Characterization of volatile organic gunshot residues in fired handgun cartridges by headspace sorptive extraction

In forensic investigation of firearm-related cases, determination of the residual amount of volatile compounds remaining inside a cartridge could be useful in estimating the time since its discharge. Published approaches are based on following the decrease of selected target compounds as a function of time by using solid phase micro-extraction (SPME). Naphthalene, as well as an unidentified decomposition product of nitrocellulose (referred to as "TEA2"), are usually employed for this purpose. However, reliability can be brought into question given their high volatility and the low reproducibility of their extracted quantities. In order to identify alternatives and therefore develop improved dating methods, an extensive study on the composition and variability of volatile residues in nine different types of cartridges was carried out. Analysis was performed using headspace sorptive extraction (HSSE), which is a more exhaustive technique compared to SPME. 166 compounds were identified (several of which for the first time), and it was observed that the final compositional characteristics of each residue were strongly dependent on its source. Variability of single identified compounds within and between different types of cartridge, as well as their evolution over time, was also studied. Many explosion products containing up to 4 aromatic rings were found to be globally present in high proportions amongst residues. 27 of them (excluding naphthalene) also presented detectable decreases during the first 24 h. Therefore, they could be used as complementary target analytes in future dating methods.

Manual para buenos directivos de PYMES que quieren innovar: Empresas 2.0

Estamos viviendo desde la entrada al siglo XXI una explosión acelerada de las tecnologías, de las TIC’s, las redes sociales en internet, etc. que están modificando enormemente los hábitos de consumo y los principios de la sociedad. A todo ello, hay que añadir la situación de crisis económica general que existe en el mundo, y que afecta enormemente a las empresas y al tejido empresarial de un país. En este entorno, las compañías deben basar sus estrategias en estar cerca del cliente y ser capaces de visualizar necesidades no cubiertas. Sobre todo, las empresas deben transformarse para crear organizaciones humanizadas capaces de generar innovación y adaptarse rápidamente a los nuevos entornos que van surgiendo. Para poder hacer frente a esta nueva situación las empresas deben poner en valor el talento de todas las personas que forman parte de la organización. El activo más importante y escaso, para poder desarrollar estrategias triunfadoras. El trabajo pretende resumir la situación actual para las empresas, recoger todas las ideas y nuevas tendencias que existen en cuanto a la gestión del talento, la organización del trabajo y la creación de estructuras que permitan innovar. A lo largo del trabajo se van desarrollando las diferentes herramientas, sistemas y disciplinas que están a disposición de las empresas para crear un entorno que favorezca la innovación, como camino para mantenerse en el mercado global.

LS 5039: A runaway microquasar ejected from the galactic plane

We have compiled optical and radio astrometric data of the microquasar LS 5039 and derived its proper motion. This, together with the distance and radial velocity of the system, allows us to state that this source is escaping from its own regional standard of rest, with a total systemic velocity of about 150 km/s and a component perpendicular to the galactic plane larger than 100 km/s. This is probably the result of an acceleration obtained during the supernova event that created the compact object in this binary system. We have computed the trajectory of LS 5039 in the past, and searched for OB associations and supernova remnants in its path. In particular, we have studied the possible association between LS 5039 and the supernova remnant G016.8-01.1, which, despite our efforts, remains dubious. We have also discovered and studied an HI cavity in the ISM, which could have been created by the stellar wind of LS 5039 or by the progenitor of the compact object in the system. Finally, in the symmetric supernova explosion scenario, we estimate that at least 17 solar masses were lost in order to produce the high eccentricity observed. Such a mass loss could also explain the observed runaway velocity of the microquasar.

Les Neurosciences au Tribunal: de la responsabilité à la dangerosité

In recent years, an explosion of interest in neuroscience has led to the development of "Neuro-law," a new multidisciplinary field of knowledge whose aim is to examine the impact and role of neuroscientific findings in legal proceedings. Neuroscientific evidence is increasingly being used in US and European courts in criminal trials, as part of psychiatric testimony, nourishing the debate about the legal implications of brain research in psychiatric-legal settings. During these proceedings, the role of forensic psychiatrists is crucial. In most criminal justice systems, their mission consists in accomplishing two basic tasks: assessing the degree of responsibility of the offender and evaluating their future dangerousness. In the first part of our research, we aim to examine the impact of Neuroscientific evidence in the assessment of criminal responsibility, a key concept of law. An initial jurisprudential research leads to conclude that there are significant difficulties and limitations in using neuroscience for the assessment of criminal responsibility. In the current socio-legal context, responsibility assessments are progressively being weakened, whereas dangerousness assessments gain increasing importance in the field of forensic psychiatry. In the second part of our research we concentrate on the impact of using neuroscience for the assessment of dangerousness. We argue that in the current policy era of zero tolerance, judges, confronted with the pressure to ensure public security, may tend to interpret neuroscientific knowledge and data as an objective and reliable way of evaluating one's dangerousness and risk of reoffending, rather than their responsibility. This tendency could be encouraged by a utilitarian approach to punishment, advanced by some recent neuroscientific research which puts into question the existence of free will and responsibility and argues for a rejection of the retributive theory of punishment. Although this shift away from punishment aimed at retribution in favor of a consequentialist approach to criminal law is advanced by some authors as a more progressive and humane approach, we believe that it could lead to the instrumentalisation of neuroscience in the interest of public safety, which can run against the proper exercise of justice and civil liberties of the offenders. By advancing a criminal law regime animated by the consequentialist aim of avoiding social harms through rehabilitation, neuroscience promotes a return to a therapeutical approach to crime which can have serious impact on the kind and the length of sentences imposed on the offenders; if neuroscientific data are interpreted as evidence of dangerousness, rather than responsibility, it is highly likely that judges impose heavier sentences, or/and security measures (in civil law systems), which can be indeterminate in length. Errors and epistemic traps of past criminological movements trying to explain the manifestation of a violent and deviant behavior on a biological and deterministic basis stress the need for caution concerning the use of modern neuroscientific methods in criminal proceedings.

Imaging of the adrenal gland lesions

With the steep increase in the use of cross-sectional imaging in recent years, the incidentally detected adrenal lesion, or "incidentaloma", has become an increasingly common diagnostic problem for the radiologist, and a need for an approach to classifying these lesions as benign, malignant or indeterminate with imaging has spurred an explosion of research. While most incidentalomas represent benign disease, typically an adenoma, the possibility of malignant involvement of the adrenal gland necessitates a reliance on imaging to inform management decisions. In this article, we review the literature on adrenal gland imaging, with particular emphasis on computed tomography, magnetic resonance imaging, and photon-emission tomography, and discuss how these findings relate to clinical practice. Emerging technologies, such as contrast-enhanced ultrasonography, dual-energy computed tomography, and magnetic resonance spectroscopic imaging will also be briefly addressed.

Turvallisuusanalyysi korkeajännitesähkönpurkauslaitteistolle

Työssä tehtiin turvallisuusanalyysi Lappeenrannan teknillisen yliopiston tutkimuskäyttöön tarkoitetulle korkeajännitesähkönpurkauslaitteistolle. Sähkönpurkauslaite on uutta teknologiaa jätevedenkäsittelyyn. Työssä tutkittiin useita eri analyysimenetelmiä turvallisuusanalyysin tekemiseen, jotta löydettäisiin sopiva menetelmä korkeajännitesähkönpurkauslaitteistolle. Tutustuttiin lähemmin kolmeen analyysimenetelmään, jotka olivat Dow’s Fire And Explosion Index, HAZOP-poikkeamatarkastelu ja vaarallisten skenaarioiden analyysi HAZSCAN. Lopullinen turvallisuusanalyysi tehtiin HAZSCAN-turvallisuusanalyysimenetelmän avulla. HAZSCAN valittiin koska se oli vaihtoehdoista joustavin ja sen avulla oli mahdollista tutkia kaikkia turvallisuuden osa-alueita. Suurimmaksi turvallisuusriskiksi havaittiin korkeajännitesähkönpurkauslaitteiston kennoston kuumeneminen. Riskien vähyys johtuu lähinnä siitä, että tutkimuskäytössä oleva laite on pienessä mittakaavassa. Tehty turvallisuusanalyysi ei itsessään parantanut laboratoriomittakaavassa olevan laitteen turvallisuutta, sillä toistaiseksi muutosten täytäntöönpanosta ei ole tehty päätöstä. Turvallisuusanalyysi ei sovellu suoraan käytettäväksi teollisuudessa, sillä se on tehty tutkimuskäytössä olevalle korkeajännitesähkönpurkauslaitteistolle. Se toimii kuitenkin hyvänä pohjana jatkossa tehtäville turvallisuusanalyyseille.

The chemistry involved in the steam treatment of lignocellulosic materials

Pretreatment of lignocellulosic materials is essential for bioconversion because of the various physical and chemical barriers that greatly inhibit their susceptibility to bioprocesses such as hydrolysis and fermentation. The aim of this article is to review some of the most important pretreatment methods developed to date to enhance the conversion of lignocellulosics. Steam explosion, which precludes the treatment of biomass with high-pressure steam under optimal conditions, is presented as the pretreatment method of choice and its mode of action on lignocellulosics is discussed. The optimal pretreatment conditions for a given plant biomass are defined as those in which the best substrate for hydrolysis is obtained with the least amount of soluble sugars lost to side reactions such as dehydration. Therefore, pretreatment optimization results from a compromise between two opposite trends because hemicellulose recovery in acid hydrolysates can only be maximized at lower pretreatment severities, whereas the development of substrate accessibility requires more drastic pretreatment conditions in which sugar losses are inevitable. To account for this heterogeneity, the importance of several process-oriented parameters is discussed in detail, such as the pretreatment temperature, residence time into the steam reactor, use of an acid catalyst, susceptibility of the pretreated biomass to bioconversion, and process design.

Control and femtosecond time-resolved imaging of torsion in a chiral molecule

We study how the combination of long and short laser pulses can be used to induce torsion in an axially chiral biphenyl derivative (3,5-difluoro-3 ,5 -dibromo-4 -cyanobiphenyl). A long, with respect to the molecular rotational periods, elliptically polarized laser pulse produces 3D alignment of the molecules, and a linearly polarized short pulse initiates torsion about the stereogenic axis. The torsional motion is monitored in real-time by measuring the dihedral angle using femtosecond time-resolved Coulomb explosion imaging. Within the first 4 picoseconds (ps), torsion occurs with a period of 1.25 ps and an amplitude of 3◦ in excellent agreement with theoretical calculations. At larger times, the quantum states of the molecules describing the torsional motion dephase and an almost isotropic distribution of the dihedral angle is measured.We demonstrate an original application of covariance analysis of two-dimensional ion images to reveal strong correlations between specific ejected ionic fragments from Coulomb explosion. This technique strengthens our interpretation of the experimental data

Muutosilmiöt soodakattilakeossa

Soodakattilan sulakeon epästationaarinen käyttäytyminen sekä keon pitkä jäähtymisaika alasajon jälkeen ovat aiheuttaneet ongelmia kattilan taloudellisessa käytettävyydessä. Keon käyttäytymisestä on luotu CFD-malleja, joiden tavoitteena on havainnollistaa keon lämpötilajakaumaa ja rakennetta. Mallien ongelmana on se, että niissä huomioidaan vain keon aktiivinen pintakerros. Keon sisäosan rakennetta ja siinä tapahtuvia prosesseja ei toistaiseksi tunneta kunnolla luotettavan, koko keon kattavan mallin luomiseen. Tässä työssä tutkittiin sulakeon käytön aikana havaittuja muutosilmiöitä, jotka vaikuttavat keon rakenteeseen ja ominaisuuksiin sekä tutkittiin ilmiöiden taustalla olevia tekijöitä. Näitä tekijöitä ovat keon sisässä tapahtuvat kemialliset ja fyysiset prosessit, jotka aiheuttavat muutoksia niin lämpöteknisesti kuin fyysisesti sekä ulkoapäin tulevat tekijät, jotka aiheutuvat ajotilanteiden seurauksena tapahtuvista muutoksista. Työn kokeellisena osana luotiin sulakeon jäähtymismalli käyttäen 1-dimensionaalista ADL-mallia. Mallin pohjana käytettiin StoraEnso Oy:ltä Oulun soodakattilan sulakeosta saatua mittausraporttia. ADL-mallin avulla luotiin keon jäähtymiskäyrät lämpötilan ja syvyyden funktiona. Saadut käyrät täsmäsivät hyvin mittausraportin tuloksiin. Mallin avulla keolle saatiin muodostettua energiatase, jonka tuloksena keosta 12 tunnin aikana poistuva lämpövirta pinnalla oli noin 9.8kW/m2 ja pinnan lämmönsiirtokerroin 58.3W/m²°C. Pohjan poistuvaksi lämpövirraksi saatiin 14.1kW/m2 ja lämmönsiirtokertoimeksi 75.4W/m²°C. Termiseksi diffuusiokertoimeksi saatiin 3.9•10-7m²/s.

Reações de organocatálise com aminas quirais: aspectos mecanísticos e aplicações em síntese orgânica

The philosophy of organocatalysis is based on the utilization of organic compounds to catalyze organic transformations without the intervention of metals. This area has attracted much attention of the synthetic chemistry community on the last years, which can be confirmed by the explosion of published papers dealing with this subject. Phosphorus compounds, urea and thiourea derivatives, alkaloids, guanidine derivatives, for example, have already been used as organocatalysts. In this review we have focused on the use of chiral amines as organocatalyst. We have also chosen some outstanding examples to demonstrate the potentiality of this strategy in the synthesis of natural products and biologically active compounds.

Efeito do teor de umidade sobre o pré-tratamento a vapor e a hidrólise enzimática do bagaço de cana-de-açúcar

The effect of moisture content in the steam treatment and enzymatic hydrolysis of sugarcane bagasse was evaluated. Steam treatment was perfomed at 195-210 ºC for 4-8 min using cane bagasse with moisture contents in the range 16-100 wt% (dry basis). Increased moisture contents not only had a positive influence in recovery of main cane biomass components but also resulted in better substrates for enzymatic hydrolysis. As a result, drying is not required for optimal pretreatment and enzymatic hydrolysis of sugarcane bagasse, which can be processed into second generation ethanol immediately after crushing and hot water washing.

Kiihtyvä evoluutio

Kirjallisuusarvostelu

Simulation of hydrogen peroxide direct synthesis in a microreactor

A set of models in Aspen plus was built to simulate the direct synthesis process of hydrogen peroxide in a micro-reactor system. This process model can be used to carry out material balance calculation under various experimental conditions. Three thermodynamic property methods were compared by calculating gas solubility and Uniquac-RK method was finally selected for process model. Two different operation modes with corresponding operation conditions were proposed as the starting point of future experiments. Simulations for these two modes were carried out to get the information of material streams. Moreover, some hydrodynamic parameters such as gas/liquid superficial velocity, gas holdup were also calculated with improved process model. These parameters proved the proposed experimental conditions reasonable to some extent. The influence of operation conditions including temperature, pressure and circulation ratio was analyzed for the first operation mode, where pure oxygen was fed into dissolving tank and hydrogen-carbon dioxide mixture was fed into microreactor directly. The preferred operation conditions for the system are low temperature (2°C) and high pressure (30 bar) in dissolving tank. High circulation ratio might be good in the sense that more oxygen could be dissolved and fed into reactor for reactions, but meanwhile hydrodynamics of microreactor should be considered. Furthermore, more operation conditions of reactor gas/liquid feeds in both of two operation modes were proposed to provide guidance for future experiment design and corresponding hydrodynamic parameters were also calculated. Finally, safety issue was considered from thermodynamic point of view and there is no explosion danger at given experimental plan since the released reaction heat will not cause solvent vaporization inside the microchannels. The improvement of process model still needs further study based on the future experimental results.

Ballistisen simuloinnin liikeidean kehittämismahdollisuudet

Asevaikutusta laukaisusta kohteeseen simuloiva integroitu laskentaketju koostuu sisä-, ulko- ja maaliballistiikan malleista. Ulkoballistiikka kattaa laskentamallit radanlaskennan, sääkorjauksen ja ammusaerodynamiikan alueilla. Graafisella käyttöliittymällä toteutetulla, fysikaalisesti tarkkaan mallinnukseen perustuvalla ja kokonaisuuden kattavalla laskentajärjestelmällä on kasvavaa tarvetta teknisiä ja koulutuksellisia tarkoituksia varten. Erikoisesti, jos laskentaketjuun lisätään räjähdysvaikutuksen mallintaminen, voidaan simuloida asejärjestelmien vaikutusta kohteessa käyttäjien arvostamalla tavalla. Tietointensiiviset ballistiikan laskentamallit ovat välttämättömiä työkaluja teknisen suunnitteluosaamisen kattamiseksi ja kilpailuedun luomiseksi verkostoituneessa yritysympäristössä. Yliopistotutkimuksen tuottamien laskennallisten menetelmien hyötykäyttö yritysten suunnittelujärjestelmissä syventää teknistä osaamista, jolla on myös henkilöstöä motivoiva vaikutus teknisesti vaikeutuvilla markkinoilla. Työssä arvioidaan toimialaa analysoimalla eri käyttötarpeita samoille tietokantoihin tukeutuville laskentamalleille. Tarkastellaan teknisiä perusteita, käyttöympäristöjä ja markkinoita liiketoimintamahdollisuuksien tunnistamiseksi. Työn tuloksena syvennetään näkemystä ydinosaamisista ja visioidaan liikeidean erottumista kilpailijoista, markkinoita ja sen kehittämistä.

Miehistönkuljetusajoneuvon rungon suunnittelu

Tämän diplomityön tavoitteena oli suunnitella miehistönkuljetusajoneuvon runko. Rungosta suunniteltiin mahdollisimman hyvin energiaa absorboiva. Rakenne toteutettiin kennora-kenteena. Suunnittelussa sovellettiin koneensuunnittelun periaatteiden lisäksi energiaa ab-sorboivien rakenteiden suunnittelun periaatteita. Myös valmistustekniset näkökohdat otet-tiin huomioon. Rakenteessa hyödynnettiin Ruukki Oy:n Ramor 500 suojausterästä sekä OPTIM 500 MC terästä. Lisäksi erilaisten täyteaineiden käyttöä tutkittiin. Suunnittelun työkaluna käytettiin epälineaarista elementtimenetelmää, koska energiaa ab-sorboivien rakenteiden suunnittelussa on otettava huomioon materiaalien epälineaarinen käyttäytyminen. Rakenteen suunnittelu jakaantui viiteen vaiheeseen. Aluksi rakenteeseen kohdistuvat kuormitukset laskettiin elementtimenetelmän avulla. Esisuunnittelussa lasket-tiin plastisuusteorian avulla alustavasti tarvittavat materiaalipaksuudet. Tämän jälkeen ra-kenteen ydingeometria optimoitiin mahdollisimman hyvin energiaa absorboivaksi. Opti-moinnissa hyödynnettiin elementtimenetelmää. Seuraavassa vaiheessa varmistettiin raken-teen globaalit ominaisuudet. Lopuksi rakenteen kestävyyttä tarkasteltiin elementtimene-telmällä. Runko ei mallien mukaan kestänyt siltä vaadittuja kuormitustapauksia. Mallin kaikki ole-tukset pidettiin varmalla puolella. Reunaehdot oletettiin todellisuutta jäykemmiksi. Myös-kään materiaalin venymänopeudesta johtuvaa lujittumista ei otettu huomioon. Koska mii-naräjähdys on monimutkainen tapahtuma, rungon todellinen kestävyys joudutaan ar-viomaan räjähdystesteillä. Elementtimallien perusteella voidaan kuitenkin sanoa, että ener-giaa absorboiva ajoneuvon runko on mahdollista toteuttaa kennorakenteena. Lisäksi voi-daan todeta, että elementtimenetelmää sopii työvälineeksi tämän tyyppisten rakenteiden suunnitteluun.