2,230 research outputs found
Scientific research on animal biodiversity is systematically biased towards vertebrates and temperate regions.
Over the last 25 years, research on biodiversity has expanded dramatically, fuelled by increasing threats to the natural world. However, the number of published studies is heavily weighted towards certain taxa, perhaps influencing conservation awareness of and funding for less-popular groups. Few studies have systematically quantified these biases, although information on this topic is important for informing future research and conservation priorities. We investigated: i) which animal taxa are being studied; ii) if any taxonomic biases are the same in temperate and tropical regions; iii) whether the taxon studied is named in the title of papers on biodiversity, perhaps reflecting a perception of what biodiversity is; iv) the geographical distribution of biodiversity research, compared with the distribution of biodiversity and threatened species; and v) the geographical distribution of authors' countries of origin. To do this, we used the search engine Web of Science to systematically sample a subset of the published literature with 'biodiversity' in the title. In total 526 research papers were screened-5% of all papers in Web of Science with biodiversity in the title. For each paper, details on taxonomic group, title phrasing, number of citations, study location, and author locations were recorded. Compared to the proportions of described species, we identified a considerable taxonomic weighting towards vertebrates and an under-representation of invertebrates (particularly arachnids and insects) in the published literature. This discrepancy is more pronounced in highly cited papers, and in tropical regions, with only 43% of biodiversity research in the tropics including invertebrates. Furthermore, while papers on vertebrate taxa typically did not specify the taxonomic group in the title, the converse was true for invertebrate papers. Biodiversity research is also biased geographically: studies are more frequently carried out in developed countries with larger economies, and for a given level of species or threatened species, tropical countries were understudied relative to temperate countries. Finally, biodiversity research is disproportionately authored by researchers from wealthier countries, with studies less likely to be carried out by scientists in lower-GDP nations. Our results highlight the need for a more systematic and directed evaluation of biodiversity studies, perhaps informing more targeted research towards those areas and taxa most depauperate in research. Only by doing so can we ensure that biodiversity research yields results that are relevant and applicable to all regions and that the information necessary for the conservation of threatened species is available to conservation practitioners
Novel partners support two-way by-product mutualism in a converted ecosystem
Dissertação de Mestrado em Química Medicinal apresentada à Faculdade de Ciências e Tecnologia da Universidade de Coimbra.Nas sociedades modernas assiste-se a um aumento crescente do número de bactérias e
vírus com resistência aos fármacos atualmente disponibilizados pela indústria farmacêutica. Dada a
relevância da problemática mencionada, o objetivo central do trabalho apresentado nesta
dissertação consiste no desenvolvimento de métodos de síntese de novas entidades químicas
biocompatíveis constituídas por macrociclos tetrapirrólicos e sulfonamidas, tendo em vista a sua
futura potencial aplicação dual como antibacteriano per si e como fotossensibilizador para inativação
de bactérias recorrendo a terapia fotodinâmica. A combinação destas duas famílias de compostos
pode ocorrer por ligação covalente ou via self-assembly, subdividindo o trabalho apresentado.
No capítulo 1 apresenta-se uma revisão crítica e selecionada da literatura subjacente aos
diferentes tópicos estudados. No capítulo 2 descreve-se uma estratégia de síntese de macrociclos
tetrapirrólicos e sulfonamidas unidas por ligação covalente. Neste começa-se por selecionar a a
5,10,15,20-tetraquis(pentafluorofenil)porfirina como porfirina base para realizar os estudos de
otimização da sua derivatização com a metanosulfonamida, conseguindo-se obter com sucesso
condições de síntese seletivas para a formação da 5-[2’,3’,5’,6’-tetrafluoro-4’-
metanosulfamoil)fenil]-10,15,20-tri-[(2’,3’,4’,5’,6’-pentafluoro)fenil]porfirina (composto
monossubstituido) ou da 5,10,15,20-tetra-[2’,3’,5’,6’-tetrafluoro-4’-metanosulfamoil)fenil]porfirina
(composto tetrassubstituído) com rendimentos de 19% e 70%, respetivamente. Com o intuito de
avaliar o efeito da estrutura da sulfonamida na reatividade alargaram-se os estudos utilizando como
nucleófilo duas sulfonamidas previamente sintetizadas no decorrer do trabalho: ptoluenosulfonamida
e N-metil-p-toluenosulfonamida. Através deste estudo foi possível sintetizar e
isolar os compostos mono e dissubstituídos da família da p-toluenosulfonamida (5-[(2’,3’,5’,6’-
tetrafluoro-4’-p-toluenosulfamoil)fenil]-10,15,20-tri-[(2’,3’,4’,5’,6’-pentafluoro)fenil]porfirina e
mistura de 5,10-[(2’,3’,5’,6’-tetrafluoro-4’-p-toluenosulfamoil)fenil]-15,20-dis-[(2’,3’,4’,5’,6’-
pentafluoro)fenil]porfirina e 5,15-[(2’,3’,5’,6’-tetrafluoro-4’-p-toluenosulfamoil)fenil]-10,20-
[(2’,3’,4’,5’,6’-pentafluoro)fenil]porfirina) e os compostos mono, di e trissubstituído referentes à
substituição com a N-metil-p-toluenosulfonamida (5-[(2’,3’,5’,6’-tetrafluoro-4’-N-metil-ptoluenosulfamoil)
fenil]-10,15,20-tri-[(2’,3’,4’,5’,6’-pentafluoro)fenil] porfirina, mistura de 5,10-
[(2’,3’,5’,6’-tetrafluoro-4’-N-metil-p-toluenosulfamoil)fenil]-15,20-dis-[(2’,3’,4’,5’,6’-
pentafluoro)fenil]porfirina e 5,15-[(2’,3’,5’,6’-tetrafluoro-4’-N-metil-p-toluenosulfamoil)fenil]-10,20-
[(2’,3’,4’,5’,6’-pentafluoro)fenil]porfirina e 5,10,15-tri-[(2’,3’,5’,6’-tetrafluoro-4’-N-metil-ptoluenosulfamoil)
fenil]-20-[(2’,3’,4’,5’,6’-pentafluoro)fenil]porfirina) com baixos rendimentos (0.6 a
4.5%). A título de exemplo, adotaram-se as condições otimizadas para a síntese da porfirina
tetrassubstituída contendo a N-metil-p-toluenosulfonamida como substituinte, obtendo-se a correspondente 5,10,15,20-tetra-[(2’,3’,5’,6’-tetrafluoro-4’-N-metil-p-toluenosulfamoil)fenil]
porfirina com um rendimento de 20%. Dado o nosso interesse no desenvolvimento de potenciais
fotossensibilizadores com espectros de absorção na designada “janela terapêutica”., prosseguimos
com estudos de redução de uma das porfirinas com hidrazina aquosa (NH2NH2·H2O) e cloreto de
ferro(III)hexahidratado (FeCl3·6H2O), tendo-se obtido a correspondente 5,10,15,20-tetra-
[2’,3’,5’,6’-tetrafluoro-4’-metanosulfamoil)fenil]clorina com rendimento de produto isolado elevado
(65%). Para além disso com recurso ao método de redução de porfirinas com ptoluenosulfonilhidrazina
sem solvente conseguiu-se obter a 5,10,15,20-tetra-[2’,3’,5’,6’-tetrafluoro-
4’-metanosulfamoil)fenil]bacterioclorina um rendimento de 70%.
Os compostos foram caracterizados fotofísicamente, tendo revelado possuir características
bastante promissoras para aplicação como fotossensibilizadores, tais como, baixos rendimentos
quânticos de fluorescência (фF≤0.1375) e rendimentos quânticos de formação de oxigénio singleto
adequados (фΔ≥0.59). Para avaliar a lipofilicidade e a interação com a membrana lipídica procedeuse
ao cálculo do coeficiente de partição das porfirinas 5-[2’,3’,5’,6’-tetrafluoro-4’-
metanosulfamoil)fenil]-10,15,20-tri-[(2’,3’,4’,5’,6’-pentafluoro)fenil]porfirina e 5,10,15,20-tetra-
[2’,3’,5’,6’-tetrafluoro-4’-metanosulfamoil)fenil]porfirina através de duas metodologias, uma delas
recorrendo à mistura octanol-água e a outra a vesículas unilamelares lipídicas (LUVs). Em suma,
verificou-se que o número de derivatizações com grupos metanosulfonamida é crucial para modular
a anfifilicidade dos compostos, sendo que estes apresentam variações significativas nos seus
coeficientes de partição octanol-água (0.94≤LogP≤4). Apesar destes valores díspares, ambos
apresentam uma elevada afinidade para as membranas lipídicas. Por fim, realizaram-se estudos
preliminares de citotoxicidade no escuro, com a linha celular 3T3, demonstrando-se que o
composto não apresenta toxicidade in vitro.
No capítulo 3 desenvolve-se uma metodologia baseada no conceito de self-assembly, para a
preparação de estruturas contendo porfirinas catiónicas descritas na inativação de bactérias [iodeto
de 5,10,15,20-tetraquis(4-metilpiridil)porfirinato de zinco (II) e iodeto de 5,10,15,20-tetraquis(1,3-
dimetilimidazol-2-il)porfirinato de zinco (II)] e a Sulfadiazina, uma sulfonamida com atividade
bacteriostática comprovada.
No capítulo 4 apresenta-se detalhadamente os procedimentos experimentais referentes a
todos os capítulos da tese bem como a caracterização química completa de todas as moléculas
sintetizadas no decorrer do trabalho (1H RMN, 19F RMN, espectrometria de massa e absorção UVVisModern society is witnessing an increasing number of drug-resistant bacteria and viruses.
Due to the relevance of the subject, this work presents new methods for the synthesis of
biocompatible conjugates of sulfonamides and tetrapyrrolic macrocycles for dual chemo and
photodynamic therapy. The combination of these two families of compounds may occur by
covalent binding or by self-assembly. Therefore, the work here presented is subdivided.
The chapter 1 presents a critical and selected review of the literature underlying to
differentstudy topics. The chapter 2 describes a synthetic strategy for preparing tetrapyrrolic
macrocycles substituted with sulfonamides by covalent binding. First, we selected 5,10,15,20-
tetrakis(pentafluorophenyl)porphyrin as starting material to carry out the methanesulfonamide
derivatization optimization studies. Selective synthesis conditions were successfully obtained for the
formation of 5-[2’,3’,5’,6’-tetrafluoro-4’-methanesulfamoyl)phenyl]-10,15,20-tri-[(2’,3’,4’,5’,6’-
pentafluoro)phenyl]porphyrin (mono-substituted compound) or 5,10,15,20-tetra-[(2’,3’,5’,6’-
tetrafluoro-4’-methanesulfamoyl)phenyl]porphyrin (tetra-substituted compound) in 19% and 70 %,
yields, respectively. In order to evaluate the effect of the sulfonamide structure in the reactivity, we
extended the studies using two sulfonamides previously synthesized in this work as nucleophiles: ptoluenesulfonamide
and N-methyl-p-toluenesulfonamide. From this study, it was possible to
synthesize and isolate the mono and disubstituted compounds of the p-toluenesulfonamide family
(5-[(2’,3’,5’,6’-tetrafluoro-4’-p-toluenesulfamoyl)phenyl]-10,15,20-tri-[(2’,3’,4’,5’,6’-
pentafluoro)phenyl]porphyrin, mixture of 5,10-[(2’,3’,5’,6’-tetrafluoro-4’-ptoluenesulfamoyl)
phenyl]-15,20-dis-[(2’,3’,4’,5’,6’-pentafluoro)phenyl]porphyrin and 5,15-
[(2’,3’,5’,6’-tetrafluoro-4’-p-toluenesulfamoyl)phenyl]-10,20-[(2’,3’,4’,5’,6’-
pentafluoro)phenyl]porphyrin) and the mono-, di- and tri-substituted compounds related to
substitution with the N-methyl-p-toluenesulfonamide (5-[(2’,3’,5’,6’-tetrafluoro-4’-N-methyl-ptoluenesulfamoyl)
phenyl]-10,15,20-tri-[(2’,3’,4’,5’,6’-pentafluoro)phenyl]porphyrin, mixture of 5,10-
[(2’,3’,5’,6’-tetrafluoro-4’-N-methyl-p-toluenesulfamoyl)phenyl]-15,20-dis-[(2’,3’,4’,5’,6’-pentafluoro)
phenyl]porphyrin and 5,15-[(2’,3’,5’,6’-tetrafluoro-4’-N-methyl-p-toluenesulfamoyl)phenyl]-10,20-
[(2’,3’,4’,5’,6’-pentafluoro)phenyl]porphyrin and 5,10,15-tri-[(2’,3’,5’,6’-tetrafluoro-4’-N-methyl-ptoluenesulfamoyl)
phenyl]-20-[(2’,3’,4’,5’,6’-pentafluoro)phenyl]porphyrin) in low yields (0.6 to
4.5%). The optimized conditions for the synthesis of tetra-substituted porphyrin were adopted
using the N-methyl-p-toluenesulfonamide as nucleophile. We obtained the corresponding
5,10,15,20-tetra[(2',3',5',6'-tetrafluoro-4'-N-methyl-p-toluenesulfamoyl) phenyl]porphyrin in 20%
yield . We proceeded with the reduction studies of one of the synthesized porphyrins, using
catalytic amounts of ferric chloride hexahydrate (FeCl3·6H2O) and aqueous hydrazine
(NH2NH2·H2O), affording the corresponding 5,10,15,20-tetra [2 ', 3', 5 ', 6'-tetrafluoro-4'-
methanesulfamoyl) phenyl] chlorin in high yield (65%). Furthermore, we used the solvent free
synthetic methodology via reduction with p-toluenesulfonylhydrazide to obtain the 5,10,15,20-
tetra[2 ', 3', 5 ', 6'-tetrafluoro-4'- methanesulfamoyl) phenyl]bacteriochlorin in 70% yield.
The photophysical assessment shows that the compounds have very promising
characteristics to be used as photosensitizers, such as low fluorescence quantum yields (фF≤0.1375)
and suitable quantum yields of singlet oxygen formation (фΔ≥0.59). The lipophilicity and the
interaction with the lipid membrane was evaluated by calculating the partition coefficient of 5-
[2’,3’,5’,6’-tetrafluoro-4’-methanesulfamoyl)phenyl]-10,15,20-tri-[(2’,3’,4’,5’,6’-
pentafluoro)phenyl]porphyrin and 5,10,15,20-tetra-[(2’,3’,5’,6’-tetrafluoro-4’-
methanesulfamoyl)phenyl]porphyrin using two methods, the octanol/water partition coefficients
and lipid unilamellar vesicles (LUVs). From the values obtained, we can assume that the number of
metanesulfonamide fragments is crucial to modulate the amphiphilicity of the compounds. While
the mono-substituted porphyrin display a logPow>4, the tetra-substituted porphyrin shows a value
of log Pow =0.937. Despite these distinct values, both display high lipid membrane affinity. Finally,
preliminary in vitro tests with 3T3 fibroblast cell line show that the compound is not toxic.
In chapter 3 a methodology based on the self-assembly concept is developed for the
preparation of structures containing cationic porphyrins described in bacteria inactivation
[5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrinate zinc (II) tetraiodide, 5,10,15,20-
tetrakis(1,3-dimethylimidazolium-2-yl) porphyrinate zinc (II) tetraiodide] and Sulfadiazine, a
sulfonamide with proven bacteriostatic activity.
The chapter 4 presents detailed experimental procedures relating to all the chapters of this
thesis, as well as complete chemical characterization of all synthesized compounds (1H NMR, 19F
NMR, mass spectrometry and UV-Vis absorption)
Image-based analyses from an online repository provide rich information on long-term changes in morphology and human perceptions of rhinos
Online image repositories can offer a freely accessible, information-rich and cost-effective alternative to museum collections for studying long-term changes in human interactions with nature and ecological and evolutionary change. The Rhino Resource Center (RRC) is one example, curated by experts and holding a collection of >4000 rhino images, including both artistic portrayals (1481-2021) and photographs (taken between 1862-2021), and representing a potentially valuable case study to investigate the utility of online image repositories for research into large vertebrates and, potentially, other well-recorded smaller taxa. The five extant species of rhino are all threatened by habitat loss and human hunting and therefore are an important focus for conservation research. We used the RRC for two separate research approaches: (i) assessing the changing representations and human interactions with rhinos using 3158 images (1531 pieces of artwork and 1627 photographs); and (ii) determining to what extent morphological data can be extracted from photographs to assess changes in horn length over time, using a sample size of 80 photographs of rhinos taken in profile view. We found that African rhino species have become more commonly depicted in images, compared to Asian rhino species over time. During the age of European imperialism (between the 16th and 20th centuries), rhinos were commonly portrayed as hunting trophies, but since the mid-20th century, they have been increasingly portrayed in a conservation context, reflecting a change in emphasis from a more to less consumptive relationship between humans and rhinos. Finally, we found evidence for declining horn length over time across species, perhaps related to selective pressure of hunting, and indicating a utility for image-based approaches in understanding societal perceptions of large vertebrates and trait evolution. Read the free Plain Language Summary for this article on the Journal blog.Peer reviewe
Treatment of lung disease in alpha-1 antitrypsin deficiency: a systematic review - Supplementary Material
Research data used in the paper 'Treatment of lung disease in alpha-1 antitrypsin deficiency: a systematic review.', Edgar RG, Patel M, Bayliss S, Crossley D, Sapey E, Turner AM, forthcoming in The International Journal of Chronic Obstructive Pulmonary Disease (2017
Immunogenicity and safety of three consecutive production lots of the non replicating smallpox vaccine MVA: A randomised, double blind, placebo controlled phase III trial
<div><p>Background</p><p>Modified Vaccinia Ankara (MVA) is a live, viral vaccine under advanced development as a non-replicating smallpox vaccine. A randomised, double-blind, placebo-controlled phase III clinical trial was conducted to demonstrate the humoral immunogenic equivalence of three consecutively manufactured MVA production lots, and to confirm the safety and tolerability of MVA focusing on cardiac readouts.</p><p>Methods</p><p>The trial was conducted at 34 sites in the US. Vaccinia-naïve adults aged 18-40 years were randomly allocated to one of four groups using a 1:1:1:1 randomization scheme. Subjects received either two MVA injections from three consecutive lots (Groups 1-3), or two placebo injections (Group 4), four weeks apart. Everyone except personnel involved in vaccine handling and administration was blinded to treatment. Safety assessment focused on cardiac monitoring throughout the trial. Vaccinia-specific antibody titers were measured using a Plaque Reduction Neutralization Test (PRNT) and an Enzyme-Linked Immunosorbent Assay (ELISA). The primary immunogenicity endpoint was Geometric Mean Titers (GMTs) after two MVA vaccinations measured by PRNT at trial visit 4. This trial is registered with ClinicalTrials.gov, number NCT01144637.</p><p>Results</p><p>Between March 2013 and May 2014, 4005 subjects were enrolled and received at least one injection of MVA (n = 3003) or placebo (n = 1002). The three MVA lots induced equivalent antibody titers two weeks after the second vaccination, with seroconversion rates of 99·8% (PRNT) and 99·7% (ELISA). Overall, 180 (6·0%) subjects receiving MVA and 29 (2·9%) subjects in the placebo group reported at least one unsolicited Adverse Event (AE) that was considered trial-related. Vaccination was well tolerated without significant safety concerns, particularly regarding cardiac assessment.</p><p>Conclusions</p><p>The neutralizing and total antibody titers induced by each of the three lots were equivalent. No significant safety concerns emerged in this healthy trial population, especially regarding cardiac safety, thus confirming the excellent safety and tolerability profile of MVA.</p><p>Trial registration</p><p>ClinicalTrials.gov <a href="https://clinicaltrials.gov/ct2/show/NCT01144637" target="_blank">NCT01144637</a></p></div
Whole-ecosystem experimental manipulations of tropical forests.
Tropical forests are highly diverse systems involving extraordinary numbers of interactions between species, with each species responding in a different way to the abiotic environment. Understanding how these systems function and predicting how they respond to anthropogenic global change is extremely challenging. We argue for the necessity of 'whole-ecosystem' experimental manipulations, in which the entire ecosystem is targeted, either to reveal the functioning of the system in its natural state or to understand responses to anthropogenic impacts. We survey the current range of whole-ecosystem manipulations, which include those targeting weather and climate, nutrients, biotic interactions, human impacts, and habitat restoration. Finally we describe the unique challenges and opportunities presented by such projects and suggest directions for future experiments.This review was initiated during a symposium on ‘The effects of large
scale manipulations of tropical forests on arthropod assemblages’ at the
INTECOL 2013 congress, London 18–23 August 2013. T.M.F. is funded
by the Australian Research Council (DP140101541), T.M.F. and R.M.E.
by Yayasan Sime Darby, TMF and Y.B. by the project Biodiversity
of Forest Ecosystems (CZ.1.07/2.3.00/20.0064) co-financed by the
European Social Fund and the state budget of the Czech Republic,
and T.M.F. Y.B. and V.N. by the Czech Science Foundation (GACR
14-32302S, 14-36098G, 14-04258S respectively). Y.B. is also supported
by the Sistema Nacional de Investigacio´n of Panama. E.C.T. is
supported by funds from PT SMART Research Institute and the Isaac
Newton Trust, Cambridge. R.M.E. is supported by European Research
Council Project number 281986. We are grateful to Maureen Fayle,
Andrew Hector, Jan Leps, Scott Miller, Kalsum M. Yusah, Paul Craze,
and two anonymous reviewers for advice during the drafting of the
manuscript, and Jennifer Balch for additional information regarding
her burning experiments.This is the final published version. It first appeared at http://www.cell.com/trends/ecology-evolution/abstract/S0169-5347%2815%2900069-5
Passing to an effective 4D phantom cosmology from 5D vacuum theory of gravity
Starting from a five-dimensional (5D) vacuum theory of gravity where the
extra coordinate is considered as noncompact, we investigate the possibility of
inducing four-dimensional (4D) phantom scenarios by applying form-invariance
symmetry transformations. In particular we obtain phantom scenarios for two
cosmological frameworks. In the first framework we deal with an induced 4D
de-Sitter expansion and in the second one a 4D induced model where the
expansion of the universe is dominated by a decreasing cosmological parameter
is discussed.Comment: version accepted in Physics Letters
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