22 resultados para Side-chain Cleavage
em Repositório Científico do Instituto Politécnico de Lisboa - Portugal
Resumo:
The very high antiproliferative activity of [Co(Cl)(H2O)(phendione)(2)][BF4] (phendione is 1,10-phenanthroline-5,6-dione) against three human tumor cell lines (half-maximal inhibitory concentration below 1 mu M) and its slight selectivity for the colorectal tumor cell line compared with healthy human fibroblasts led us to explore the mechanisms of action underlying this promising antitumor potential. As previously shown by our group, this complex induces cell cycle arrest in S phase and subsequent cell death by apoptosis and it also reduces the expression of proteins typically upregulated in tumors. In the present work, we demonstrate that [Co(Cl)(phendione)(2)(H2O)][BF4] (1) does not reduce the viability of nontumorigenic breast epithelial cells by more than 85 % at 1 mu M, (2) promotes the upregulation of proapoptotic Bax and cell-cycle-related p21, and (3) induces release of lactate dehydrogenase, which is partially reversed by ursodeoxycholic acid. DNA interaction studies were performed to uncover the genotoxicity of the complex and demonstrate that even though it displays K (b) (+/- A standard error of the mean) of (3.48 +/- A 0.03) x 10(5) M-1 and is able to produce double-strand breaks in a concentration-dependent manner, it does not exert any clastogenic effect ex vivo, ruling out DNA as a major cellular target for the complex. Steady-state and time-resolved fluorescence spectroscopy studies are indicative of a strong and specific interaction of the complex with human serum albumin, involving one binding site, at a distance of approximately 1.5 nm for the Trp214 indole side chain with log K (b) similar to 4.7, thus suggesting that this complex can be efficiently transported by albumin in the blood plasma.
Resumo:
A qualidade do betão pode ser controlada pelo comportamento da fluidez da pasta de cimento, o qual está relacionado com a dispersão das partículas de cimento. Um dos maiores avanços na tecnologia do betão tem sido o desenvolvimento de aditivos. Um destes tipos de aditivos, os Superplastificantes (SP), fornecem a possibilidade de se obter uma melhor dispersão das partículas de cimento, produzindo pastas com elevada fluidez. Com o desenvolvimento de betões de alta resistência e elevado desempenho, os superplastificantes tornaram-se indispensáveis. Os superplastificantes são adsorvidos nas partículas de cimento e esta adsorção depende da composição do clínquer do cimento e do tipo de SP utilizado. Com a difusão do emprego dos aditivos redutores de água, têm surgido vários problemas de compatibilidade cimento/adjuvante. Esta investigação dedicada aos superplastificantes, fortes redutores de água, visou estudar quais as propriedades que poderiam influenciar a sua compatibilidade/robustez com o cimento. Também se procurou ganhar experiência com as técnicas analíticas de caracterização de adjuvantes. Assim, utilizou-se um tipo de cimento e dois tipos de superplastificantes (poli(étercarboxilatos) e poli(naftalenossulfonatos)) disponíveis no mercado português. Mantendo a mesma razão água/cimento (A/C), pretendeu-se determinar a natureza química, grau de funcionalização, teor e tipo de contra-ião, teor de sulfatos/sulfonatos do adjuvante e o comportamento dos superplastificantes nas pastas cimentícias, de forma a poder determinar indicadores de compatibilidade entre cimentos e superplastificantes. Constatou-se que a natureza química, o grau de funcionalização e a quantidade consumida dos superplastificantes têm influência nas pastas. Os indicadores de compatibilidade por parte dos superplastificantes parecem estar relacionados com o comprimento da cadeia lateral de éter e com o rácio CO2R/CO2 -. A alteração do momento da adição do adjuvante tem influência na compatibilidade cimento/adjuvante, sendo benéfico para os poli(étercarboxilatos) e prejudicial para o poli(naftalenossulfonato).
Resumo:
The structure of lignin and suberin, and ferulic acid (FA) content in cork from Quercus suber L. were studied. Extractive-free cork (Cork), suberin, desuberized cork (Cork(sap)), and milled-cork lignins (MCL) from Cork and Cork(sap) were isolated. Suberin composition was determined by GC-MS/FID, whereas the polymers structure in Cork, Corksap, and MCL was studied by Py-TMAH and 2D-HSQC-NMR. Suberin contained 94.4% of aliphatics and 3.2% of phenolics, with 90% of omega-hydroxyacids and alpha,omega-diacids. FA represented 2.7% of the suberin monomers, overwhelmingly esterified to the cork matrix. Py-TMAH revealed significant FA amounts in all samples, with about 3% and 6% in cork and cork lignins, respectively. Py-TMAH and 2D-HSQC-NMR demonstrated that cork lignin is a G-lignin (>96% G units), with a structure dominated by beta-O-4' alkyl-aryl ether linkages (80% and 77% of all linkages in MCL and MCLsap, respectively), followed by phenylcoumarans (18% and 20% in MCL and MCLsap, respectively), and smaller amounts of resinols (ca. 2%) and dibenzodioxocins (1%). HSQC also revealed that cork lignin is heavily acylated (ca. 50%) exclusively at the side-chain gamma-position. Ferulates possibly have an important function in the chemical assembly of cork cell walls with a cross-linking role between suberin, lignin and carbohydrates.
Resumo:
The Wyner-Ziv video coding (WZVC) rate distortion performance is highly dependent on the quality of the side information, an estimation of the original frame, created at the decoder. This paper, characterizes the WZVC efficiency when motion compensated frame interpolation (MCFI) techniques are used to generate the side information, a difficult problem in WZVC especially because the decoder only has available some reference decoded frames. The proposed WZVC compression efficiency rate model relates the power spectral of the estimation error to the accuracy of the MCFI motion field. Then, some interesting conclusions may be derived related to the impact of the motion field smoothness and the correlation to the true motion trajectories on the compression performance.
Resumo:
Novel alternating copolymers comprising biscalix[4]arene-p-phenylene ethynylene and m-phenylene ethynylene units (CALIX-m-PPE) were synthesized using the Sonogashira-Hagihara cross-coupling polymerization. Good isolated yields (60-80%) were achieved for the polymers that show M-n ranging from 1.4 x 10(4) to 5.1 x 10(4) gmol(-1) (gel permeation chromatography analysis), depending on specific polymerization conditions. The structural analysis of CALIX-m-PPE was performed by H-1, C-13, C-13-H-1 heteronuclear single quantum correlation (HSQC), C-13-H-1 heteronuclear multiple bond correlation (HMBC), correlation spectroscopy (COSY), and nuclear overhauser effect spectroscopy (NOESY) in addition to Fourier transform-Infrared spectroscopy and microanalysis allowing its full characterization. Depending on the reaction setup, variable amounts (16-45%) of diyne units were found in polymers although their photophysical properties are essentially the same. It is demonstrated that CALIX-m-PPE does not form ground-or excited-state interchain interactions owing to the highly crowded environment of the main-chain imparted by both calix[4]arene side units which behave as insulators inhibiting main-chain pi-pi staking. It was also found that the luminescent properties of CALIX-m-PPE are markedly different from those of an all-p-linked phenylene ethynylene copolymer (CALIX-p-PPE) previously reported. The unexpected appearance of a low-energy emission band at 426 nm, in addition to the locally excited-state emission (365 nm), together with a quite low fluorescence quantum yield (Phi = 0.02) and a double-exponential decay dynamics led to the formulation of an intramolecular exciplex as the new emissive species.
Resumo:
One of the most efficient approaches to generate the side information (SI) in distributed video codecs is through motion compensated frame interpolation where the current frame is estimated based on past and future reference frames. However, this approach leads to significant spatial and temporal variations in the correlation noise between the source at the encoder and the SI at the decoder. In such scenario, it would be useful to design an architecture where the SI can be more robustly generated at the block level, avoiding the creation of SI frame regions with lower correlation, largely responsible for some coding efficiency losses. In this paper, a flexible framework to generate SI at the block level in two modes is presented: while the first mode corresponds to a motion compensated interpolation (MCI) technique, the second mode corresponds to a motion compensated quality enhancement (MCQE) technique where a low quality Intra block sent by the encoder is used to generate the SI by doing motion estimation with the help of the reference frames. The novel MCQE mode can be overall advantageous from the rate-distortion point of view, even if some rate has to be invested in the low quality Intra coding blocks, for blocks where the MCI produces SI with lower correlation. The overall solution is evaluated in terms of RD performance with improvements up to 2 dB, especially for high motion video sequences and long Group of Pictures (GOP) sizes.
Resumo:
This paper is on the problem of short-term hydro scheduling (STHS), particularly concerning a head-dependent hydro chain We propose a novel mixed-integer nonlinear programming (MINLP) approach, considering hydroelectric power generation as a nonlinear function of water discharge and of the head. As a new contribution to eat her studies, we model the on-off behavior of the hydro plants using integer variables, in order to avoid water discharges at forbidden areas Thus, an enhanced STHS is provided due to the more realistic modeling presented in this paper Our approach has been applied successfully to solve a test case based on one of the Portuguese cascaded hydro systems with a negligible computational time requirement.
Resumo:
The aim of this paper is concerned with the design and development of a functional framework for maritime mode integration in European automotive supply chain management when considering outbound distribution. Furthermore, it provides a readjustment of traditional concepts and terminology with findings that the role of ro-ro port terminals should be considered as decoupling points, poles and postponement platforms. Case studies examine relevant Western European ro-ro port terminals for cars and respective links to assembly/factories of vehicles localized in the hinterland and concludes that ro-ro port terminals reduce logistical friction and impedance, as well as promote space/time compression.
Resumo:
Recently, several distributed video coding (DVC) solutions based on the distributed source coding (DSC) paradigm have appeared in the literature. Wyner-Ziv (WZ) video coding, a particular case of DVC where side information is made available at the decoder, enable to achieve a flexible distribution of the computational complexity between the encoder and decoder, promising to fulfill novel requirements from applications such as video surveillance, sensor networks and mobile camera phones. The quality of the side information at the decoder has a critical role in determining the WZ video coding rate-distortion (RD) performance, notably to raise it to a level as close as possible to the RD performance of standard predictive video coding schemes. Towards this target, efficient motion search algorithms for powerful frame interpolation are much needed at the decoder. In this paper, the RD performance of a Wyner-Ziv video codec is improved by using novel, advanced motion compensated frame interpolation techniques to generate the side information. The development of these type of side information estimators is a difficult problem in WZ video coding, especially because the decoder only has available some reference, decoded frames. Based on the regularization of the motion field, novel side information creation techniques are proposed in this paper along with a new frame interpolation framework able to generate higher quality side information at the decoder. To illustrate the RD performance improvements, this novel side information creation framework has been integrated in a transform domain turbo coding based Wyner-Ziv video codec. Experimental results show that the novel side information creation solution leads to better RD performance than available state-of-the-art side information estimators, with improvements up to 2 dB: moreover, it allows outperforming H.264/AVC Intra by up to 3 dB with a lower encoding complexity.
Resumo:
The advances made in channel-capacity codes, such as turbo codes and low-density parity-check (LDPC) codes, have played a major role in the emerging distributed source coding paradigm. LDPC codes can be easily adapted to new source coding strategies due to their natural representation as bipartite graphs and the use of quasi-optimal decoding algorithms, such as belief propagation. This paper tackles a relevant scenario in distributedvideo coding: lossy source coding when multiple side information (SI) hypotheses are available at the decoder, each one correlated with the source according to different correlation noise channels. Thus, it is proposed to exploit multiple SI hypotheses through an efficient joint decoding technique withmultiple LDPC syndrome decoders that exchange information to obtain coding efficiency improvements. At the decoder side, the multiple SI hypotheses are created with motion compensated frame interpolation and fused together in a novel iterative LDPC based Slepian-Wolf decoding algorithm. With the creation of multiple SI hypotheses and the proposed decoding algorithm, bitrate savings up to 8.0% are obtained for similar decoded quality.
Resumo:
Video coding technologies have played a major role in the explosion of large market digital video applications and services. In this context, the very popular MPEG-x and H-26x video coding standards adopted a predictive coding paradigm, where complex encoders exploit the data redundancy and irrelevancy to 'control' much simpler decoders. This codec paradigm fits well applications and services such as digital television and video storage where the decoder complexity is critical, but does not match well the requirements of emerging applications such as visual sensor networks where the encoder complexity is more critical. The Slepian Wolf and Wyner-Ziv theorems brought the possibility to develop the so-called Wyner-Ziv video codecs, following a different coding paradigm where it is the task of the decoder, and not anymore of the encoder, to (fully or partly) exploit the video redundancy. Theoretically, Wyner-Ziv video coding does not incur in any compression performance penalty regarding the more traditional predictive coding paradigm (at least for certain conditions). In the context of Wyner-Ziv video codecs, the so-called side information, which is a decoder estimate of the original frame to code, plays a critical role in the overall compression performance. For this reason, much research effort has been invested in the past decade to develop increasingly more efficient side information creation methods. This paper has the main objective to review and evaluate the available side information methods after proposing a classification taxonomy to guide this review, allowing to achieve more solid conclusions and better identify the next relevant research challenges. After classifying the side information creation methods into four classes, notably guess, try, hint and learn, the review of the most important techniques in each class and the evaluation of some of them leads to the important conclusion that the side information creation methods provide better rate-distortion (RD) performance depending on the amount of temporal correlation in each video sequence. It became also clear that the best available Wyner-Ziv video coding solutions are almost systematically based on the learn approach. The best solutions are already able to systematically outperform the H.264/AVC Intra, and also the H.264/AVC zero-motion standard solutions for specific types of content. (C) 2013 Elsevier B.V. All rights reserved.
Resumo:
In distributed video coding, motion estimation is typically performed at the decoder to generate the side information, increasing the decoder complexity while providing low complexity encoding in comparison with predictive video coding. Motion estimation can be performed once to create the side information or several times to refine the side information quality along the decoding process. In this paper, motion estimation is performed at the decoder side to generate multiple side information hypotheses which are adaptively and dynamically combined, whenever additional decoded information is available. The proposed iterative side information creation algorithm is inspired in video denoising filters and requires some statistics of the virtual channel between each side information hypothesis and the original data. With the proposed denoising algorithm for side information creation, a RD performance gain up to 1.2 dB is obtained for the same bitrate.
Resumo:
A 9.9 kb DNA fragment from the right arm of chromosome VII of Saccharomyces cerevisiae has been sequenced and analysed. The sequence contains four open reading frames (ORFs) longer than 100 amino acids. One gene, PFK1, has already been cloned and sequenced and the other one is the probable yeast gene coding for the beta-subunit of the succinyl-CoA synthetase. The two remaining ORFs share homology with the deduced amino acid sequence (and their physical arrangement is similar to that) of the YHR161c and YHR162w ORFs from chromosome VIII.
Resumo:
A 17.6 kb DNA fragment from the right arm of chromosome VII of Saccharomyces cerevisiae has been sequenced and analysed. The sequence contains twelve open reading frames (ORFs) longer than 100 amino acids. Three genes had already been cloned and sequenced: CCT, ADE3 and TR-I. Two ORFs are similar to other yeast genes: G7722 with the YAL023 (PMT2) and PMT1 genes, encoding two integral membrane proteins, and G7727 with the first half of the genes encoding elongation factors 1gamma, TEF3 and TEF4. Two other ORFs, G7742 and G7744, are most probably yeast orthologues of the human and Paracoccus denitrificans electron-transferring flavoproteins (beta chain) and of the Escherichia coli phosphoserine phosphohydrolase. The five remaining identified ORFs do not show detectable homology with other protein sequences deposited in data banks. The sequence has been deposited in the EMBL data library under Accession Number Z49133.
Resumo:
Objective - The adjusted effect of long-chain polyunsaturated fatty acid (LCPUFA) intake during pregnancy on adiposity at birth of healthy full-term appropriate-for-gestational age neonates was evaluated. Study Design - In a cross-sectional convenience sample of 100 mother and infant dyads, LCPUFA intake during pregnancy was assessed by food frequency questionnaire with nutrient intake calculated using Food Processor Plus. Linear regression models for neonatal body composition measurements, assessed by air displacement plethysmography and anthropometry, were adjusted for maternal LCPUFA intakes, energy and macronutrient intakes, prepregnancy body mass index and gestational weight gain. Result - Positive associations between maternal docosahexaenoic acid intake and ponderal index in male offspring (β=0.165; 95% confidence interval (CI): 0.031–0.299; P=0.017), and between n-6:n-3 LCPUFA ratio intake and fat mass (β=0.021; 95% CI: 0.002–0.041; P=0.034) and percentage of fat mass (β=0.636; 95% CI: 0.125–1.147; P=0.016) in female offspring were found. Conclusion - Using a reliable validated method to assess body composition, adjusted positive associations between maternal docosahexaenoic acid intake and birth size in male offspring and between n-6:n-3 LCPUFA ratio intake and adiposity in female offspring were found, suggesting that maternal LCPUFA intake strongly influences fetal body composition.