Abundance of phytoplankton, heterotrophic nanoflagellates and bacteria through the water column at time series station L4 in the Western English Channel, 2007-2013

short doi:10/rf8 full doi:10.5285/f014becf-d6d6-3bb9-e044-000b5de50f38

Dynamic responses of the benthic bacterial community at the Western English Channel observatory site L4 are driven by deposition of fresh phytodetritus

The impact of the seasonal deposition of phytoplankton and phytodetritus on surface sediment bacterial abundance and community composition was investigated at the Western English Channel site L4. Sediment and water samples were collected from January to September in 2012, increasing in frequency during periods of high water column phytoplankton abundance. Compared to the past two decades, the spring bloom in 2012 was both unusually long in duration and contained higher than average biomass. Within spring months, the phytoplankton bloom was well mixed through the water column and showed accumulations near the sea bed, as evidenced by flow cytometry measurements of nanoeukaryotes, water column chlorophyll a and the appearance of pelagic phytoplankton at the sediment. Measurements of chlorophyll and chlorophyll degradation products indicated phytoplankton material was heavily degraded after it reached the sediment surface: the nature of the chlorophyll degradation products (predominantly pheophorbide, pyropheophorbide and hydroxychlorophyllone) was indicative of grazing activity. The abundance of bacterial 16S rRNA genes g−1 sediment (used as a proxy for bacterial biomass) increased markedly with the onset of the phytoplankton bloom, and correlated with measurements of chlorophyll at the surface sediment. Together, this suggests that bacteria may have responded to nutrients released via grazing activity. In depth sequencing of the 16S rRNA genes indicated that the composition of the bacterial community shifted rapidly through-out the prolonged spring bloom period. This was primarily due to an increase in the relative sequence abundance of Flavobacteria.

Synthesis of N3- and 2-NH2-substituted 6,7-diphenylpterins and their use as intermediates for the preparation of oligonucleotide conjugates designed to target photooxidative damage on single-stranded DNA representing the bcr-abl chimeric gene

Two 17-mer oligodeoxynucleotide-5'-linked-(6,7-diphenylpterin) conjugates, 2 and 3, were prepared as photosensitisers for targeting photooxidative damage to a 34-mer DNA oligodeoxynucleotide (ODN) fragment 1 representing the chimeric bcr-abl gene that is implicated in the pathogenesis of chronic myeloid leukaemia (CML). The base sequence in the 17-mer was 3'G G T A G T T A T T C C T T C T T5'. In the first of these ODN conjugates (2) the pterin was attached at its N3 atom, via a -(CH2)3OPO(OH)- linker, to the 5'-OH group of the ODN. Conjugate 2 was prepared from 2-amino-3-(3-hydroxypropyl)-6,7-diphenyl-4(3H)-pteridinone 10, using phosphoramidite methodology. Starting material 10 was prepared from 5-amino-7-methylthiofurazano[3,4-d]pyrimidine 4 via an unusual highly resonance stabilised cation 8, incorporating the rare 2H,6H-pyrimido[6,1-b][1,3]oxazine ring system. In the characterisation of 10 two pteridine phosphazenes, 15 and 29, were obtained, as well as new products containing two uncommon tricyclic ring systems, namely pyrimido[2,1-b]pteridine (20 and 24) and pyrimido[1,2-c]pteridine (27). In the second ODN conjugate the linker was -(CH2)5CONH(CH2)6OPO(OH)- and was attached to the 2-amino group of the pterin. In the preparation of 3, the N-hydroxysuccinimide ester 37 of 2-(5-carboxypentylamino)-6,7-diphenyl-4(3H)-pteridinone was condensed with the hexylamino-modified 17-mer. Excitation of 36 with near UV light in the presence of the single-stranded target 34-mer, 5'T G A C C A T C A A T A A G14 G A A G18 A A G21 C C C T T C A G C G G C C3' 1 caused oxidative damage at guanine bases, leading to alkali-labile sites which were monitored by polyacrylamide gel electrophoresis. Cleavage was observed at all guanine sites with a marked preference for cleavage at G14. In contrast, excitation of ODN-pteridine conjugate 2 in the presence of 1 caused oxidation of the latter predominantly at G18, with a smaller extent of cleavage at G15 and G14 (in the double-stranded portion) and G21. These results contrast with our previous observation of specific cleavage at G21 with ruthenium polypyridyl sensitisers, and suggest that a different mechanism, probably one involving Type 1 photochemical electron transfer, is operative. Much lower yields were found with the ODN-pteridine conjugate 3, perhaps as a consequence of the longer linker between the ODN and the pteridine in this case.

A aceitação de alunos com necessidades educativas especiais passados 6 anos da implementação do Decreto-Lei nº3/2008:opinião de educadores de infância e de professores do 1ºciclo

Objetivo: A compreensão da Educação Especial no paradigma da inclusão envolve vontade política e social e mobiliza necessariamente os profissionais de educação, sendo fundamental conhecer a sua opinião. Em Portugal, o Decreto-Lei n.º 3/2008 trouxe mudanças significativas no papel dos docentes do ensino regular, pelo que este estudo tem como objetivo, passados 6 anos da implementação, descrever a opinião de educadores e professores do 1º ciclo acerca da inclusão de alunos com Necessidades Educativas Especiais e conhecer os fatores que justificam as suas opiniões. Método: Foram inquiridos 244 docentes, 122 educadores de infância e 122 professores do 1º ciclo de escolas públicas e privadas, da Área Metropolitana do Porto, os instrumentos usados foram uma folha de caracterização individual e um questionário de vinhetas com descrições do funcionamento de crianças, onde os respondentes se posicionavam, para cada uma, quanto à sua aceitação nas salas. Resultados /Discussão: Os resultados apontam que as vinhetas que descreviam funcionamentos de crianças compatíveis com Perturbação de Espetro de Autismo e Paralisia Cerebral, foram as menos, sendo as justificações a falta de formação e a impossibilidade de despender o tempo necessário devido à exigência de bons resultados académicos. Aferimos que a formação em Educação Especial apenas estava associada à aceitação de alunos com Paralisia Cerebral. Aferimos que a função do docente-educador vs professor do 1ºciclo- apenas é influenciadora de aceitação no caso de alunos com Perturbação de Espetro de Autismo, Paralisia Cerebral e Atraso Global de Desenvolvimento/Dificuldades de Aprendizagem. O facto de se tratar de uma escola pública ou privada influencia a aceitação dos alunos, com os docentes do ensino privado a evidenciarem maior aceitação dos alunos do que os do ensino público.

Libro de lectura, N°3 : o sea Autores selectos Españoles e Hispano-americanos

UANL

Deutsch als L4 für Muttersprachler des Persischen

Das Erkenntnisinteresse der vorliegenden Arbeit besteht darin, im Rahmen einer explorativ-interpretativen Querschnittstudie vertiefte Einblicke in den Sprachgebrauch von mehrsprachigen Deutschlernenden am Beispiel von Verb-Nomen Kollokationen zu gewinnen. Unter Berücksichtigung der in diesem Zusammenhang bisher nicht untersuchten Sprachenkonstellation L1 Persisch, L2 Englisch, L3 Arabisch und L4 Deutsch sollen die von den Lernenden angewendeten lexikalischen Transferstrategien erforscht werden. Der Untersuchungsgegenstand sind die soziokognitiven Löseprozesse der ProbandInnen bei der dyadischen Bearbeitung von Kollokationsaufgaben. Zur Identifizierung der Transferphänomene und der TL-Strategien (Target Language-Strategien) werden Gesprächs-protokolle ausgewählter Dyaden analysiert. Überdies werden zwecks Rekonstruktion und Interpretation der Löseprozesse stimulated recall-Interviews mit den ProbandInnen herangezogen, wodurch die Datensets miteinander trianguliert werden. Zudem wird ermittelt, inwieweit ausgewählte Faktoren (Psychotypologie, Kompetenz in der Zielsprache und Kompetenz in den zuvor gelernten Sprachen) den Transferprozess beeinflussen. Hierzu dienen die Erkenntnisse aus begleitend durchgeführten Leitfadeninterviews und Sprachstandstests (TOEFL- und Arabischtest). Ferner wird der Arbeitsstil der ProbandInnen bei der dyadischen Aufgabenbearbeitung anhand des Fragebogens Style Analysis Survey von Oxford (1995) bestimmt. An der Studie, die im Deutschen Sprachinstitut Teheran durchgeführt wurde, nahmen 14 iranische Deutschlernende auf dem Niveau B2.1 und C2.2 teil. Sie wurden aufgrund ihrer mittels eines Fragebogens erhobenen Sprachlernbiografien ausgewählt. Die Gesprächsprotokolle der Dyadenarbeit und die Interviews wurden vollständig transkribiert bzw. transliteriert und anschließend qualitativ-interpretativ ausgewertet. Um ihre Wissenslücken bei der Bearbeitung der Kollokationsaufgaben zu kompensieren, setzten die ProbandInnen verschiedene inter- und intralinguale Strategien ein. Dabei ist der L1 Persisch und der L4 Deutsch insgesamt der größte Einfluss beizumessen. Diesbezüglich wird deutlich, dass zwischen Sprachniveau und Transferverhalten der Lernenden ein Zusammenhang besteht, insofern als fortgeschrittene Lernende stärker zu intralingualem Transfer neigen. Zudem lässt sich festhalten, dass ein Zusammenhang zwischen der empfundenen psychotypologischen Distanz und der Rolle der Muttersprache besteht, d.h. bei als größer empfundener psychotypologischer Distanz zwischen Persisch und Deutsch wird seltener aus dem Persischen transferiert. Überdies ist festzustellen, dass die L2 Englisch zwar gelegentlich mitaktiviert wird, jedoch nur eine untergeordnete Rolle spielt. Ein Einfluss der L3 Arabisch kann aus verschiedenen Gründen (u.a. geringes Niveau und mangelnder Gebrauch dieser Sprache) nicht festgestellt werden. Die vorliegende Arbeit versteht sich als ein Plädoyer für die Relevanz der Schulung von Kollokationen im Fremdsprachenunterricht, da die produktive Kollokationskompetenz der ProbandInnen auch auf einem hohen Niveau gravierende Defizite aufweist.

Synthesis, structure and magnetic properties of mono- and di-nuclear nickel(II) thiocyanate complexes with tridentate N3 donor Schiff bases

The 1:1 condensation of N-methyl-1,3-diaminopropane and N,N-diethyl-1,2-diminoethane with 2-acetylpyridine, respectively at high dilution gives the tridentate mono-condensed Schiff bases N-methyl-N'-(1-pyridin-2-yl-ethylidene)-propane-1,3-diamine (L-1) and N,N-diethyl-N'-(1-pyridin-2-yl-ethylidene)-ethane-1,2-diamine (L-2). The tridentate ligands were allowed to react with methanol solutions of nickel(II) thiocyanate to prepare the complexes [Ni(L-1)(SCN)(2)(OH2) (1) and [{Ni(L-2)(SCN)}(2)] (2). Single crystal X-ray diffraction was used to confirm the structures of the complexes. The nickel(II) in complex 1 is bonded to three nitrogen donor atoms of the ligand L-1 in a mer orientation, together with two thiocyanates bonded through nitrogen and a water molecule, and it is the first Schiff base complex of nickel(II) containing both thiocyanate and coordinated water. The coordinated water initiates a hydrogen bonded 2D network. In complex 2, the nickel ion occupies a slightly distorted octahedral coordination sphere, being bonded to three nitrogen atoms from the ligand L-2, also in a mer orientation, and two thiocyanate anions through nitrogen. In contrast to 1, the sixth coordination site is occupied by a sulfur atom from a thiocyanate anion in an adjacent molecule, thus creating a centrosymmetric dimer. A variable temperature magnetic study of complex 2 indicates the simultaneous presence of zero-field splitting, weak intramolecular ferromagnetic coupling and intermolecular antiferromagnetic interactions between the nickel(II) centers.

N3-Dye-Induced Visible Laser Anatase-to-Rutile Phase Transition on Mesoporous TiO(2) Films

Titanium dioxide has been extensively used in photocatalysis and dye-sensitized solar cells, where control of the anatase-to-rutile phase transformation may allow the realization of more efficient devices exploiting the synergic effects at anatase/rutile interfaces. Thus, a systematic study showing the proof of concept of a dye-induced morphological transition and an anatase-to-rutile transition based on visible laser (532 nm) and nano/micro patterning of mesoporous anatase (Degussa P25 TiO(2)) films is described for the first time using a confocal Raman microscope. At low laser intensities, only the bleaching of the adsorbed N3 dye was observed. However, high enough temperatures to promote melting/densification processes and create a deep hole at the focus and an extensive phase transformation in the surrounding material were achieved using Is laser pulses of 25-41 mW/cm(2), in resonance with the MLCT band. The dye was shown to play a key role, being responsible for the absorption and efficient conversion of the laser light into heat. As a matter of fact, the dye is photothermally decomposed to amorphous carbon or to gaseous species (CO(x), NO(x), and H(2)O) under a N(2) or O(2) atmosphere, respectively.

N3-substituted xanthines as irreversible adenosine receptor antagonists

8-Cyclopentyl-3-(3-(4-fluorosulfonylbenzoyl)oxy)propyl-propylxanthine (44, FSCPX) has been reported to exhibit potent and selective irreversible antagonism of the A1 adenosine receptor when using in vitro biological preparations. However, FSCPX (44) suffers from cleavage of the ester linkage separating the reactive 4-(fluorosulfonyl)phenyl moiety from the xanthine pharmacophore when used in in vivo biological preparations or preparations containing significant enzyme activity, presumably by esterases. Cleavage of the ester linkage renders FSCPX (44) inactive in terms of irreversible receptor binding. In order to obtain an irreversible A1 adenosine receptor antagonist with improved stability, and to further elucidate the effects of linker structure on pharmacological characteristics, several FSCPX (44) analogues incorporating the chemoreactive 4-(fluorosulfonyl)phenyl moiety were targeted, where the labile ester linkage has been replaced by more stable functionalites. In particular, ether, alkyl, amide and ketone linkers were targeted, where the length of the alkyl chain was varied from between one to five atoms. Synthesis of the target compounds was achieved via direct attachment of the N-3 substituent to the xanthine. These compounds were then tested for their biological activity at the A1 adenosine receptor via their ability to irreversibly antagonise the binding of [3H]-8-cyclopentyl-1,3-dipropylxanthine ([3H]DPCPX, ( 9) to the A1 adenosine receptor of DDT1 MF-2 cells. For comparison, the xanthines were also tested for their ability to inhibit the binding of [3H]-4-(2-[7-amino-2-{furyl} {1,2,4}- triazolo{2,3-a} {1,3,5}triazin-5-ylamino-ethyl)]phenol ([3H]ZM241385, 36) to the A2A adenosine receptor of PC-12 cells. The results suggest that the length and chemical composition of the linker separating the reactive 4-(fluorosulfonyl)phenyl moiety from the xanthine ring contribute to the potency and efficacy of the irreversible A1 adenosine receptor ligands. Like FSCPX (44, IC50 A1 = 11.8 nM), all derivatives possessed IC50 values in the low nM range under in vitro conditions. Compounds 94 (IC50 A1 = 165 nM), 95 (IC50 A1 = 112 nM) and 96 (IC50 A1 = 101 nM) possessing one, three and five methylene spacers within the linkage respectively, exhibited potent and selective binding to the A1 adenosine receptor versus the A2A adenosine receptor. Compound 94 did not exhibit any irreversible binding at A1 adenosine receptors, while 95 and 96 exhibit only weak irreversible binding at A1 adenosine receptors. Those compounds containing a benzylic carbonyl separating the 4-(fluorosulfonyl)phenyl moiety from the xanthine ring in the form of an amide (119, IC50 A1 = 24.9 nM, and 120, IC50 A1 = 21 nM) or ketone (151, IC50 A1 = 14 nM) proved to be the most potent, with compound 120 exhibiting the highest selectivity of 132-fold for the A receptor over the A2A receptor. compounds 119, 120 and 151 also strongly inhibited the binding of [3H]DPCPX irreversibly (82%, 83% and 78% loss of [3H]DPCPX binding at 100 nM respectively). compounds 120 and 151 are currently being evaluated for use in in vivo studies. Structure-activity studies suggest that altering the 8-cycloalkyl group of A1 selective xanthines for a 3-substituted or 2,3-disubstituted styryl, combined with N-7 methyl substitution will produce a compound with high affinity and selectivity for the A2A adenosine receptor over the A1 adenosine receptor. Compound 167 (IC50 A2A = 264 nM) possessing 8-(m-chloro)styryl substitution and the reactive 4-(fluorosulfonyl)phenyl moiety separated from the xanthine ring via an amide linker in the 3-position (as for 119 and 120), exhibited relatively potent binding to the A2A adenosine receptor of PC-12 cells, with a 16-fold selectivity for that receptor over the A1 adenosine receptor. However, compound 167 exhibited only very weak irreversible binding at A2A adenosine receptors. Overall, at this stage of biological testing, compound 120 appears to possess the most advantageous characteristics as an irreversible antagonist for the A1 adenosine receptor. This can be attributed to its high selectivity for the A1 adenosine receptor as compared to the A2A adenosine receptor. It also has relatively high potency for the A1 adenosine receptor, a concentration-dependent and selective inactivation of A1 adenosine receptors, and unbound ligand is easily removed (washed out) from biological membranes. These characteristics mean compound 151 has the potential to be a useful tool for the further study of the structure and function of the A1 adenosine receptor.

Spin-crossover, mesomorphic and thermoelectrical properties of cobalt(II) complexes with alkylated N3-Schiff bases

Three new cobalt(ii) complexes, [Co(L12)2](BF4)2 (1), [Co(L14)2](BF4)2·H2O (2) and [Co(L16)2](BF4)2·H2O (3), where L12-16 are N3-Schiff bases appended with linear C12-16 carbon chains at the nitrogen atoms, were obtained in good yields by facile one-pot reactions. The single crystal X-ray structure of complex 1 shows a tetragonally compressed CoN6 coordination geometry. The melting temperatures of 1-3 were lower than 373 K, while their decomposition temperatures were above 473 K. All complexes have high-spin Co(ii) centres at 300 K and exhibit a columnar mesophase above 383 K. Complexes 1 and 3 showed normal thermal spin-crossover behaviour with weak hysteresis loops at about 320 K. Hence, these complexes showed uncoupled phase transitions (class iiia). The values for the Seebeck coefficient (Se) of the cobalt redox couples formed from 1 and 2 were 1.89 ± 0.02 mV K-1 and 1.92 ± 0.08 mV K-1, respectively, identifying them as potential thermoelectrochemical materials.

L4-L5-S1 human dermatomes: a clinical, electromyographical, imaging and surgical findings

There is substantial controversy in literature about human dermatomes. We studied L4, L5, and S1 inferior limb dermatomes by comparing clinical signs and symptoms with conduction studies, electromyographical data, neurosurgical findings, and imaging data from computerized tomography (CT) or magnetic resonance imaging (MRI). After analyzing 60 patients, we concluded that L4 is probably located in the medial aspect of the leg, L5 in the lateral aspect of the leg and foot dorsus, and S1 in the posterior aspect of the backside, tight, leg and plantar foot skin. This is the first time that these human dermatomes have been evaluated by combined analysis of clinical, electromyographical, neurosurgical, and imaging data.