906 resultados para trophic cascade
Resumo:
The diterpenoid constituents of the Isodon plants have attracted reasearchers interested in both their chemical structures and biological properties for more than a half-century. In recent years, the isolations of new members displaying previously unprecedented ring systems and highly selective biological properties have piqued interest from the synthetic community in this class of natural products.
Reported herein is the first total synthesis of such a recently isolated diterpenoid, (–)-maoecrystal Z. The principal transformations implemented in this synthesis include two highly diastereoselective radical cyclization reactions: a Sm(II)-mediated reductive cascade cyclization, which forms two rings and establishes four new stereocenters in a single step, and a Ti(III)-mediated reductive epoxide-acrylate coupling that yields a functionalized spirolactone product, which forms a core bicycle of maoecrystal Z.
The preparation of two additional ent-kauranoid natural products, (–)-trichorabdal A and (–)-longikaurin E, is also described from a derivative of this key spirolactone. These syntheses are additionally enabled by the palladium-mediated oxidative cyclization reaction of a silyl ketene acetal precursor that is used to install the bridgehead all-carbon quaternary stereocenter and bicyclo[3.2.1]octane present in each natural product. These studies have established a synthetic relationship among three architecturally distinct ent-kaurane diterpenoids and have forged a path for the preparation of interesting unnatural ent-kauranoid structural analogs for more thorough biological study.
Resumo:
Efficient and accurate localization of membrane proteins is essential to all cells and requires a complex cascade of interactions between protein machineries. This is exemplified in the recently discovered Guided Entry of Tail-anchored protein pathway, in which the central targeting factor Get3 must sequentially interact with three distinct binding partners (Get4, Get1 and Get2) to ensure the targeted delivery of Tail-anchored proteins to the endoplasmic reticulum membrane. To understand the molecular and energetic principles that provide the vectorial driving force of these interactions, we used a quantitative fluorescence approach combined with mechanistic enzymology to monitor the effector interactions of Get3 at each stage of Tail-anchored protein targeting. We show that nucleotide and membrane protein substrate generate a gradient of interaction energies that drive the cyclic and ordered transit of Get3 from Get4 to Get2 and lastly to Get1. These data also define how the Get3/Tail-anchored complex is captured, handed over, and disassembled by the Get1/2 receptor at the membrane, and reveal a novel role for Get4/5 in recycling Get3 from the endoplasmic reticulum membrane at the end of the targeting reaction. These results provide general insights into how complex cascades of protein interactions are coordinated and coupled to energy inputs in biological systems.
Resumo:
We simulate incompressible, MHD turbulence using a pseudo-spectral code. Our major conclusions are as follows.
1) MHD turbulence is most conveniently described in terms of counter propagating shear Alfvén and slow waves. Shear Alfvén waves control the cascade dynamics. Slow waves play a passive role and adopt the spectrum set by the shear Alfvén waves. Cascades composed entirely of shear Alfvén waves do not generate a significant measure of slow waves.
2) MHD turbulence is anisotropic with energy cascading more rapidly along k⊥ than along k∥, where k⊥ and k∥ refer to wavevector components perpendicular and parallel to the local magnetic field. Anisotropy increases with increasing k⊥ such that excited modes are confined inside a cone bounded by k∥ ∝ kγ⊥ where γ less than 1. The opening angle of the cone, θ(k⊥) ∝ k-(1-γ)⊥, defines the scale dependent anisotropy.
3) MHD turbulence is generically strong in the sense that the waves which comprise it suffer order unity distortions on timescales comparable to their periods. Nevertheless, turbulent fluctuations are small deep inside the inertial range. Their energy density is less than that of the background field by a factor θ2 (k⊥)≪1.
4) MHD cascades are best understood geometrically. Wave packets suffer distortions as they move along magnetic field lines perturbed by counter propagating waves. Field lines perturbed by unidirectional waves map planes perpendicular to the local field into each other. Shear Alfvén waves are responsible for the mapping's shear and slow waves for its dilatation. The amplitude of the former exceeds that of the latter by 1/θ(k⊥) which accounts for dominance of the shear Alfvén waves in controlling the cascade dynamics.
5) Passive scalars mixed by MHD turbulence adopt the same power spectrum as the velocity and magnetic field perturbations.
6) Decaying MHD turbulence is unstable to an increase of the imbalance between the flux of waves propagating in opposite directions along the magnetic field. Forced MHD turbulence displays order unity fluctuations with respect to the balanced state if excited at low k by δ(t) correlated forcing. It appears to be statistically stable to the unlimited growth of imbalance.
7) Gradients of the dynamic variables are focused into sheets aligned with the magnetic field whose thickness is comparable to the dissipation scale. Sheets formed by oppositely directed waves are uncorrelated. We suspect that these are vortex sheets which the mean magnetic field prevents from rolling up.
8) Items (1)-(5) lend support to the model of strong MHD turbulence put forth by Goldreich and Sridhar (1995, 1997). Results from our simulations are also consistent with the GS prediction γ = 2/3. The sole not able discrepancy is that the 1D power law spectra, E(k⊥) ∝ k-∝⊥, determined from our simulations exhibit ∝ ≈ 3/2, whereas the GS model predicts ∝ = 5/3.
Resumo:
In this paper, the background to the development of an analytical quality control procedure for the Trophic Diatom Index (TDI) is explained, highlighting some of the statistical and taxonomic problems encountered, and going on to demonstrate how the system works in practice. Most diatom-based pollution indices, including the TDI, use changes in the relative proportions of different taxa to indicate changing environmental conditions. The techniques involved are therefore much simpler than those involved in many studies of phytoplankton, for example, where absolute numbers are required.
Resumo:
I. Foehn winds of southern California.
An investigation of the hot, dry and dust laden winds
occurring in the late fall and early winter in the Los Angeles
Basin and attributed in the past to the influences of the desert
regions to the north revealed that these currents were of a
foehn nature. Their properties were found to be entirely due
to dynamical heating produced in the descent from the high level
areas in the interior to the lower Los Angeles Basin. Any dust
associated with the phenomenon was found to be acquired from the
Los Angeles area rather than transported from the desert. It was
found that the frequency of occurrence of a mild type foehn of this
nature during this season was sufficient to warrant its classification
as a winter monsoon. This results from the topography of
the Los Angeles region which allows an easy entrance to the air
from the interior by virtue of the low level mountain passes north
of the area. This monsoon provides the mild winter climate of
southern California since temperatures associated with the foehn
currents are far higher than those experienced when maritime air
from the adjacent Pacific Ocean occupies the region.
II. Foehn wind cyclo-genesis.
Intense anticyclones frequently build up over the high level
regions of the Great Basin and Columbia Plateau which lie between
the Sierra Nevada and Cascade Mountains to the west and the Rocky
Mountains to the east. The outflow from these anticyclones produce
extensive foehns east of the Rockies in the comparatively low
level areas of the middle west and the Canadian provinces of
Alberta and Saskatchewan. Normally at this season of the year very
cold polar continental air masses are present over this territory
and with the occurrence of these foehns marked discontinuity surfaces
arise between the warm foehn current, which is obliged to slide over
a colder mass, and the Pc air to the east. Cyclones are
easily produced from this phenomenon and take the form of unstable
waves which propagate along the discontinuity surface between the
two dissimilar masses. A continual series of such cyclones was
found to occur as long as the Great Basin anticyclone is maintained
with undiminished intensity.
III. Weather conditions associated with the Akron disaster.
This situation illustrates the speedy development and
propagation of young disturbances in the eastern United States
during the spring of the year under the influence of the conditionally
unstable tropical maritime air masses which characterise the
region. It also furnishes an excellent example of the superiority
of air mass and frontal methods of weather prediction for aircraft
operation over the older methods based upon pressure distribution.
IV. The Los Angeles storm of December 30, 1933 to January 1, 1934.
This discussion points out some of the fundamental interactions
occurring between air masses of the North Pacific Ocean in connection
with Pacific Coast storms and the value of topographic and
aerological considerations in predicting them. Estimates of rainfall
intensity and duration from analyses of this type may be made and
would prove very valuable in the Los Angeles area in connection with
flood control problems.
Resumo:
The energy spectra of 235U atoms sputtered from a 93% enriched 235U metal foil and a hot pressed 235U02 pellet by an 80 keV 40Ar+ beam have been measured in the range 1 eV to 1 keV. The measurements were made using a mechanical time-of-flight spectrometer in conjunction with the fission track technique for detecting 235U. The design and construction of this spectrometer are discussed in detail, and its operation is mathematically analyzed.
The results of the experiment are discussed in the context of the random collision cascade model of sputtering. The spectrum obtained by the sputtering of the 235U metal target was found to be well described by the functional form E(E+Eb)-2.77, where Eb = 5.4 eV. The 235U02 target produced a spectrum that peaked at a lower energy (~ 2 eV) and decreased somewhat more rapidly for E ≳ 100 eV.
Resumo:
Nitrogen-containing heterocycles, such as indolines and pyrroloindolines, are prevalent in a variety of diverse natural products, many of which exhibit remarkable biological activities. These frameworks have inspired innovative research aimed at discovering novel methods for their stereoselective preparation.
We have developed an enantioselective synthesis of pyrroloindolines based on a formal (3 + 2) cycloaddition of indoles and 2-amidoacrylates. This reaction is promoted by (R)-BINOL•SnCl4; this complex is a Lewis acid-assisted Brønsted acid that effects a highly face-selective catalyst-controlled protonation of an enolate. Mechanistic studies also determined that the initial product of this reaction is an indolinium ion, which upon aqueous workup undergoes cyclization to the pyrroloindoline.
Based on this result, we investigated alternative nucleophiles to trap the indolinium ion. First, addition of sodium borohydride to the optimized reaction conditions yields indoline-containing amino acid derivatives.
Next, carbon nucleophiles were explored. Indole substrates incorporating a tethered alkene were exposed to the conditions for the formal (3 + 2) cycloaddition, resulting in a conjugate addition/asymmetric protonation/Prins cyclization cascade. In this transformation, the indolinium ion is attacked by the olefin, and the resulting carbocation is quenched by a chloride ion. Zirconium tetrachloride was found to be the optimal Lewis acid. Stoichiometric proton and chloride sources were also found to be crucial for reactivity.
Resumo:
Herein are described the total syntheses of all members of the transtaganolide and basiliolide natural product family. Utilitzation of an Ireland–Claisen rearrangement/Diels–Alder cycloaddition cascade (ICR/DA) allowed for rapid assembly of the transtaganolide and basiliolide oxabicyclo[2.2.2]octane core. This methodology is general and was applicable to all members of the natural product family.
A brief introduction outlines all the synthetic progress previously disclosed by Lee, Dudley, and Johansson. This also includes the initial syntheses of transtaganolides C and D, as well as basiliolide B and epi-basiliolide B accomplished by Stoltz in 2011. Lastly, we discuss our racemic synthesis of basililide C and epi-basiliolide C, which utilized an ICR/DA cascade to constuct the oxabicyclo[2.2.2]octane core and formal [5+2] annulation to form the ketene-acetal containing 7-membered C-ring.
Next, we describe a strategy for an asymmetric ICR/DA cascade, by incorporation of a chiral silane directing group. This allowed for enantioselective construction of the C8 all-carbon quaternary center formed in the Ireland–Claisen rearrangement. Furthermore, a single hydride reduction and subsequent translactonization of a C4 methylester bearing oxabicyclo[2.2.2]octane core demonstrated a viable strategy for the desired skeletal rearrangement to obtain pentacyclic transtaganolides A and B. Application of the asymmetric strategy culminated in the total syntheses of (–)-transtaganolide A, (+)-transtaganolide B, (+)-transtaganolide C, and (–)-transtaganolide D. Comparison of the optical rotation data of the synthetically derived transtaganolides to that from the isolated counterparts has overarching biosynthetic implications which are discussed.
Lastly, improvement to the formal [5+2] annulation strategy is described. Negishi cross-coupling of methoxyethynyl zinc chloride using a palladium Xantphos catalyst is optimized for iodo-cyclohexene. Application of this technology to an iodo-pyrone geranyl ester allowed for formation and isolation of the eneyne product. Hydration of the enenye product forms natural metabolite basiliopyrone. Furthermore, the eneyne product can undergo an ICR/DA cascade and form transtaganolides C and D in a single step from an achiral monocyclic precursor.
Resumo:
根据透镜的傅里叶变换性质,提出了采用光学傅里叶变换加级联光学成像放大并结合有限口径接收的方法来实现自由空间激光光束远距离传输的实验室模拟。由此原理设计了自由空间激光远距离传输模拟装置,该装置主要由大口径、长焦距的傅里叶变换平行光管和三级成像放大镜所组成,最大等效传输距离达2.4×10^5km,可用于星间激光通信终端综合通信性能的评估,在设定的误码率下测量终端可能的通信距离,或者在设定的作用通信距离下检测通信的误码率。
Resumo:
As the worldwide prevalence of diabetes mellitus continues to increase, diabetic retinopathy remains the leading cause of visual impairment and blindness in many developed countries. Between 32 to 40 percent of about 246 million people with diabetes develop diabetic retinopathy. Approximately 4.1 million American adults 40 years and older are affected by diabetic retinopathy. This glucose-induced microvascular disease progressively damages the tiny blood vessels that nourish the retina, the light-sensitive tissue at the back of the eye, leading to retinal ischemia (i.e., inadequate blood flow), retinal hypoxia (i.e., oxygen deprivation), and retinal nerve cell degeneration or death. It is a most serious sight-threatening complication of diabetes, resulting in significant irreversible vision loss, and even total blindness.
Unfortunately, although current treatments of diabetic retinopathy (i.e., laser therapy, vitrectomy surgery and anti-VEGF therapy) can reduce vision loss, they only slow down but cannot stop the degradation of the retina. Patients require repeated treatment to protect their sight. The current treatments also have significant drawbacks. Laser therapy is focused on preserving the macula, the area of the retina that is responsible for sharp, clear, central vision, by sacrificing the peripheral retina since there is only limited oxygen supply. Therefore, laser therapy results in a constricted peripheral visual field, reduced color vision, delayed dark adaptation, and weakened night vision. Vitrectomy surgery increases the risk of neovascular glaucoma, another devastating ocular disease, characterized by the proliferation of fibrovascular tissue in the anterior chamber angle. Anti-VEGF agents have potential adverse effects, and currently there is insufficient evidence to recommend their routine use.
In this work, for the first time, a paradigm shift in the treatment of diabetic retinopathy is proposed: providing localized, supplemental oxygen to the ischemic tissue via an implantable MEMS device. The retinal architecture (e.g., thickness, cell densities, layered structure, etc.) of the rabbit eye exposed to ischemic hypoxic injuries was well preserved after targeted oxygen delivery to the hypoxic tissue, showing that the use of an external source of oxygen could improve the retinal oxygenation and prevent the progression of the ischemic cascade.
The proposed MEMS device transports oxygen from an oxygen-rich space to the oxygen-deficient vitreous, the gel-like fluid that fills the inside of the eye, and then to the ischemic retina. This oxygen transport process is purely passive and completely driven by the gradient of oxygen partial pressure (pO2). Two types of devices were designed. For the first type, the oxygen-rich space is underneath the conjunctiva, a membrane covering the sclera (white part of the eye), beneath the eyelids and highly permeable to oxygen in the atmosphere when the eye is open. Therefore, sub-conjunctival pO2 is very high during the daytime. For the second type, the oxygen-rich space is inside the device since pure oxygen is needle-injected into the device on a regular basis.
To prevent too fast or too slow permeation of oxygen through the device that is made of parylene and silicone (two widely used biocompatible polymers in medical devices), the material properties of the hybrid parylene/silicone were investigated, including mechanical behaviors, permeation rates, and adhesive forces. Then the thicknesses of parylene and silicone became important design parameters that were fine-tuned to reach the optimal oxygen permeation rate.
The passive MEMS oxygen transporter devices were designed, built, and tested in both bench-top artificial eye models and in-vitro porcine cadaver eyes. The 3D unsteady saccade-induced laminar flow of water inside the eye model was modeled by computational fluid dynamics to study the convective transport of oxygen inside the eye induced by saccade (rapid eye movement). The saccade-enhanced transport effect was also demonstrated experimentally. Acute in-vivo animal experiments were performed in rabbits and dogs to verify the surgical procedure and the device functionality. Various hypotheses were confirmed both experimentally and computationally, suggesting that both the two types of devices are very promising to cure diabetic retinopathy. The chronic implantation of devices in ischemic dog eyes is still underway.
The proposed MEMS oxygen transporter devices can be also applied to treat other ocular and systemic diseases accompanied by retinal ischemia, such as central retinal artery occlusion, carotid artery disease, and some form of glaucoma.
Resumo:
Microalgas e cianobactérias têm sido amplamente recomendadas para biomonitoração de metais pesados e outros poluentes, sendo considerados indicadores sensíveis às alterações ambientais e utilizados como organismos testes na regulamentação dos níveis de metal. Estes micro-organismos fotossintetizantes são produtores primários da base da cadeia alimentar aquática e são os primeiros a serem afetados pela poluição por metais pesados. O cobre é um metal normalmente considerado como nutriente essencial para a vida aquática mas pode ser tóxico para algumas espécies. Portanto, neste estudo foram avaliados o efeito tóxico e a bioacumulação de cobre (II) em quatro espécies de micro-organismos fotoautotróficos componentes do fitoplâncton dulcícola, duas cianobactérias filamentosas (Anabaena sp. e Oscillatoria sp) e duas microalgas da classe das clorofíceas (Monorraphidium sp. e Scenedesmus sp.). O meio de cultivo utilizado nos ensaios foi o ASM-1 com e sem a presença de cobre (0,6 mg/L a 12 mg Cu2+/L) onde, o efeito tóxico do metal foi monitorado por contagem celular para as microalgas e por peso seco para as cianobactérias. A bioacumulação do metal foi avaliada da mesma forma para todos os micro-organismos, através de coletas de amostras no decorrer do experimento e determinação da concentração de cobre em solução por espectrometria de absorção atômica com chama. Os resultados obtidos mostram que o efeito tóxico do metal é diretamente proporcional à concentração inicial para os micro-organismos estudados, mas que o cobre (II) foi mais tóxico para as cianobactérias que para as microalgas verdes. A bioacumulação teve uma relação direta com o efeito tóxico do metal sobre os micro-organismos. Os resultados obtidos permitem sugerir que cobre (II) tem efeito negativo no fitoplâncton, inibindo o crescimento e alterando parâmetros metabólicos como a fotossíntese. A bioacumulação do metal pode comprometer os níveis tróficos da cadeia alimentar, afetando seu transporte para seres superiores
Experimental, Numerical and Analytical Studies of the MHD-driven plasma jet, instabilities and waves
Resumo:
This thesis describes a series of experimental, numerical, and analytical studies involving the Caltech magnetohydrodynamically (MHD)-driven plasma jet experiment. The plasma jet is created via a capacitor discharge that powers a magnetized coaxial planar electrodes system. The jet is collimated and accelerated by the MHD forces.
We present three-dimensional ideal MHD finite-volume simulations of the plasma jet experiment using an astrophysical magnetic tower as the baseline model. A compact magnetic energy/helicity injection is exploited in the simulation analogous to both the experiment and to astrophysical situations. Detailed analysis provides a comprehensive description of the interplay of magnetic force, pressure, and flow effects. We delineate both the jet structure and the transition process that converts the injected magnetic energy to other forms.
When the experimental jet is sufficiently long, it undergoes a global kink instability and then a secondary local Rayleigh-Taylor instability caused by lateral acceleration of the kink instability. We present an MHD theory of the Rayleigh-Taylor instability on the cylindrical surface of a plasma flux rope in the presence of a lateral external gravity. The Rayleigh-Taylor instability is found to couple to the classic current-driven instability, resulting in a new type of hybrid instability. The coupled instability, produced by combination of helical magnetic field, curvature of the cylindrical geometry, and lateral gravity, is fundamentally different from the classic magnetic Rayleigh-Taylor instability occurring at a two-dimensional planar interface.
In the experiment, this instability cascade from macro-scale to micro-scale eventually leads to the failure of MHD. When the Rayleigh-Taylor instability becomes nonlinear, it compresses and pinches the plasma jet to a scale smaller than the ion skin depth and triggers a fast magnetic reconnection. We built a specially designed high-speed 3D magnetic probe and successfully detected the high frequency magnetic fluctuations of broadband whistler waves associated with the fast reconnection. The magnetic fluctuations exhibit power-law spectra. The magnetic components of single-frequency whistler waves are found to be circularly polarized regardless of the angle between the wave propagation direction and the background magnetic field.
Resumo:
No decorrer das últimas décadas a pesquisa relacionada à contaminação de organismos marinhos por compostos organoclorados (OCs) se intensificou aliada à utilização de algumas espécies como sentinelas da qualidade ambiental quanto aos poluentes orgânicos. Dentre essas espécies, podem-se destacar os cetáceos, animais que entre outras características possuem grande longevidade, alta porcentagem lipídica em seus tecidos e são predadores de topo de cadeia trófica, tendendo assim a acumular altos níveis de OCs em seus tecidos. O presente estudo teve por objetivo determinar as concentrações de OCs de origem industrial e agrícola (PCBs, HCB e DDTs) em tecido hepático de oito diferentes espécies de cetáceos delfinídeos pertencentes a três distintas áreas oceânicas do Estado do Rio de Janeiro, são elas a região costeira, a plataforma continental e a região oceânica. A determinação foi realizada em cromatógrafo a gás (GC - Agilent 6890) conectado a um espectrômetro de massa (MS - Agilent 5973). Os valores de DDTs (1263617272 ng.g -1 lip.) e PCBs (7648877288 ng.g -1 lip.) aqui encontrados estão entre os mais altos já reportados para o táxon. Em todas as áreas observou-se uma predominância do ΣPCB, seguida do ΣDDT e HCB, em níveis que refletem o caráter fortemente industrial da região analisada. Entre os PCBs, a maior contribuição advém dos hexabifenis, seguida dos hepta e pentabifenis, sendo os congêneres 153, 138 e 180 os principais em todas as áreas. A razão p,pDDE/ΣDp,pDDT foi alta em todas as regiões (0,9), refletindo um input antigo do poluente na área. Foram realizadas correlações entre as concentrações de OCs e os parâmetros biológicos das espécies, como idade, sexo e comprimento total. A transferência placentária de OCs foi analisada em dois pares de fêmea-feto de Sotalia guianensis, mostrando uma maior transferência dos compostos com menor log Kow. Como esperado, foi encontrada uma diferença significativa no perfil de contaminação entre as espécies das diferentes regiões, relacionada à proximidade da fonte, características espécie-específicas e ao arranjo trófico das espécies.
Resumo:
Os diversos tipos de lançamentos de cargas poluidoras podem tornar a qualidade da água inadequada para os usos benéficos previstos. Entre as causas desta queda na qualidade da água, pode-se citar a eutrofização. O grau de trofia pode ser estimado através da utilização de índices, destacando-se o Índice do Estado Trófico desenvolvido por Carlson (1977) e o Índice do Estado Trófico desenvolvido por Carlson, modificado por Toledo et al. (1984). O presente estudo teve como principal objetivo analisar a variação espaço-temporal entre o período de 1980 a 2008, a fim de verificar o estado trófico das águas da Lagoa Rodrigo de Freitas (RJ) e do Complexo Lagunar de Jacarepaguá (RJ), através do uso destes índices. As variáveis utilizadas foram clorofila-a, transparência da água e fósforo total, e para o IETm, foi acrescido a variável ortofosfato dissolvido. Os resultados obtidos indicaram que tanto a Lagoa Rodrigo de Freitas, quanto o Complexo Lagunar de Jacarepaguá estão classificados como ambientes hipereutróficos no índice de Carlson e como eutróficos no índice modificado por Toledo. Entretanto, estes corpos dágua encontram-se em fases distintas. Para a Lagoa Rodrigo de Freitas, foi observada uma melhora na qualidade de suas águas nas últimas décadas, já para o Complexo Lagunar de Jacarepaguá, foi constatado uma piora significativa da qualidade de suas águas, principalmente nesta última década. A aplicação dos índices do estado trófico demonstrou-se uma ferramenta de avaliação do grau de trofia dos corpos dágua bastante prática, de fácil interpretação e divulgação dos dados obtidos a partir de um monitoramento sistemático
Resumo:
Recent surveys have indicated an increase in haplochromine biomass recorded from the bottom trawl and in the beam trawl. The haplochromines recovering in the offshore waters belong to three species in the zooplanktivorous trophic group: Yssichromis laparogramma (Greenwood and Gee), Yssichromis fusiformis (Greenwood and Gee) and Astatotilapia lacrimosa (Boulenger). In this paper, the species composition and relative abundance of the zooplanktivorous haplochromines recorded from the bottom and frame trawl surveys in the various parts of the Ugandan waters of Lake Victoria are discussed.