustannussäästöjä tärkeämpänä syynä sertifikaattien yhdistämiseen. Se yhtenäistää toimintatapoja ja lisää yhteistyötä, mikä vaikuttaa ympäristöpolitiikan yhtenäiseen toteutumiseen.

Characteristics of 2D convective structures in Catalonia (NE Spain): an analysis using radar data and GIS

Flood simulation studies use spatial-temporal rainfall data input into distributed hydrological models. A correct description of rainfall in space and in time contributes to improvements on hydrological modelling and design. This work is focused on the analysis of 2-D convective structures (rain cells), whose contribution is especially significant in most flood events. The objective of this paper is to provide statistical descriptors and distribution functions for convective structure characteristics of precipitation systems producing floods in Catalonia (NE Spain). To achieve this purpose heavy rainfall events recorded between 1996 and 2000 have been analysed. By means of weather radar, and applying 2-D radar algorithms a distinction between convective and stratiform precipitation is made. These data are introduced and analyzed with a GIS. In a first step different groups of connected pixels with convective precipitation are identified. Only convective structures with an area greater than 32 km2 are selected. Then, geometric characteristics (area, perimeter, orientation and dimensions of the ellipse), and rainfall statistics (maximum, mean, minimum, range, standard deviation, and sum) of these structures are obtained and stored in a database. Finally, descriptive statistics for selected characteristics are calculated and statistical distributions are fitted to the observed frequency distributions. Statistical analyses reveal that the Generalized Pareto distribution for the area and the Generalized Extreme Value distribution for the perimeter, dimensions, orientation and mean areal precipitation are the statistical distributions that best fit the observed ones of these parameters. The statistical descriptors and the probability distribution functions obtained are of direct use as an input in spatial rainfall generators.

Deep radio images of the HEGRA and Whipple TeV sources in the Cygnus OB2 region.

The modern generation of Cherenkov telescopes has revealed a new population of gamma-ray sources in the Galaxy. Some of them have been identified with previously known X-ray binary systems while other remain without clear counterparts a lower energies. Our initial goal here was reporting on extensive radio observations of the first extended and yet unidentified source, namely TeV J2032+4130. This object was originally detected by the HEGRA telescope in the direction of the Cygnus OB2 region and its nature has been a matter of debate during the latest years. The situation has become more complex with the Whipple and MILAGRO telescopes new TeV detections in the same field which could be consistent with the historic HEGRA source, although a different origin cannot be ruled out. Aims.We aim to pursue our radio exploration of the TeV J2032+4130 position that we initiated in a previous paper but taking now into account the latest results from new Whipple and MILAGRO TeV telescopes. The data presented here are an extended follow up of our previous work. Methods.Our investigation is mostly based on interferometric radio observations with the Giant Metre Wave Radio Telescope (GMRT) close to Pune (India) and the Very Large Array (VLA) in New Mexico (USA). We also conducted near infrared observations with the 3.5 m telescope and the OMEGA2000 camera at the Centro Astronómico Hispano Alemán (CAHA) in Almería (Spain). Results.We present deep radio maps centered on the TeV J2032+4130 position at different wavelengths. In particular, our 49 and 20 cm maps cover a field of view larger than half a degree that fully includes the Whipple position and the peak of MILAGRO emission. Our most important result here is a catalogue of 153 radio sources detected at 49 cm within the GMRT antennae primary beam with a full width half maximum (FWHM) of 43 arc-minute. Among them, peculiar sources inside the Whipple error ellipse are discussed in detail, including a likely double-double radio galaxy and a one-sided jet source of possible blazar nature. This last object adds another alternative counterpart possibility to be considered for both the HEGRA, Whipple and MILAGRO emission. Moreover, our multi-configuration VLA images reveal the non-thermal extended emission previously reported by us with improved angular resolution. Its non-thermal spectral index is also confirmed thanks to matching beam observations at the 20 and 6 cm wavelengths.

Analysis of bulk and surface contributions in the neutron skin of nuclei

The neutron skin thickness of nuclei is a sensitive probe of the nuclear symmetry energy and has multiple implications for nuclear and astrophysical studies. However, precision measurements of this observable are difficult to obtain. The analysis of the experimental data may imply some assumptions about the bulk or surface nature of the formation of the neutron skin. Here we study the bulk or surface character of neutron skins of nuclei following from calculations with Gogny, Skyrme, and covariant nuclear mean-field interactions. These interactions are successful in describing nuclear charge radii and binding energies but predict different values for neutron skins. We perform the study by fitting two-parameter Fermi distributions to the calculated self-consistent neutron and proton densities. We note that the equivalent sharp radius is a more suitable reference quantity than the half-density radius parameter of the Fermi distributions to discern between the bulk and surface contributions in neutron skins. We present calculations for nuclei in the stability valley and for the isotopic chains of Sn and Pb.

El cos molest en l'obra d'Epictet

The work by Epictetus shows a remarkable amount of allusions to unpleasant aspects of the human body. It deals with expressions which sometimes could be almost considered aischrologia and, on other occasions, they really are. Our contribution approaches this subject and asks which might be the origin of this practice. We suggest the use of those expressions describes the body in terms fitting with Epictetus" stoic philosophy aimed to establish an inner separation between body and the right use of reason leading us into virtue. Furthermore his humble origin as a slave could help him in using unpleasant words without prejudices. Also Arrian could insist on that characteristic when transmitting Epictetus" teachings.

Elastic properties and secondary structure formation of single-stranded DNA at monovalent and divalent salt conditions

Single-stranded DNA (ssDNA) plays a major role in several biological processes. It is therefore of fundamental interest to understand how the elastic response and the formation of secondary structures are modulated by the interplay between base pairing and electrostatic interactions. Here we measure force-extension curves (FECs) of ssDNA molecules in optical tweezers set up over two orders of magnitude of monovalent and divalent salt conditions, and obtain its elastic parameters by fitting the FECs to semiflexible models of polymers. For both monovalent and divalent salts, we find that the electrostatic contribution to the persistence length is proportional to the Debye screening length, varying as the inverse of the square root of cation concentration. The intrinsic persistence length is equal to 0.7 nm for both types of salts, and the effectivity of divalent cations in screening electrostatic interactions appears to be 100-fold as compared with monovalent salt, in line with what has been recently reported for single-stranded RNA. Finally, we propose an analysis of the FECs using a model that accounts for the effective thickness of the filament at low salt condition and a simple phenomenological description that quantifies the formation of non-specific secondary structure at low forces.

Classical line shapes based on analytical solutions of bimolecular trajectories in collision induced emission. II. Reactive collisions

The classical theory of collision induced emission (CIE) from pairs of dissimilar rare gas atoms was developed in Paper I [D. Reguera and G. Birnbaum, J. Chem. Phys. 125, 184304 (2006)] from a knowledge of the straight line collision trajectory and the assumption that the magnitude of the dipole could be represented by an exponential function of the inter-nuclear distance. This theory is extended here to deal with other functional forms of the induced dipole as revealed by ab initio calculations. Accurate analytical expression for the CIE can be obtained by least square fitting of the ab initio values of the dipole as a function of inter-atomic separation using a sum of exponentials and then proceeding as in Paper I. However, we also show how the multi-exponential fit can be replaced by a simpler fit using only two analytic functions. Our analysis is applied to the polar molecules HF and HBr. Unlike the rare gas atoms considered previously, these atomic pairs form stable bound diatomic molecules. We show that, interestingly, the spectra of these reactive molecules are characterized by the presence of multiple peaks. We also discuss the CIE arising from half collisions in excited electronic states, which in principle could be probed in photo-dissociation experiments.

Fluoroscopic-Guided Radial Endobronchial Ultrasound Without Guide Sheath For Peripheral Pulmonary Lesions: A Safe And Efficient Combination.

BACKGROUND: Several guidelines recommend computed tomography scans for populations with high-risk for lung cancer. The number of individuals evaluated for peripheral pulmonary lesions (PPL) will probably increase, and with it non-surgical biopsies. Associating a guidance method with a target confirmation technique has been shown to achieve the highest diagnostic yield, but the utility of bronchoscopy with radial probe endobronchial ultrasound using fluoroscopy as guidance without a guide sheath has not been reported. METHODS: We conducted a retrospective analysis of bronchoscopy with radial probe endobronchial ultrasound using fluoroscopy procedures for the investigation of PPL performed by experienced bronchoscopists with no specific previous training in this particular technique. Operator learning curves and radiological predictors were assessed for all consecutive patients examined during the first year of application of the technique. RESULTS: Fifty-one PPL were investigated. Diagnostic yield and visualization yield were 72.5 and 82.3% respectively. The diagnostic yield was 64.0% for PPL ≤20mm, and 80.8% for PPL>20mm. No false-positive results were recorded. The learning curve of all diagnostic tools showed a DY of 72.7% for the first sub-group of patients, 81.8% for the second, 72.7% for the third, and 81.8% for the last. CONCLUSION: Bronchoscopy with radial probe endobronchial ultrasound using fluoroscopy as guidance is safe and simple to perform, even without specific prior training, and diagnostic yield is high for PPL>and ≤20mm. Based on these findings, this method could be introduced as a first-line procedure for the investigation of PPL, particularly in centers with limited resources.

A statistical shape model of the human second cervical vertebra.

PURPOSE: Statistical shape and appearance models play an important role in reducing the segmentation processing time of a vertebra and in improving results for 3D model development. Here, we describe the different steps in generating a statistical shape model (SSM) of the second cervical vertebra (C2) and provide the shape model for general use by the scientific community. The main difficulties in its construction are the morphological complexity of the C2 and its variability in the population. METHODS: The input dataset is composed of manually segmented anonymized patient computerized tomography (CT) scans. The alignment of the different datasets is done with the procrustes alignment on surface models, and then, the registration is cast as a model-fitting problem using a Gaussian process. A principal component analysis (PCA)-based model is generated which includes the variability of the C2. RESULTS: The SSM was generated using 92 CT scans. The resulting SSM was evaluated for specificity, compactness and generalization ability. The SSM of the C2 is freely available to the scientific community in Slicer (an open source software for image analysis and scientific visualization) with a module created to visualize the SSM using Statismo, a framework for statistical shape modeling. CONCLUSION: The SSM of the vertebra allows the shape variability of the C2 to be represented. Moreover, the SSM will enable semi-automatic segmentation and 3D model generation of the vertebra, which would greatly benefit surgery planning.

Direct noninvasive estimation of myocardial tricarboxylic acid cycle flux in vivo using hyperpolarized (13)C magnetic resonance.

BACKGROUND: The heart relies on continuous energy production and imbalances herein impair cardiac function directly. The tricarboxylic acid (TCA) cycle is the primary means of energy generation in the healthy myocardium, but direct noninvasive quantification of metabolic fluxes is challenging due to the low concentration of most metabolites. Hyperpolarized (13)C magnetic resonance spectroscopy (MRS) provides the opportunity to measure cellular metabolism in real time in vivo. The aim of this work was to noninvasively measure myocardial TCA cycle flux (VTCA) in vivo within a single minute. METHODS AND RESULTS: Hyperpolarized [1-(13)C]acetate was administered at different concentrations in healthy rats. (13)C incorporation into [1-(13)C]acetylcarnitine and the TCA cycle intermediate [5-(13)C]citrate was dynamically detected in vivo with a time resolution of 3s. Different kinetic models were established and evaluated to determine the metabolic fluxes by simultaneously fitting the evolution of the (13)C labeling in acetate, acetylcarnitine, and citrate. VTCA was estimated to be 6.7±1.7μmol·g(-1)·min(-1) (dry weight), and was best estimated with a model using only the labeling in citrate and acetylcarnitine, independent of the precursor. The TCA cycle rate was not linear with the citrate-to-acetate metabolite ratio, and could thus not be quantified using a ratiometric approach. The (13)C signal evolution of citrate, i.e. citrate formation was independent of the amount of injected acetate, while the (13)C signal evolution of acetylcarnitine revealed a dose dependency with the injected acetate. The (13)C labeling of citrate did not correlate to that of acetylcarnitine, leading to the hypothesis that acetylcarnitine formation is not an indication of mitochondrial TCA cycle activity in the heart. CONCLUSIONS: Hyperpolarized [1-(13)C]acetate is a metabolic probe independent of pyruvate dehydrogenase (PDH) activity. It allows the direct estimation of VTCA in vivo, which was shown to be neither dependent on the administered acetate dose nor on the (13)C labeling of acetylcarnitine. Dynamic (13)C MRS coupled to the injection of hyperpolarized [1-(13)C]acetate can enable the measurement of metabolic changes during impaired heart function.