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1.
Proc Natl Acad Sci U S A ; 118(19)2021 05 11.
Artigo em Inglês | MEDLINE | ID: mdl-33941703

RESUMO

Stable carbon and nitrogen isotope analyses are widely used to infer diet and mobility in ancient and modern human populations, potentially providing a means to situate humans in global food webs. We collated 13,666 globally distributed analyses of ancient and modern human collagen and keratin samples. We converted all data to a common "Modern Diet Equivalent" reference frame to enable direct comparison among modern human diets, human diets prior to the advent of industrial agriculture, and the natural environment. This approach reveals a broad diet prior to industrialized agriculture and continued in modern subsistence populations, consistent with the human ability to consume opportunistically as extreme omnivores within complex natural food webs and across multiple trophic levels in every terrestrial and many marine ecosystems on the planet. In stark contrast, isotope dietary breadth across modern nonsubsistence populations has compressed by two-thirds as a result of the rise of industrialized agriculture and animal husbandry practices and the globalization of food distribution networks.


Assuntos
Isótopos de Carbono/análise , Dieta/história , Saúde Global/estatística & dados numéricos , Isótopos de Nitrogênio/análise , Algoritmos , Osso e Ossos/química , Colágeno/análise , Geografia , Cabelo/química , História do Século XX , História do Século XXI , História Antiga , Humanos , Queratinas/análise , Unhas/química
2.
Environ Sci Technol ; 57(35): 13067-13078, 2023 09 05.
Artigo em Inglês | MEDLINE | ID: mdl-37603309

RESUMO

Aerosol black carbon (BC) is a short-lived climate pollutant. The poorly constrained provenance of tropical marine aerosol BC hinders the mechanistic understanding of extreme climate events and oceanic carbon cycling. Here, we collected PM2.5 samples during research cruise NORC2016-10 through South China Sea (SCS) and Northeast Indian Ocean (NEIO) and measured the dual-carbon isotope compositions (δ13C-Δ14C) of BC using hydrogen pyrolysis technique. Aerosol BC exhibits six different δ13C-Δ14C isotopic spaces (i.e., isotope provinces). Liquid fossil fuel combustion, from shipping emissions and adjacent land, is the predominant source of BC over isotope provinces "SCS close to Chinese Mainland" (53.5%), "Malacca Strait" (53.4%), and "Open NEIO" (40.7%). C3 biomass burning is the major contributor to BC over isotope provinces "NEIO close to Southeast Asia" (55.8%), "Open NEIO" (41.3%), and "Open SCS" (40.0%). Coal combustion and C4 biomass burning show higher contributions to BC over "Sunda Strait" and "Open SCS" than the others. Overall, NEIO near the Bay of Bengal, Malacca Strait, and north SCS are three hot spots of fossil fuel-derived BC; the first two areas are also hot spots of biomass-derived BC. The comparable δ13C-Δ14C between BC in aerosol and dissolved BC in surface seawater may suggest atmospheric BC deposition as a potential source of oceanic dissolved BC.


Assuntos
Combustíveis Fósseis , Oceano Índico , Aerossóis , Isótopos de Carbono , China
3.
Proc Natl Acad Sci U S A ; 117(8): 3996-4006, 2020 02 25.
Artigo em Inglês | MEDLINE | ID: mdl-32047039

RESUMO

The future response of the Antarctic ice sheet to rising temperatures remains highly uncertain. A useful period for assessing the sensitivity of Antarctica to warming is the Last Interglacial (LIG) (129 to 116 ky), which experienced warmer polar temperatures and higher global mean sea level (GMSL) (+6 to 9 m) relative to present day. LIG sea level cannot be fully explained by Greenland Ice Sheet melt (∼2 m), ocean thermal expansion, and melting mountain glaciers (∼1 m), suggesting substantial Antarctic mass loss was initiated by warming of Southern Ocean waters, resulting from a weakening Atlantic meridional overturning circulation in response to North Atlantic surface freshening. Here, we report a blue-ice record of ice sheet and environmental change from the Weddell Sea Embayment at the periphery of the marine-based West Antarctic Ice Sheet (WAIS), which is underlain by major methane hydrate reserves. Constrained by a widespread volcanic horizon and supported by ancient microbial DNA analyses, we provide evidence for substantial mass loss across the Weddell Sea Embayment during the LIG, most likely driven by ocean warming and associated with destabilization of subglacial hydrates. Ice sheet modeling supports this interpretation and suggests that millennial-scale warming of the Southern Ocean could have triggered a multimeter rise in global sea levels. Our data indicate that Antarctica is highly vulnerable to projected increases in ocean temperatures and may drive ice-climate feedbacks that further amplify warming.

4.
Early Child Educ J ; : 1-14, 2022 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-35967911

RESUMO

Findings suggest that an eight-week mindfulness compassion-based program, Cultivating Healthy Intentional Mindful Educators (CHIME), is a feasible professional development intervention for early childhood (EC) teachers to support their emotion regulation and psychological and workplace well-being. We offer preliminary evidence that learning about mindfulness, self-compassion, and social-emotional learning supports EC teachers in strengthening their knowledge and application of practices to be more mindful and less emotionally reactive and emotionally exhausted at work. In analyzing both EC teacher feedback and survey data from two pilot studies, there was promising evidence that participating in CHIME enhanced awareness of emotions and the development of strategies to manage emotions. As CHIME is further developed and refined it will be integral to have collaborative engagement and participation from EC teachers and programs to ensure that learning these practices are relevant, helpful, meaningful, and sustainable.

5.
J Strength Cond Res ; 35(6): 1542-1546, 2021 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-33927119

RESUMO

ABSTRACT: Mann, JB, Bird, M, Signorile, JF, Brechue, WF, and Mayhew, JL. Prediction of anaerobic power from standing long jump in NCAA Division IA football players. J Strength Cond Res 35(6): 1542-1546, 2021-Despite the popularity of the standing long jump (SLJ), limited research has explored the estimation of power developed during this test. The purpose of this study was to determine SLJ power from jump distance and selected anthropometric measures in NCAA Division IA football players. Height (Ht), body mass (Wt), thigh length, and lower leg length (LL) were measured in 58 players, allowing calculation of leg ratios of thigh length·Ht-1, LL·Ht-1, and TL·SL-1. Players performed 2-3 maximal familiarization trials of SLJ followed by 2 maximal jumps from a 3-dimension force plate sampling at 1,000 Hz. Standing long jump distance (intraclass correlation coefficient [ICC] = 0.944) and power (ICC = 0.926) calculated from resultant force and velocity vectors were highly reliable. Standing Ht (r = 0.40), Wt (r = 0.36), lower leg length (r = 0.43), total leg length (thigh + LLs) (r = 0.38), and best SLJ (r = 0.52) were significantly related (p < 0.05) to peak power, but none accounted for more than 27% of the common variance. Step-wise multiple regression identified SLJ and body mass as the only significant variables necessary to predict peak power (Power [W] = 32.49·SLJ [cm] + 39.69·Wt [kg] - 7,608, R = 0.86, SEE = 488 W, CV% = 9.3%). Standing long jump contributed 56.8% to the known variance, whereas Wt contributed 43.2%. Thus, a combination of SLJ and Wt can be used to effectively estimate explosive power in Division IA college football players.


Assuntos
Desempenho Atlético , Futebol Americano , Futebol , Anaerobiose , Teste de Esforço , Humanos , Força Muscular , Coxa da Perna
6.
Glob Chang Biol ; 26(10): 5899-5913, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-32686242

RESUMO

The magnitude of the terrestrial carbon (C) sink may be overestimated globally due to the difficulty of accounting for all C losses across heterogeneous landscapes. More complete assessments of net landscape C balances (NLCB) are needed that integrate both emissions by fire and transfer to aquatic systems, two key loss pathways of terrestrial C. These pathways can be particularly significant in the wet-dry tropics, where fire plays a fundamental part in ecosystems and where intense rainfall and seasonal flooding can result in considerable aquatic C export (ΣFaq ). Here, we determined the NLCB of a lowland catchment (~140 km2 ) in tropical Australia over 2 years by evaluating net terrestrial productivity (NEP), fire-related C emissions and ΣFaq (comprising both downstream transport and gaseous evasion) for the two main landscape components, that is, savanna woodland and seasonal wetlands. We found that the catchment was a large C sink (NLCB 334 Mg C km-2  year-1 ), and that savanna and wetland areas contributed 84% and 16% to this sink, respectively. Annually, fire emissions (-56 Mg C km-2  year-1 ) and ΣFaq (-28 Mg C km-2  year-1 ) reduced NEP by 13% and 7%, respectively. Savanna burning shifted the catchment to a net C source for several months during the dry season, while ΣFaq significantly offset NEP during the wet season, with a disproportionate contribution by single major monsoonal events-up to 39% of annual ΣFaq was exported in one event. We hypothesize that wetter and hotter conditions in the wet-dry tropics in the future will increase ΣFaq and fire emissions, potentially further reducing the current C sink in the region. More long-term studies are needed to upscale this first NLCB estimate to less productive, yet hydrologically dynamic regions of the wet-dry tropics where our result indicating a significant C sink may not hold.


Assuntos
Carbono , Ecossistema , Austrália , Carbono/análise , Dióxido de Carbono/análise , Pradaria
7.
Ecol Appl ; 30(8): e02192, 2020 12.
Artigo em Inglês | MEDLINE | ID: mdl-32510803

RESUMO

As tropical savannas are undergoing rapid conversion to other land uses, native C3 -C4 vegetation mixtures are often transformed to C3 - or C4 -dominant systems, resulting in poorly understood changes to the soil carbon (C) cycle. Conventional models of the soil C cycle are based on assumptions that more labile components of the heterogenous soil organic C (SOC) pool decompose at faster rates. Meanwhile, previous work has suggested that the C4 -derived component of SOC is more labile than C3 -derived SOC. Here we report on long-term (18 months) soil incubations from native and transformed tropical savannas of northern Australia. We test the hypothesis that, regardless of the type of land conversion, the C4 component of SOC will be preferentially decomposed. We measured changes in the SOC and pyrogenic carbon (PyC) pools, as well as the carbon isotope composition of SOC, PyC and respired CO2 , from 63 soil cores collected intact from different land use change scenarios. Our results show that land use change had no consistent effect on the size of the SOC pool, but strong effects on SOC decomposition rates, with slower decomposition rates at C4 -invaded sites. While we confirm that native savanna soils preferentially decomposed C4 -derived SOC, we also show that transformed savanna soils preferentially decomposed the newly added pool of labile SOC, regardless of whether it was C4 -derived (grass) or C3 -derived (forestry) biomass. Furthermore, we provide evidence that in these fire-prone landscapes, the nature of the PyC pool can shed light on past vegetation composition: while the PyC pool in C4 -dominant sites was mainly derived from C3 biomass, PyC in C3-dominant sites and native savannas was mainly derived from C4 biomass. We develop a framework to systematically assess the effects of recent land use change vs. prior vegetation composition.


Assuntos
Pradaria , Solo , Austrália , Biomassa , Carbono/análise
8.
Rapid Commun Mass Spectrom ; 34(10): e8737, 2020 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-31981268

RESUMO

RATIONALE: Rapid, reliable isolation of pyrogenic carbon (PyC; also known as char, soot, black carbon, or biochar) for the determination of stable carbon isotope (δ13 C) composition and radiocarbon (14 C) dating is needed across multiple fields of research in geoscience, environmental science and archaeology. Many current techniques do not provide reliable isolation from contaminating organics and/or are relatively time-consuming. Hydrogen pyrolysis (HyPy) does provide reliable isolation of PyC, but the current methodology is time consuming. METHODS: We explored the potential for subjecting multiple samples to HyPy analysis by placing up to nine individual samples in custom-designed borosilicate sample vessels in a single reactor run. We tested for cross-contamination between samples in the same run using materials with highly divergent radiocarbon activities (~0.04-116.3 pMC), δ13 C values (-11.9 to -26.5‰) and labile carbon content. We determined 14 C/13 C using accelerator mass spectrometry and δ13 C values using an elemental analyser coupled to a continuous flow isotope ratio mass spectrometer. RESULTS: Very small but measurable transfer between samples of highly divergent isotope composition was detectable. For samples having a similar composition, this cross-contamination is considered negligible with respect to measurement uncertainty. For samples having divergent composition, we found that placing a sample vessel loaded with silica mesh adsorbent between samples eliminated measurable cross-contamination in all cases for both 14 C/13 C and δ13 C values. CONCLUSIONS: It is possible to subject up to seven samples to HyPy in the same reactor run for the determination of radiocarbon content and δ13 C value without diminishing the precision or accuracy of the results. This approach enables an increase in sample throughput of 300-600%. HyPy process background values are consistently lower than the nominal laboratory process background for quartz tube combustion in the NERC Radiocarbon Laboratory, indicating that HyPy may also be advantageous as a relatively 'clean' radiocarbon pre-treatment method.

9.
J Toxicol Environ Health B Crit Rev ; 22(7-8): 288-359, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31631808

RESUMO

This review summarizes the carcinogenic mechanisms for 109 Group 1 human carcinogens identified as causes of human cancer through Volume 106 of the IARC Monographs. The International Agency for Research on Cancer (IARC) evaluates human, experimental and mechanistic evidence on agents suspected of inducing cancer in humans, using a well-established weight of evidence approach. The monographs provide detailed mechanistic information about all carcinogens. Carcinogens with closely similar mechanisms of action (e.g. agents emitting alpha particles) were combined into groups for the review. A narrative synopsis of the mechanistic profiles for the 86 carcinogens or carcinogen groups is presented, based primarily on information in the IARC monographs, supplemented with a non-systematic review. Most carcinogens included a genotoxic mechanism.


Assuntos
Carcinogênese/induzido quimicamente , Carcinógenos/toxicidade , Neoplasias/induzido quimicamente , Animais , Humanos , Mutagênicos/toxicidade , Neoplasias/patologia
10.
J Toxicol Environ Health B Crit Rev ; 22(7-8): 237-243, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31612803

RESUMO

Volume 100 in the series of IARC Monographs on the Evaluation of Carcinogenic Risks to Humans comprises an update and review of relevant information on all agents determined to induce cancer in humans. These Group 1 agents are categorized in 6 Monographs (Volumes 100A-F) published in 2012. This paper describes the methodology and stringent criteria used in the creation of a comprehensive database on tumors noted in animals and humans for the carcinogens reviewed in Volume 100, and for additional Group 1 agents that were identified in subsequent Monographs through Volume 109. The development of this database involved the systematic collection of relevant data on tumors detected in humans and experimental animals identified by the Working Groups that conducted evaluations reported in the IARC Monographs. The database includes all human tumor sites identified by the Working Groups, along with all tumor sites for which there was sufficient evidence in experimental animals. This database provides a basis for assessing the degree of concordance between tumor sites observed in humans and experimental animals for Group 1 agents identified through Volume 109.


Assuntos
Carcinógenos/toxicidade , Bases de Dados Factuais , Neoplasias/induzido quimicamente , Animais , Animais de Laboratório , Humanos , Neoplasias/patologia
11.
J Toxicol Environ Health B Crit Rev ; 22(7-8): 264-287, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31379270

RESUMO

A database on mechanistic characteristics of human carcinogenic agents was developed by collecting mechanistic information on agents identified as human carcinogens (Group 1) by the International Agency for Research on Cancer (IARC) in the IARC Monographs on the Evaluation of Carcinogenic Risks to Humans. A two-phase process is described for the construction of the database according to 24 toxicological endpoints, derived from appropriate test systems that were acquired from data obtained from the mechanisms sections of the IARC Monographs (Section 4) and a supplementary PubMed search. These endpoints were then aligned with 10 key characteristics of human carcinogens that reflect the broader attributes of these agents relating to the development of cancer in humans. The considerations involved in linking of toxicological endpoints to key characteristics are described and specific examples of the determination of key characteristics for six specific agents (tamoxifen, hepatitis B virus, arsenic, ultraviolet and solar radiation, tobacco smoking, and dioxin) are provided. Data for humans and animals were tabulated separately, as were results for in-vivo and for in-vitro sources of information. The database was constructed to support a separate analysis of the expression of these endpoints by 86 Group 1 carcinogens, in-vivo and in-vitro along with an analysis of the key characteristics of these agents.


Assuntos
Carcinógenos/toxicidade , Bases de Dados Factuais , Neoplasias/induzido quimicamente , Animais , Carcinogênese/induzido quimicamente , Testes de Carcinogenicidade , Humanos
12.
J Toxicol Environ Health B Crit Rev ; 22(7-8): 203-236, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31795923

RESUMO

Since the inception of the IARC Monographs Programme in the early 1970s, this Programme has developed 119 Monograph Volumes on more than 1000 agents for which there exists some evidence of cancer risk to humans. Of these, 120 agents were found to meet the criteria for classification as carcinogenic to humans (Group 1). Volume 100 of the IARC Monographs, compiled in 2008-2009 and published in 2012, provided a review and update of the 107 Group 1 agents identified as of 2009. These agents were divided into six broad categories: (I) pharmaceuticals; (II) biological agents; (III) arsenic, metals, fibers and dusts; (IV) radiation; (V) personal habits and indoor combustions; and (VI) chemical agents and related occupations. The Group I agents reviewed in Volume 100, as well as five additional Group 1 agents defined in subsequent Volumes of the Monographs, were used to assess the degree of concordance between sites where tumors originate in humans and experimental animals including mice, rats, hamsters, dogs, and non-human primates using an anatomically based tumor nomenclature system, representing 39 tumor sites and 14 organ and tissue systems. This evaluation identified 91 Group 1 agents with sufficient evidence (82 agents) or limited evidence (9 agents) of carcinogenicity in animals. The most common tumors observed in both humans and animals were those of the respiratory system including larynx, lung, and lower respiratory tract. In humans, respiratory system tumors were noted for 31 of the 111 distinct Group 1 carcinogens identified up to and including Volume 109 of the IARC Monographs, comprising predominantly 14 chemical agents and related occupations in category VI; seven arsenic, metals, fibers, and dusts in category III, and five personal habits and indoor combustions in category V. Subsequent to respiratory system tumors, those in lymphoid and hematopoietic tissues (26 agents), the urothelium (18 agents), and the upper aerodigestive tract (16 agents) were most often seen in humans, while tumors in digestive organs (19 agents), skin (18 agents), and connective tissues (17 agents) were frequently seen in animals. Exposures to radiation, particularly X- and γ-radiation, and tobacco smoke were associated with tumors at multiple sites in humans. Although the IARC Monographs did not emphasize tumor site concordance between animals and humans, substantial concordance was detected for several organ and tissue systems, even under the stringent criteria for sufficient evidence of carcinogenicity used by IARC. Of the 60 agents for which at least one tumor site was identified in both humans and animals, 52 (87%) exhibited tumors in at least one of the same organ and tissue systems in humans and animals. It should be noted that some caution is needed in interpreting concordance at sites where sample size is particularly small. Although perfect (100%) concordance was noted for agents that induce tumors of the mesothelium, only two Group 1 agents that met the criteria for inclusion in the concordance analysis caused tumors at this site. Although the present analysis demonstrates good concordance between animals and humans for many, but not all, tumor sites, limitations of available data may result in underestimation of concordance.


Assuntos
Carcinogênese/induzido quimicamente , Carcinógenos/toxicidade , Neoplasias/induzido quimicamente , Animais , Animais de Laboratório , Humanos , Neoplasias/patologia , Especificidade da Espécie
13.
J Toxicol Environ Health B Crit Rev ; 22(7-8): 244-263, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31637961

RESUMO

Since the inception of the International Agency for Research on Cancer (IARC) in the early 1970s, the IARC Monographs Programme has evaluated more than 1000 agents with respect to carcinogenic hazard; of these, up to and including Volume 119 of the IARC Monographs, 120 agents met the criteria for classification as carcinogenic to humans (Group 1). Volume 100 of the IARC Monographs provided a review and update of Group 1 carcinogens. These agents were divided into six broad categories: (I) pharmaceuticals; (II) biological agents; (III) arsenic, metals, fibers, and dusts; (IV) radiation; (V) personal habits and indoor combustions; and (VI) chemical agents and related occupations. Data on biological mechanisms of action (MOA) were extracted from the Monographs to assemble a database on the basis of ten key characteristics attributed to human carcinogens. After some grouping of similar agents, the characteristic profiles were examined for 86 Group 1 agents for which mechanistic information was available in the IARC Monographs up to and including Volume 106, based upon data derived from human in vivo, human in vitro, animal in vivo, and animal in vitro studies. The most prevalent key characteristic was "is genotoxic", followed by "alters cell proliferation, cell death, or nutrient supply" and "induces oxidative stress". Most agents exhibited several of the ten key characteristics, with an average of four characteristics per agent, a finding consistent with the notion that cancer development in humans involves multiple pathways. Information on the key characteristics was often available from multiple sources, with many agents demonstrating concordance between human and animal sources, particularly with respect to genotoxicity. Although a detailed comparison of the characteristics of different types of agents was not attempted here, the overall characteristic profiles for pharmaceutical agents and for chemical agents and related occupations appeared similar. Further in-depth analyses of this rich database of characteristics of human carcinogens are expected to provide additional insights into the MOA of human cancer development.


Assuntos
Carcinógenos/toxicidade , Mutagênicos/toxicidade , Neoplasias/induzido quimicamente , Animais , Carcinogênese/induzido quimicamente , Testes de Carcinogenicidade , Humanos , Agências Internacionais , Mutagênese , Neoplasias/patologia
14.
Proc Natl Acad Sci U S A ; 113(41): 11477-11482, 2016 10 11.
Artigo em Inglês | MEDLINE | ID: mdl-27671630

RESUMO

The Pleistocene global dispersal of modern humans required the transit of arid and semiarid regions where the distribution of potable water provided a primary constraint on dispersal pathways. Here, we provide a spatially explicit continental-scale assessment of the opportunities for Pleistocene human occupation of Australia, the driest inhabited continent on Earth. We establish the location and connectedness of persistent water in the landscape using the Australian Water Observations from Space dataset combined with the distribution of small permanent water bodies (springs, gnammas, native wells, waterholes, and rockholes). Results demonstrate a high degree of directed landscape connectivity during wet periods and a high density of permanent water points widely but unevenly distributed across the continental interior. A connected network representing the least-cost distance between water bodies and graded according to terrain cost shows that 84% of archaeological sites >30,000 y old are within 20 km of modern permanent water. We further show that multiple, well-watered routes into the semiarid and arid continental interior were available throughout the period of early human occupation. Depletion of high-ranked resources over time in these paleohydrological corridors potentially drove a wave of dispersal farther along well-watered routes to patches with higher foraging returns.


Assuntos
Migração Humana , Água , Arqueologia , Austrália , Geografia , Humanos , Modelos Teóricos , Recursos Hídricos
15.
Rapid Commun Mass Spectrom ; 32(12): 1008-1014, 2018 Jun 30.
Artigo em Inglês | MEDLINE | ID: mdl-29603458

RESUMO

RATIONALE: Continuous measurement of stable O and H isotope compositions in water vapour requires automated calibration for remote field deployments. We developed a new low-cost device for calibration of both water vapour mole fraction and isotope composition. METHODS: We coupled a commercially available dew point generator (DPG) to a laser spectrometer and developed hardware for water and air handling along with software for automated operation and data processing. We characterised isotopic fractionation in the DPG, conducted a field test and assessed the influence of critical parameters on the performance of the device. RESULTS: An analysis time of 1 hour was sufficient to achieve memory-free analysis of two water vapour standards and the δ18 O and δ2 H values were found to be independent of water vapour concentration over a range of ≈20,000-33,000 ppm. The reproducibility of the standard vapours over a 10-day period was better than 0.14 ‰ and 0.75 ‰ for δ18 O and δ2 H values, respectively (1 σ, n = 11) prior to drift correction and calibration. The analytical accuracy was confirmed by the analysis of a third independent vapour standard. The DPG distillation process requires that isotope calibration takes account of DPG temperature, analysis time, injected water volume and air flow rate. CONCLUSIONS: The automated calibration system provides high accuracy and precision and is a robust, cost-effective option for long-term field measurements of water vapour isotopes. The necessary modifications to the DPG are minor and easily reversible.

16.
Bioorg Med Chem Lett ; 28(16): 2679-2681, 2018 09 01.
Artigo em Inglês | MEDLINE | ID: mdl-29739642

RESUMO

The benzimidazole moiety is a ubiquitous pharmacophore present in numerous anthelmintic, antibacterial, antiviral, antineoplastic, and antifungal drugs. While the polypharmacology of this heterocycle has spurred the development of numerous solution-phase syntheses, only a handful of disparate and inefficient methods detailing its synthesis on-resin have been reported. Here we report the concise and expedient syntheses of internal and C-terminal peptidic benzimidazoles - an emerging class of peptide deformylase (PDF)-inhibiting antimicrobials. This method benefits from being performed wholly on solid-phase at room temperature resulting in minimal purification and tolerance of temperature-sensitive functionality.


Assuntos
Benzimidazóis/síntese química , Oligopeptídeos/síntese química , Resinas Sintéticas/química , Técnicas de Química Sintética/métodos
17.
Angew Chem Int Ed Engl ; 57(36): 11634-11639, 2018 09 03.
Artigo em Inglês | MEDLINE | ID: mdl-29908104

RESUMO

Facile synthesis of C-terminal thioesters is integral to native chemical ligation (NCL) strategies for chemical protein synthesis. We introduce a new method of mild peptide activation, which leverages solid-phase peptide synthesis (SPPS) on an established resin linker and classical heterocyclic chemistry to convert C-terminal peptide hydrazides into their corresponding thioesters via an acyl pyrazole intermediate. Peptide hydrazides, synthesized on established trityl chloride resins, can be activated in solution with stoichiometric acetyl acetone (acac), readily proceed to the peptide acyl pyrazoles. Acyl pyrazoles are mild acylating agents and are efficiently exchanged with an aryl thiol, which can then be directly utilized in NCL. The mild, chemoselective, and stoichiometric activating conditions allow this method to be utilized through multiple sequential ligations without intermediate purification steps.


Assuntos
Peptídeos/síntese química , Pirazóis/síntese química , Técnicas de Síntese em Fase Sólida/métodos , Acilação , Sequência de Aminoácidos , Ésteres/síntese química , Ésteres/química , Peptídeos/química , Pirazóis/química , Técnicas de Síntese em Fase Sólida/economia , Compostos de Enxofre/síntese química , Compostos de Enxofre/química
19.
Glob Chang Biol ; 23(11): 4873-4883, 2017 11.
Artigo em Inglês | MEDLINE | ID: mdl-28560838

RESUMO

Our ability to model global carbon fluxes depends on understanding how terrestrial carbon stocks respond to varying environmental conditions. Tropical forests contain the bulk of the biosphere's carbon. However, there is a lack of consensus as to how gradients in environmental conditions affect tropical forest carbon. Papua New Guinea (PNG) lies within one of the largest areas of contiguous tropical forest and is characterized by environmental gradients driven by altitude; yet, the region has been grossly understudied. Here, we present the first field assessment of aboveground biomass (AGB) across three main forest types of PNG using 193 plots stratified across 3,100-m elevation gradient. Unexpectedly, AGB had no direct relationship to rainfall, temperature, soil, or topography. Instead, natural disturbances explained most variation in AGB. While large trees (diameter at breast height > 50 cm) drove altitudinal patterns of AGB, resulting in a major peak in AGB (2,200-3,100 m) and some of the most carbon-rich forests at these altitudes anywhere. Large trees were correlated to a set of climatic variables following a hump-shaped curve. The set of "optimal" climatic conditions found in montane cloud forests is similar to that of maritime temperate areas that harbor the largest trees in the world: high ratio of precipitation to evapotranspiration (2.8), moderate mean annual temperature (13.7°C), and low intra-annual temperature range (7.5°C). At extreme altitudes (2,800-3,100 m), where tree diversity elsewhere is usually low and large trees are generally rare or absent, specimens from 18 families had girths >70 cm diameter and maximum heights 20-41 m. These findings indicate that simple AGB-climate-edaphic models may not be suitable for estimating carbon storage in forests where optimal climate niches exist. Our study, conducted in a very remote area, suggests that tropical montane forests may contain greater AGB than previously thought and the importance of securing their future under a changing climate is therefore enhanced.


Assuntos
Altitude , Biomassa , Clima , Florestas , Árvores/fisiologia , Mudança Climática , Papua Nova Guiné
20.
Nature ; 476(7358): 51-6, 2011 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-21814275

RESUMO

The role of African savannahs in the evolution of early hominins has been debated for nearly a century. Resolution of this issue has been hindered by difficulty in quantifying the fraction of woody cover in the fossil record. Here we show that the fraction of woody cover in tropical ecosystems can be quantified using stable carbon isotopes in soils. Furthermore, we use fossil soils from hominin sites in the Awash and Omo-Turkana basins in eastern Africa to reconstruct the fraction of woody cover since the Late Miocene epoch (about 7 million years ago). (13)C/(12)C ratio data from 1,300 palaeosols at or adjacent to hominin sites dating to at least 6 million years ago show that woody cover was predominantly less than ∼40% at most sites. These data point to the prevalence of open environments at the majority of hominin fossil sites in eastern Africa over the past 6 million years.


Assuntos
Evolução Biológica , Ecossistema , Hominidae/fisiologia , Árvores , África Oriental , Animais , Calibragem , Isótopos de Carbono/análise , Fósseis , Marcha/fisiologia , Hominidae/anatomia & histologia , Paleontologia , Folhas de Planta/crescimento & desenvolvimento , Poaceae/crescimento & desenvolvimento , Dinâmica Populacional , Solo/química , Árvores/crescimento & desenvolvimento , Clima Tropical , Meio Selvagem , Madeira
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