Untersuchung des Aggregationsverhaltens amphiphiler Diblockcopolymere in überkritischem Kohlendioxid mittels dynamischer Lichtstreuung

„Untersuchung des Aggregationsverhaltens amphiphiler Diblockcopolymere in überkritischem Kohlendioxid mittels dynamischer Lichtstreuung“ In der vorliegenden Arbeit wurde die Mizellenbildung von Diblockcopolymeren des Typs PS-b-PDMS in überkritischem Kohlendioxid (CO2,SC) mittels dynamischer Lichtstreuung (DLS) charakterisiert. Zu diesem Zweck wurden Mischungen aus den Diblockcopolymeren in CO2,SC mit Styrol als Monomer druckabhängig auf diese Fähigkeit hin untersucht. Eine Mizellenbildung konnte anhand der gemessenen hydrodynamischen Radien Rh gezeigt werden. Um eine Vergleichsmöglichkeit gegenüber den mit Styrol gefüllten Kern-Hüllen-Mizellen zu bekommen, wurde das Diblockcopolymer PS-b-PDMS (9/27) zunächst ohne Styrol auf die Fähigkeit hin untersucht ungefüllte Mizellen zu bilden. Durch Druckvariation konnte ein kritischer Mizellendruck von ca. 46,7 MPa bei einer Temperatur von 338 K im Experiment bestätigt werden, der gefundene Rh liegt bei ca. 34 nm. Dagegen setzt die Aggregation bei einer PS-b-PDMS (9/27)/Styrol/CO2,SC- Mischung bei einem wesentlich niedrigeren Druck ein. Durch Druckvariation zwischen 38 MPa und 45,7 MPa wurde eine Größenänderung der Mizellen beobachtet. Durch zeitabhängige-DLS-Messungen am gleichen System bei einem bestimmten Druck wurde ein langsames Schrumpfen der Mizellen gefunden. Um den Einfluß der Blockgröße der verwendeten Amphiphile auf die Mizellenbildung zu untersuchen wurde das System PS-b-PDMS(6/37)/Styrol/CO2,SC mit Hilfe der DLS im Bereich zwischen 39,4 MPa und 43,1 MPa untersucht. Die Druckänderung zeigte für Rh ein nahezu invariantes Verhalten, daß durch eine verlängerte PDMS-Blocklänge und eine damit verbundene Kompensation der verschiedenen Wechselwirkungskräfte zwischen Mizellenkern, -hülle und CO2,SC erklärt werden kann. Im System PS-b-PDMS(6/16)/Styrol/CO2,SC konnte experimentell mit Hilfe der DLS erst nach einer ver-änderten molaren Zusammensetzung eine Mizellenbildung ab 40 MPa ermöglicht werden. Allerdings ändert sich auch in diesem System der hydrodynamische Radius ebenfalls mit dem Druck. Je nach Druck-, Temperatur- und molarer Zusammensetzung variiert die Tendenz der Systeme, Mizellen zu bilden die eine Emulsion stabilisieren können. Für die in Dispersions-Polymerisationsreaktionen eingesetzten Diblockcopolymere bedeutet dieses Ergebnis differenzierte Applikationsmöglichkeiten. Mit den ermittelten Konzentrationsverhältnissen an Amphiphil und Monomer konnte ein Bereich gefunden werden, in dem die thermodynamischen Bedingungen für die Mizellenbildung einerseits und die Vorraussetzungen für die DLS andererseits gegeben sind.

Two-dimensional balanced sampling plans excluding contiguous units

A balanced sampling plan excluding contiguous units (or BSEC for short) was first introduced by Hedayat, Rao and Stufken in 1988. These designs can be used for survey sampling when the units are arranged in one-dimensional ordering and the contiguous units in this ordering provide similar information. In this paper, we generalize the concept of a BSEC to the two-dimensional situation and give constructions of two-dimensional BSECs with block size 3. The existence problem is completely solved in the case where lambda = 1.

A Flexible Architecture for the Computation of Direct and Inverse Transforms in H.264/AVC Video Codecs

A new high throughput and scalable architecture for unified transform coding in H.264/AVC is proposed in this paper. Such flexible structure is capable of computing all the 4x4 and 2x2 transforms for Ultra High Definition Video (UHDV) applications (4320x7680@ 30fps) in real-time and with low hardware cost. These significantly high performance levels were proven with the implementation of several different configurations of the proposed structure using both FPGA and ASIC 90 nm technologies. In addition, such experimental evaluation also demonstrated the high area efficiency of theproposed architecture, which in terms of Data Throughput per Unit of Area (DTUA) is at least 1.5 times more efficient than its more prominent related designs(1).

Cartografia geotécnica subterrânea do maciço granítico de Arca D'Água (sector de Carvalhido–Burgães): implicações para o modelo geomecânico comportamental

Este trabalho pretende enfatizar a importância da elaboração de uma base de dados extensa e robusta para o melhoramento da cartografia geotécnica subterrânea do maciço granítico do sector de Carvalhido–Burgães (Porto). Este estudo envolveu a análise e o refinamento das principais características geomecânicas ao longo de um traçado com cerca de 1220 m, para a caracterização do maciço rochoso da galeria subterrânea Carvalhido–Burgães. Para esta caracterização foram coligidos e uniformizados dados geológicos, geotécnicos e geomecânicos relativos a várias campanhas de campo, realizadas entre 2005 e 2011, tendo estado a técnica da amostragem linear aplicada ao grau de compartimentação do maciço rochoso na base do seu estudo. Além disso, procedeu‐se a um tratamento estatístico das descontinuidades, bem como dos parâmetros geológico‐geotécnicos e geomecânicos a estas associados. O zonamento geotécnico do maciço granítico foi realizado sempre em estreita ligação com o conhecimento das características do maciço in situ. Pretende‐se que esta metodologia contribua para um melhor conhecimento da compartimentação dos maciços rochosos em geral e, em particular, do modelo geomecânico comportamental do maciço rochoso do Porto.

Cartografia de zonamento geotécnico no apoio ao planeamento e valorização da exploração do georrecurso: o caso do maciço rochoso da Curviã (Joane)

Este trabalho centra-se no estudo do aproveitamento expectável do maciço rochoso da pedreira da Curviã N.o 2 (Joane, Vila Nova de Famalicão, no N Portugal), através da obtenção de um bloco unitário tipo que forneça indicações para a exploração do recurso geológico para fins industriais e/ou ornamentais. Desta forma, investiga-se se num dado limite de zona geotécnica do maciço rochoso e propicio a obtenção de blocos com dimensão, avaliados apos o processo de transformação, nomeadamente, para enrocamento em obras marítimas ou balastro em obras ferroviárias. Foram seleccionados diversos afloramentos, tendo-se recorrido a técnica de amostragem linear as superfícies expostas do maciço. Esta técnica e uma das formas mais expeditas de coligir dados geológico-geotécnicos relativos as descontinuidades. Procedeu-se, ainda, a um tratamento estatístico das descontinuidades, bem como dos parâmetros geológico-geotécnicos e geomecânicos a estas associadas, propostos pela Sociedade Internacional de Mecânica das Rochas (ISRM). Todos os dados foram representados cartograficamente numa base apoiada pelos Sistemas de Informação Geográfica (SIG) e utilizadas as ferramentas de geologia estrutural, analise morfotectónica, modelação digital de terreno e cartografia de zonamento geotécnico. O zonamento geotécnico do maciço granítico foi realizado sempre em estreita ligação com o conhecimento das características do maciço ”in situ”. Pretende-se que esta metodologia contribua para um melhor conhecimento da compartimentação dos maciços rochosos em geral e, em particular, do modelo geotécnico comportamental do maciço rochoso da Curviã N.o2.

Estudo da antiga mina de volfrâmio das Aveleiras (Mire de Tibães): cartografia geotécnica e avaliação geomecânica

Este trabalho tem como objetivo sublinhar a importância de um estudo geológico‐geotécnico para apoiar a cartografia geotécnica do maciço rochoso subterrâneo da antiga mina de volfrâmio das Aveleiras (Mosteiro de Tibães, Braga). Foi realizado um trabalho de campo sistemático, ao longo de uma rede de galerias subterrâneas com uma extensão aproximada de 155 m. Estas galerias são constituídas, principalmente, por rochas metassedimentares, embora aflorem rochas graníticas num pequeno trecho de uma das galerias. A técnica de amostragem linear de descontinuidades aplicada ao grau de compartimentação do maciço rochoso esteve na base de todos os dados geológicos, geotécnicos e geomecânicos. Além disso, foram coligidos e integrados os dados de campanhas de campo anteriores, realizadas entre 2006 e 2011. Foram igualmente descritos os métodos de avaliação dos dados de campo, bem como a análise estatística dos parâmetros geológico‐geotécnicos. O zonamento geotécnico do maciço rochoso das Aveleiras foi desenvolvido tendo em conta o comportamento do maciço rochoso in situ, e foi apoiado por ensaios laboratoriais de resistência do material‐rocha através do Ensaio de Carga Pontual. Apresenta‐se uma proposta preliminar de zonamento geomecânico com o objectivo de apoiar o projeto de engenharia de maciços rochosos.

Cartografia de zonamento geotécnico em frentes de escavação de maciços rochosos heterogéneos (túnel do Marão): aplicação da classificação geomecânica GSI|2013

Este estudo pretende discutir a validade da aplicação da mais recente versão do “GSI – Geological Strength Index” (Hoek et al., 2013) em maciços rochosos heterogéneos por aplicação num projecto de obra subterrânea em execução. O estudo envolveu a caracterização geológicageotécnica nas duas frentes de escavação da frente “Poente” da empreitada de construção do Túnel do Marão (N de Portugal) tendo sido cartografados 305 metros no conjunto das duas frentes em 74 avanços consecutivos. Para esta caracterização foram coligidos e uniformizados dados geológicos, geotécnicos e geomecânicos relativos aos levantamentos realizados a cada avanço. A técnica da amostragem linear foi aplicada para a cartografia das descontinuidades que permitiu estabelecer o grau de compartimentação do maciço rochoso. Além disso, procedeu‐se a um tratamento estatístico das descontinuidades, bem como dos parâmetros geológico‐geotécnicos e geomecânicos associados. Os zonamentos geotécnicos e geomecânicos das secções em análise foram realizados sempre em estreita ligação com o conhecimento das características do maciço in situ. Procurou‐se estabelecer termos de comparação entre a versão do GSI|2013 e as versões anteriores (GSI|98, GSI|2001) por aplicação para os avanços cartografados. Pretende‐se que este trabalho contribua para um maior conhecimento da mais recente versão do “Geological Strength Index” (2013) para a sua aplicabilidade em projectos de geoengenharia.

Reproductive ecology of the invader species gekkonid lizard Hemidactylus mabouia in an area of southeastern Brazil

Hemidactylus mabouia Moreau de Jonnés, 1818 is a "fixed" clutch size exotic species well established in Brazil. In this paper we investigate some reproductive strategies adopted to minimize the costs of invariant clutch size to this invader species living in an environment with marked climatic seasonality in Southeastern Brazil (22°56’S; 46°55’W). The study was carried out from April 2002 to March 2003. Females and males attain maturity at 47.9mm and 46.9mm SVL, respectively. Larger females tended to produce larger eggs. The reproduction occurred throughout the year, but only at the wet season the females increase the clutch frequency. There was a significant variation in mean testis volume among the months throughout the year and the largest means were recorded between August and December. Maternal investment on egg size, increase on clutch frequency and seasonal increase on testis volume can represent important reproductive strategies of this invader species living in an non-urban habitat whit climatic seasonality (dry and cold weather season).

Improved nonparametric confidence intervals in time series regressions

Condence intervals in econometric time series regressions suffer fromnotorious coverage problems. This is especially true when the dependencein the data is noticeable and sample sizes are small to moderate, as isoften the case in empirical studies. This paper suggests using thestudentized block bootstrap and discusses practical issues, such as thechoice of the block size. A particular data-dependent method is proposedto automate the method. As a side note, it is pointed out that symmetricconfidence intervals are preferred over equal-tailed ones, since theyexhibit improved coverage accuracy. The improvements in small sampleperformance are supported by a simulation study.

Fragmentation energy in rock avalanches

La fragmentation est un des mécanismes opérant lors d'avalanche rocheuses. La quantification de l'énergie associée à ce mécanisme permettrait d'apprécier l'influence de celui-ci sur la phase post-rupture d'une avalanche rocheuse. Dans cet article, les distributions des tailles des blocs du massif rocheux et des débris sont présentées et comparées pour neuf cas d'avalanches rocheuses : cinq dans les montagnes Rocheuses canadiennes et quatre dans les Alpes européennes. Des degrés de fragmentation ont pu être estimés. Pour évaluer l'énergie de fragmentation, deux méthodes on été examinées : l'une est basée sur l'énergie de concassage et l'autre est basée sur l'énergie de sautage utilisée dans le domaine minier. Les résultats obtenus portent à croire qu'il y aurait une relation entre l'indice de réduction de taille (Rr = D50/d50) et l'énergie potentielle par unité de volume, normalisée par la résistance au double poinçonnement (?HG/?c). Les énergies de fragmentation calculées pour les neuf cas étudiés donne en moyenne 20 % de l'énergie potentielle. Une relation empirique entre Rr et ?HG/?c est proposée, et est par la suite utilisée pour définir un indice de désintégration (ID). Cet indice reflète la physique du processus de désintégration puisqu'il considère que l'indice de réduction de taille est fonction de l'énergie dissipée et de la résistance de la roche. Ces facteurs connus depuis longtemps n'avaient jamais été présentés d'une façon cohérente pour des cas d'avalanches rocheuses.Mots clés : avalanches rocheuses, désintégration, énergie de fragmentation, Rocheuses canadiennes, Alpes européennes.

Panitumumab plus radiotherapy versus chemoradiotherapy in patients with unresected, locally advanced squamous-cell carcinoma of the head and neck (CONCERT-2): a randomised, controlled, open-label phase 2 trial.

BACKGROUND: We aimed to compare panitumumab, a fully human monoclonal antibody against EGFR, plus radiotherapy with chemoradiotherapy in patients with unresected, locally advanced squamous-cell carcinoma of the head and neck. METHODS: In this international, open-label, randomised, controlled, phase 2 trial, we recruited patients with locally advanced squamous-cell carcinoma of the head and neck from 22 sites in eight countries worldwide. Patients aged 18 years and older with stage III, IVa, or IVb, previously untreated, measurable (≥10 mm for at least one dimension), locally advanced squamous-cell carcinoma of the head and neck (non-nasopharygeal) and an Eastern Cooperative Oncology Group performance status of 0-1 were randomly assigned (2:3) by an independent vendor to open-label chemoradiotherapy (two cycles of cisplatin 100 mg/m(2) during radiotherapy) or to radiotherapy plus panitumumab (three cycles of panitumumab 9 mg/kg every 3 weeks administered with radiotherapy) using a stratified randomisation with a block size of five. All patients received 70-72 Gy to gross tumour and 54 Gy to areas of subclinical disease with accelerated fractionation radiotherapy. The primary endpoint was local-regional control at 2 years, analysed in all randomly assigned patients who received at least one dose of their assigned protocol-specific treatment (chemotherapy, radiation, or panitumumab). The trial is closed and this is the final analysis. This study is registered with ClinicalTrials.gov, number NCT00547157. FINDINGS: Between Nov 30, 2007, and Nov 16, 2009, 152 patients were enrolled, and 151 received treatment (61 in the chemoradiotherapy group and 90 in the radiotherapy plus panitumumab group). Local-regional control at 2 years was 61% (95% CI 47-72) in the chemoradiotherapy group and 51% (40-62) in the radiotherapy plus panitumumab group. The most frequent grade 3-4 adverse events were mucosal inflammation (25 [40%] of 62 patients in the chemoradiotherapy group vs 37 [42%] of 89 patients in the radiotherapy plus panitumumab group), dysphagia (20 [32%] vs 36 [40%]), and radiation skin injury (seven [11%] vs 21 [24%]). Serious adverse events were reported in 25 (40%) of 62 patients in the chemoradiotherapy group and in 30 (34%) of 89 patients in the radiotherapy plus panitumumab group. INTERPRETATION: Panitumumab cannot replace cisplatin in the combined treatment with radiotherapy for unresected stage III-IVb squamous-cell carcinoma of the head and neck, and the role of EGFR inhibition in locally advanced squamous-cell carcinoma of the head and neck needs to be reassessed. FUNDING: Amgen.

Regional deterministic characterization of fracture networks and its application to GIS-based rock fall risk assessment

The study investigates the possibility to incorporate fracture intensity and block geometry as spatially continuous parameters in GIS-based systems. For this purpose, a deterministic method has been implemented to estimate block size (Bloc3D) and joint frequency (COLTOP). In addition to measuring the block size, the Bloc3D Method provides a 3D representation of the shape of individual blocks. These two methods were applied using field measurements (joint set orientation and spacing) performed over a large field area, in the Swiss Alps. This area is characterized by a complex geology, a number of different rock masses and varying degrees of metamorphism. The spatial variability of the parameters was evaluated with regard to lithology and major faults. A model incorporating these measurements and observations into a GIS system to assess the risk associated with rock falls is proposed. The analysis concludes with a discussion on the feasibility of such an application in regularly and irregularly jointed rock masses, with persistent and impersistent discontinuities.

Intensified chemotherapy with ACVBP plus rituximab versus standard CHOP plus rituximab for the treatment of diffuse large B-cell lymphoma (LNH03-2B): an open-label randomised phase 3 trial.

BACKGROUND: The outcome of diffuse large B-cell lymphoma has been substantially improved by the addition of the anti-CD20 monoclonal antibody rituximab to chemotherapy regimens. We aimed to assess, in patients aged 18-59 years, the potential survival benefit provided by a dose-intensive immunochemotherapy regimen plus rituximab compared with standard treatment plus rituximab. METHODS: We did an open-label randomised trial comparing dose-intensive rituximab, doxorubicin, cyclophosphamide, vindesine, bleomycin, and prednisone (R-ACVBP) with subsequent consolidation versus standard rituximab, doxorubicin, cyclophosphamide, vincristine, and prednisone (R-CHOP). Random assignment was done with a computer-assisted randomisation-allocation sequence with a block size of four. Patients were aged 18-59 years with untreated diffuse large B-cell lymphoma and an age-adjusted international prognostic index equal to 1. Our primary endpoint was event-free survival. Our analyses of efficacy and safety were of the intention-to-treat population. This study is registered with ClinicalTrials.gov, number NCT00140595. FINDINGS: One patient withdrew consent before treatment and 54 did not complete treatment. After a median follow-up of 44 months, our 3-year estimate of event-free survival was 81% (95% CI 75-86) in the R-ACVBP group and 67% (59-73) in the R-CHOP group (hazard ratio [HR] 0·56, 95% CI 0·38-0·83; p=0·0035). 3-year estimates of progression-free survival (87% [95% CI, 81-91] vs 73% [66-79]; HR 0·48 [0·30-0·76]; p=0·0015) and overall survival (92% [87-95] vs 84% [77-89]; HR 0·44 [0·28-0·81]; p=0·0071) were also increased in the R-ACVBP group. 82 (42%) of 196 patients in the R-ACVBP group experienced a serious adverse event compared with 28 (15%) of 183 in the R-CHOP group. Grade 3-4 haematological toxic effects were more common in the R-ACVBP group, with a higher proportion of patients experiencing a febrile neutropenic episode (38% [75 of 196] vs 9% [16 of 183]). INTERPRETATION: Compared with standard R-CHOP, intensified immunochemotherapy with R-ACVBP significantly improves survival of patients aged 18-59 years with diffuse large B-cell lymphoma with low-intermediate risk according to the International Prognostic Index. Haematological toxic effects of the intensive regimen were raised but manageable. FUNDING: Groupe d'Etudes des Lymphomes de l'Adulte and Amgen.

On the robust measurement of inflectional diversity

Lexical diversity measures are notoriously sensitive to variations of sample size and recent approaches to this issue typically involve the computation of the average variety of lexical units in random subsamples of fixed size. This methodology has been further extended to measures of inflectional diversity such as the average number of wordforms per lexeme, also known as the mean size of paradigm (MSP) index. In this contribution we argue that, while random sampling can indeed be used to increase the robustness of inflectional diversity measures, using a fixed subsample size is only justified under the hypothesis that the corpora that we compare have the same degree of lexematic diversity. In the more general case where they may have differing degrees of lexematic diversity, a more sophisticated strategy can and should be adopted. A novel approach to the measurement of inflectional diversity is proposed, aiming to cope not only with variations of sample size, but also with variations of lexematic diversity. The robustness of this new method is empirically assessed and the results show that while there is still room for improvement, the proposed methodology considerably attenuates the impact of lexematic diversity discrepancies on the measurement of inflectional diversity.

Speech sample estimation from composite zerocrossings and encoding via adaptive switching of transforms

This thesis investigates the potential use of zerocrossing information for speech sample estimation. It provides 21 new method tn) estimate speech samples using composite zerocrossings. A simple linear interpolation technique is developed for this purpose. By using this method the A/D converter can be avoided in a speech coder. The newly proposed zerocrossing sampling theory is supported with results of computer simulations using real speech data. The thesis also presents two methods for voiced/ unvoiced classification. One of these methods is based on a distance measure which is a function of short time zerocrossing rate and short time energy of the signal. The other one is based on the attractor dimension and entropy of the signal. Among these two methods the first one is simple and reguires only very few computations compared to the other. This method is used imtea later chapter to design an enhanced Adaptive Transform Coder. The later part of the thesis addresses a few problems in Adaptive Transform Coding and presents an improved ATC. Transform coefficient with maximum amplitude is considered as ‘side information’. This. enables more accurate tfiiz assignment enui step—size computation. A new bit reassignment scheme is also introduced in this work. Finally, sum ATC which applies switching between luiscrete Cosine Transform and Discrete Walsh-Hadamard Transform for voiced and unvoiced speech segments respectively is presented. Simulation results are provided to show the improved performance of the coder