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1.
Sci Rep ; 14(1): 11194, 2024 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-38773130

RESUMO

We present a multi-proxy investigation of a lower Carnian basinal succession from Polzberg in the Northern Calcareous Alps (Lower Austria). A section comprising a unique Konservat-Lagerstätte was studied based on bio- and chemostratigraphy along with geophysical methods, yielding a detailed and robust stratigraphic calibration of the Polzberg succession. The Polzberg section revealed the paleoceanographic history and helped to identify a global climatic reversal, the Carnian Pluvial Episode. The age of the Upper Triassic Reingraben formation in the Northern Calcareous Alps is refined as the Austrotrachyceras austriacum Zone within the lower Carnian (Julian 2). Ammonoids and conodonts provide a detailed biostratigraphic subdivision that serves as a basis for analyses of the faunal distribution and the paleoenvironmental evolution of the Upper Triassic Reifling Basin. The succession includes lithological and facies changes similar to those of coeval units in the Tethys. The Carnian was characterized by a weak (~ 1‰) positive δ13C trend, punctuated by a negative shift during the lower Carnian corresponding to the initiation of the Carnian Pluvial Episode, a period representing the onset of early/late Carnian transitional global greenhouse conditions. Organic maturity parameters and the conodont alteration index (CAI) show that the thermal overprint of the Polzberg section is low. Biomarker proxies suggest that the organic matter of the uppermost Göstling formation is a mixture of marine and terrestrial material deposited in a dysoxic environment. Within the overlaying Reingraben formation, the amount of marine biomass decreased gradually upwards. Oxygen-depleted conditions, probably due to water-column stratification, continued during deposition of the Reingraben formation. Bacterial sulfate reduction played a major role in organic matter degradation.

2.
Int J Earth Sci ; 112(7): 1901-1921, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37664825

RESUMO

Seal quality assessment is not only essential in petroleum systems studies but also in the context of other geo energy applications such as underground hydrogen storage. Capillary breakthrough pressure controls top seal capacity in the absence of faults or other discontinuities. In basins that lack measured capillary pressure data (e.g., from drill cores), regional compaction-porosity trends can be used as a first prediction tool to estimate the capillary properties of mudstones. Mathematical compaction models exist but need to be calibrated for each basin. This study aims to establish a compaction trend based on theoretical models, then compare it with theoretical maximum hydrocarbon column heights inferred from true measured capillary pressure curves. Middle to upper Miocene mudstone core samples from the Vienna Basin, covering a broad depth interval from 700 to 3400 m, were investigated by X-ray diffractometry, with an Eltra C/S analyzer, and by Rock-Eval pyrolysis for bulk mineralogy, total organic carbon, and free hydrocarbon contents. Broad ion beam-scanning electron microscopy, mercury intrusion capillary porosimetry, and helium pycnometry were applied to obtain pore structural properties to compare the mathematical compaction models with actual porosity data from the Vienna Basin. Clear decreasing porosity depth trends imply that mechanical compaction was rather uniform in the central Vienna Basin. Comparing the Vienna Basin trend to global mudstone compaction trends, regional uplift causing erosion of up to ~ 500 m upper Miocene strata is inferred. A trend of increasing Rock-Eval parameters S1 and production index [PI = S1/(S1 + S2)] with decreasing capillary sealing capacity of the investigated mudstones possibly indicates vertical hydrocarbon migration through the low-permeable mudstone horizons. This observation must be considered in future top-seal studies for secondary storage applications in the Vienna Basin. Supplementary Information: The online version contains supplementary material available at 10.1007/s00531-023-02331-4.

3.
Int J Earth Sci ; 111(5): 1631-1661, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35707060

RESUMO

The Toarcian oceanic anoxic event (T-OAE) is associated with a prominent negative carbon isotope excursion (CIE; ~ 183 million years (Myr)). About 10-m-thick organic matter-rich sediments accumulated during the T-OAE in the Southwest German Basin (SWGB). Rock-Eval, maceral and biomarker analysis were used to determine variations of environmental conditions across the CIE interval. Carbon isotope records were determined for various n-alkanes, pristane and phytane to contribute to the reconstruction of the paleo-environment and to study the factors controlling molecular δ13C values. Geochemical redox indicators provide evidence for photic zone anoxia during the Toarcian CIE, which reached its maximum after deposition of the "Unterer Stein" marker horizon. The 2α-methylhopane index suggests enhanced activity of diazotrophic cyanobacteria, which is also supported by nitrogen isotope data. This distinguishes the SWGB from other basins with Toarcian black shale. Oxygen-depleted conditions, albeit with lower intensity continued after the CIE. All investigated compounds replicate the negative CIE, but the magnitudes vary considerably. The largest shift is observed for n-C27 (9‰) and reflects the combined effect of the global CIE and a major change in organic matter input (termination of terrigenous organic matter input). The shift for short-chain n-alkanes, pristane, and phytane, interpreted to reflect marine biomass, varies between 4.5 and 5.0‰. This is the highest value observed so far for any Toarcian section. δ13C values of pristane and phytane reach a minimum near the base of the CIE interval and increase upsection. Thus, the maximum negative isotope shift predates the strongest basin restriction by about 450 thousand years (kyr).

4.
Sci Total Environ ; 621: 30-39, 2018 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-29175619

RESUMO

Soil pollutants such as hydrocarbons can induce toxic effects in plants and associated arbuscular mycorrhizal fungi (AMF). This study was conducted to evaluate if the legume Lotus corniculatus and the grass Elymus trachycaulus and arbuscular mycorrhizal fungi could grow in two oil sands processing by-products after bitumen extraction from the oil sands in northern Alberta, Canada. Substrate treatments were coarse tailings sand (CTS), a mix of dry mature fine tailings (MFT) with CTS (1:1) and Pleistocene sandy soil (hydrocarbon free); microbial treatments were without AMF, with AMF and AMF plus soil bacteria isolated from oil sands reclamation sites. Plant biomass, root morphology, leaf water content, shoot tissue phosphorus content and mycorrhizal colonization were evaluated. Both plant species had reduced growth in CTS and tailings mix relative to sandy soil. AMF frequency and intensity in roots of E. trachycaulus was not influenced by soil hydrocarbons; however, it decreased significantly over time in roots of L. corniculatus without bacteria in CTS. Mycorrhizal inoculation alone did not significantly improve plant growth in CTS and tailings mix; however, inoculation with mycorrhizae plus bacteria led to a significantly positive response of both plant species in CTS. Thus, combined inoculation with selected mycorrhizae and bacteria led to synergistic effects. Such combinations may be used in future to improve plant growth in reclamation of CTS and tailings mix.


Assuntos
Elymus/crescimento & desenvolvimento , Elymus/microbiologia , Micorrizas , Campos de Petróleo e Gás , Poluição por Petróleo , Alberta , Bactérias , Biomassa , Hidrocarbonetos , Raízes de Plantas/microbiologia , Solo , Poluentes do Solo
5.
Phys Rev Lett ; 119(17): 170404, 2017 Oct 27.
Artigo em Inglês | MEDLINE | ID: mdl-29219466

RESUMO

Quantifying quantum mechanical uncertainty is vital for the increasing number of experiments that reach the uncertainty limited regime. We present a method for computing tight variance uncertainty relations, i.e., the optimal state-independent lower bound for the sum of the variances for any set of two or more measurements. The bounds come with a guaranteed error estimate, so results of preassigned accuracy can be obtained straightforwardly. Our method also works for postive-operator-valued measurements. Therefore, it can be used for detecting entanglement in noisy environments, even in cases where conventional spin squeezing criteria fail because of detector noise.

6.
Nat Commun ; 8(1): 964, 2017 10 17.
Artigo em Inglês | MEDLINE | ID: mdl-29042543

RESUMO

Quantum sensors-qubits sensitive to external fields-have become powerful detectors for various small acoustic and electromagnetic fields. A major key to their success have been dynamical decoupling protocols which enhance sensitivity to weak oscillating (AC) signals. Currently, those methods are limited to signal frequencies below a few MHz. Here we harness a quantum-optical effect, the Mollow triplet splitting of a strongly driven two-level system, to overcome this limitation. We microscopically understand this effect as a pulsed dynamical decoupling protocol and find that it enables sensitive detection of fields close to the driven transition. Employing a nitrogen-vacancy center, we detect GHz microwave fields with a signal strength (Rabi frequency) below the current detection limit, which is set by the center's spectral linewidth [Formula: see text]. Pushing detection sensitivity to the much lower 1/T 2 limit, this scheme could enable various applications, most prominently coherent coupling to single phonons and microwave photons.Dynamical decoupling protocols can enhance the sensitivity of quantum sensors but this is limited to signal frequencies below a few MHz. Here, Joas et al. use the Mollow triplet splitting in a nitrogen-vacancy centre to overcome this limitation, enabling sensitive detection of signals in the GHz range.

7.
Front Behav Neurosci ; 11: 45, 2017.
Artigo em Inglês | MEDLINE | ID: mdl-28469564

RESUMO

Larval Drosophila offer a study case for behavioral neurogenetics that is simple enough to be experimentally tractable, yet complex enough to be worth the effort. We provide a detailed, hands-on manual for Pavlovian odor-reward learning in these animals. Given the versatility of Drosophila for genetic analyses, combined with the evolutionarily shared genetic heritage with humans, the paradigm has utility not only in behavioral neurogenetics and experimental psychology, but for translational biomedicine as well. Together with the upcoming total synaptic connectome of the Drosophila nervous system and the possibilities of single-cell-specific transgene expression, it offers enticing opportunities for research. Indeed, the paradigm has already been adopted by a number of labs and is robust enough to be used for teaching in classroom settings. This has given rise to a demand for a detailed, hands-on manual directed at newcomers and/or at laboratory novices, and this is what we here provide. The paradigm and the present manual have a unique set of features: The paradigm is cheap, easy, and robust;The manual is detailed enough for newcomers or laboratory novices;It briefly covers the essential scientific context;It includes sheets for scoring, data analysis, and display;It is multilingual: in addition to an English version we provide German, French, Japanese, Spanish and Italian language versions as well.The present manual can thus foster science education at an earlier age and enable research by a broader community than has been the case to date.

8.
Nat Commun ; 6: 8795, 2015 Oct 30.
Artigo em Inglês | MEDLINE | ID: mdl-26514280

RESUMO

Secret communication over public channels is one of the central pillars of a modern information society. Using quantum key distribution this is achieved without relying on the hardness of mathematical problems, which might be compromised by improved algorithms or by future quantum computers. State-of-the-art quantum key distribution requires composable security against coherent attacks for a finite number of distributed quantum states as well as robustness against implementation side channels. Here we present an implementation of continuous-variable quantum key distribution satisfying these requirements. Our implementation is based on the distribution of continuous-variable Einstein-Podolsky-Rosen entangled light. It is one-sided device independent, which means the security of the generated key is independent of any memoryfree attacks on the remote detector. Since continuous-variable encoding is compatible with conventional optical communication technology, our work is a step towards practical implementations of quantum key distribution with state-of-the-art security based solely on telecom components.

9.
Nat Commun ; 6: 8527, 2015 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-26456017

RESUMO

We demonstrate a protocol using individual nitrogen-vacancy centres in diamond to observe the time evolution of proton spins from organic molecules located a few nanometres from the diamond surface. The protocol records temporal correlations among the interacting protons, and thus is sensitive to the local dynamics via its impact on the nuclear spin relaxation and interaction with the nitrogen vacancy. We gather information on the nanoscale rotational and translational diffusion dynamics by analysing the time dependence of the nuclear magnetic resonance signal. Applying this technique to liquid and solid samples, we find evidence that liquid samples form a semi-solid layer of 1.5-nm thickness on the surface of diamond, where translational diffusion is suppressed while rotational diffusion remains present. Extensions of the present technique could be exploited to highlight the chemical composition of molecules tethered to the diamond surface or to investigate thermally or chemically activated dynamical processes such as molecular folding.

10.
Microsc Microanal ; 21(5): 1123-37, 2015 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-26365327

RESUMO

Siliciclastic reservoir rocks of the North Alpine Foreland Basin were studied focusing on investigations of pore fillings. Conventional oil and gas production requires certain thresholds of porosity and permeability. These parameters are controlled by the size and shape of grains and diagenetic processes like compaction, dissolution, and precipitation of mineral phases. In an attempt to estimate the impact of these factors, conventional microscopy, high resolution scanning electron microscopy, and wavelength dispersive element mapping were applied. Rock types were established accordingly, considering Poro/Perm data. Reservoir properties in shallow marine Cenomanian sandstones are mainly controlled by the degree of diagenetic calcite precipitation, Turonian rocks are characterized by reduced permeability, even for weakly cemented layers, due to higher matrix content as a result of lower depositional energy. Eocene subarkoses tend to be coarse-grained with minor matrix content as a result of their fluvio-deltaic and coastal deposition. Reservoir quality is therefore controlled by diagenetic clay and minor calcite cementation.Although Eocene rocks are often matrix free, occasionally a clay mineral matrix may be present and influence cementation of pores during early diagenesis. Oligo-/Miocene deep marine rocks exhibit excellent quality in cases when early cement is dissolved and not replaced by secondary calcite, mainly bound to the gas-water contact within hydrocarbon reservoirs.

11.
Nat Nanotechnol ; 10(2): 125-8, 2015 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-25559711

RESUMO

Scanning probe microscopy is one of the most versatile windows into the nanoworld, providing imaging access to a variety of electronic, dielectric, magnetic and topographic sample properties, depending on the probe used. Here, we demonstrate a scanning probe imaging method that extends the range of accessible quantities to label-free imaging of chemical species while operating on arbitrary samples--including insulating materials--under ambient conditions. Moreover, its sensitivity extends below the surface of a sample, allowing for imaging of subsurface features. We achieve these results by recording NMR signals from a sample surface with a recently introduced scanning probe, a single nitrogen-vacancy centre in diamond. We demonstrate NMR imaging with 10 nm resolution and achieve chemically specific contrast by separating fluorine from hydrogen-rich regions. Our result opens the door to scanning probe imaging of the chemical composition and molecular structure of arbitrary samples. A method with these abilities will find widespread application in materials science, even on biological specimens down to the level of single macromolecules.


Assuntos
Microscopia de Varredura por Sonda/métodos , Modelos Teóricos , Ressonância Magnética Nuclear Biomolecular/métodos
12.
J Comp Neurol ; 522(15): 3485-500, 2014 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-24752702

RESUMO

Drosophila larvae are able to evaluate sensory information based on prior experience, similarly to adult flies, other insect species, and vertebrates. Larvae and adult flies can be taught to associate odor stimuli with sugar reward, and prior work has implicated both the octopaminergic and the dopaminergic modulatory systems in reinforcement signaling. Here we use genetics to analyze the anatomy, up to the single-cell level, of the octopaminergic/tyraminergic system in the larval brain and subesophageal ganglion. Genetic ablation of subsets of these neurons allowed us to determine their necessity for appetitive olfactory learning. These experiments reveal that a small subset of about 39 largely morphologically distinguishable octopaminergic/tyraminergic neurons is involved in signaling reward in the Drosophila larval brain. In addition to prior work on larval locomotion, these data functionally separate the octopaminergic/tyraminergic system into two sets of about 40 neurons. Those situated in the thoracic/abdominal ganglion are involved in larval locomotion, whereas the others in the subesophageal ganglion and brain hemispheres mediate reward signaling.


Assuntos
Drosophila/citologia , Drosophila/crescimento & desenvolvimento , Neurônios/fisiologia , Octopamina/metabolismo , Tiramina/metabolismo , Animais , Animais Geneticamente Modificados , Comportamento Apetitivo/fisiologia , Aprendizagem por Associação/fisiologia , Encéfalo/citologia , Encéfalo/fisiologia , Drosophila/fisiologia , Imunofluorescência , Gânglios dos Invertebrados/citologia , Gânglios dos Invertebrados/crescimento & desenvolvimento , Gânglios dos Invertebrados/fisiologia , Larva , Neurônios/citologia , Percepção Olfatória/fisiologia , Recompensa
13.
Rev Sci Instrum ; 85(1): 013701, 2014 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-24517769

RESUMO

We present the design and performance of an ultra-high vacuum (UHV) low temperature scanning probe microscope employing the nitrogen-vacancy color center in diamond as an ultrasensitive magnetic field sensor. Using this center as an atomic-size scanning probe has enabled imaging of nanoscale magnetic fields and single spins under ambient conditions. In this article we describe an experimental setup to operate this sensor in a cryogenic UHV environment. This will extend the applicability to a variety of molecular systems due to the enhanced target spin lifetimes at low temperature and the controlled sample preparation under UHV conditions. The instrument combines a tuning-fork based atomic force microscope (AFM) with a high numeric aperture confocal microscope and the facilities for application of radio-frequency (RF) fields for spin manipulation. We verify a sample temperature of <50 K even for strong laser and RF excitation and demonstrate magnetic resonance imaging with a magnetic AFM tip.

14.
Phys Rev Lett ; 111(17): 170801, 2013 Oct 25.
Artigo em Inglês | MEDLINE | ID: mdl-24206470

RESUMO

We present a novel spectroscopy protocol based on optimal control of a single quantum system. It enables measurements with quantum-limited sensitivity (η(ω)[proportionality](1/√[T(2)(*)]), T(2)(*) denoting the system's coherence time) but has an orders of magnitude larger dynamic range than pulsed spectroscopy methods previously employed for this task. We employ this protocol to image nanoscale magnetic fields with a single scanning nitrogen-vacancy center in diamond. Here, our scheme enables quantitative imaging of a strongly inhomogeneous field in a single scan without closed-loop control, which has previously been necessary to achieve this goal.

15.
Phys Rev Lett ; 111(16): 160405, 2013 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-24182239

RESUMO

While the slogan "no measurement without disturbance" has established itself under the name of the Heisenberg effect in the consciousness of the scientifically interested public, a precise statement of this fundamental feature of the quantum world has remained elusive, and serious attempts at rigorous formulations of it as a consequence of quantum theory have led to seemingly conflicting preliminary results. Here we show that despite recent claims to the contrary [L. Rozema et al, Phys. Rev. Lett. 109, 100404 (2012)], Heisenberg-type inequalities can be proven that describe a tradeoff between the precision of a position measurement and the necessary resulting disturbance of momentum (and vice versa). More generally, these inequalities are instances of an uncertainty relation for the imprecisions of any joint measurement of position and momentum. Measures of error and disturbance are here defined as figures of merit characteristic of measuring devices. As such they are state independent, each giving worst-case estimates across all states, in contrast to previous work that is concerned with the relationship between error and disturbance in an individual state.

16.
Phys Rev Lett ; 110(19): 190601, 2013 May 10.
Artigo em Inglês | MEDLINE | ID: mdl-23705697

RESUMO

We report on the experimental realization of electric quantum walks, which mimic the effect of an electric field on a charged particle in a lattice. Starting from a textbook implementation of discrete-time quantum walks, we introduce an extra operation in each step to implement the effect of the field. The recorded dynamics of such a quantum particle exhibits features closely related to Bloch oscillations and interband tunneling. In particular, we explore the regime of strong fields, demonstrating contrasting quantum behaviors: quantum resonances versus dynamical localization depending on whether the accumulated Bloch phase is a rational or irrational fraction of 2π.

17.
Science ; 339(6119): 561-3, 2013 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-23372009

RESUMO

Application of nuclear magnetic resonance (NMR) spectroscopy to nanoscale samples has remained an elusive goal, achieved only with great experimental effort at subkelvin temperatures. We demonstrated detection of NMR signals from a (5-nanometer)(3) voxel of various fluid and solid organic samples under ambient conditions. We used an atomic-size magnetic field sensor, a single nitrogen-vacancy defect center, embedded ~7 nanometers under the surface of a bulk diamond to record NMR spectra of various samples placed on the diamond surface. Its detection volume consisted of only 10(4) nuclear spins with a net magnetization of only 10(2) statistically polarized spins.

18.
PLoS One ; 7(10): e47518, 2012.
Artigo em Inglês | MEDLINE | ID: mdl-23082175

RESUMO

The Drosophila larva has turned into a particularly simple model system for studying the neuronal basis of innate behaviors and higher brain functions. Neuronal networks involved in olfaction, gustation, vision and learning and memory have been described during the last decade, often up to the single-cell level. Thus, most of these sensory networks are substantially defined, from the sensory level up to third-order neurons. This is especially true for the olfactory system of the larva. Given the wealth of genetic tools in Drosophila it is now possible to address the question how modulatory systems interfere with sensory systems and affect learning and memory. Here we focus on the serotonergic system that was shown to be involved in mammalian and insect sensory perception as well as learning and memory. Larval studies suggested that the serotonergic system is involved in the modulation of olfaction, feeding, vision and heart rate regulation. In a dual anatomical and behavioral approach we describe the basic anatomy of the larval serotonergic system, down to the single-cell level. In parallel, by expressing apoptosis-inducing genes during embryonic and larval development, we ablate most of the serotonergic neurons within the larval central nervous system. When testing these animals for naïve odor, sugar, salt and light perception, no profound phenotype was detectable; even appetitive and aversive learning was normal. Our results provide the first comprehensive description of the neuronal network of the larval serotonergic system. Moreover, they suggest that serotonin per se is not necessary for any of the behaviors tested. However, our data do not exclude that this system may modulate or fine-tune a wide set of behaviors, similar to its reported function in other insect species or in mammals. Based on our observations and the availability of a wide variety of genetic tools, this issue can now be addressed.


Assuntos
Comportamento Animal/fisiologia , Sistema Nervoso Central/anatomia & histologia , Sistema Nervoso Central/fisiologia , Drosophila melanogaster/anatomia & histologia , Drosophila melanogaster/fisiologia , Serotonina/metabolismo , Animais , Apetite/fisiologia , Contagem de Células , Cérebro/anatomia & histologia , Cérebro/citologia , Cérebro/fisiologia , Quimiotaxia/fisiologia , Comportamento de Escolha/fisiologia , Proteínas de Drosophila/metabolismo , Drosophila melanogaster/citologia , Gânglios dos Invertebrados/anatomia & histologia , Gânglios dos Invertebrados/citologia , Gânglios dos Invertebrados/fisiologia , Larva/anatomia & histologia , Larva/citologia , Larva/fisiologia , Aprendizagem/fisiologia , Luz , Neurônios Serotoninérgicos/citologia , Neurônios Serotoninérgicos/metabolismo , Olfato/fisiologia , Sinapses/metabolismo , Paladar/fisiologia , Fatores de Transcrição/metabolismo
19.
J Comp Neurol ; 520(16): 3764-85, 2012 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-22627970

RESUMO

The characteristic crawling behavior of Drosophila larvae consists of a series of rhythmic waves of peristalsis and episodes of head swinging and turning. The two biogenic amines octopamine and tyramine have recently been shown to modulate various parameters of locomotion, such as muscle contraction, the time spent in pausing or forward locomotion, and the initiation and maintenance of rhythmic motor patterns. By using mutants having altered octopamine and tyramine levels and by genetic interference with both systems we confirm that signaling of these two amines is necessary for larval locomotion. We show that a small set of about 40 octopaminergic/tyraminergic neurons within the ventral nerve cord is sufficient to trigger proper larval locomotion. Using single-cell clones, we describe the morphology of these neurons individually. Given various potential roles of octopamine and tyramine in the larval brain, such as locomotion, learning and memory, stress-induced behaviors or the regulation of the energy state, functions that are often not easy to discriminate, we dissect here for the first time a subset of this complex circuit that modulates specifically larval locomotion. Thus, these data will help to understand-for a given neuronal modulator-how specific behavioral functions are executed within distinct subcircuits of a complex neuronal network.


Assuntos
Comportamento Animal/fisiologia , Drosophila/fisiologia , Locomoção/fisiologia , Octopamina/metabolismo , Tiramina/metabolismo , Animais , Encéfalo/metabolismo , Imuno-Histoquímica , Larva/fisiologia , Músculo Esquelético/inervação , Neurônios/metabolismo
20.
Spectrochim Acta A Mol Biomol Spectrosc ; 81(1): 583-9, 2011 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-21764360

RESUMO

The thermotropic phase behavior of a suite of newly developed self-forming synthetic biopolymers has been investigated by variable-temperature Fourier transform infrared (FT-IR) absorption spectroscopy. The temperature-induced infrared spectra of these artificial biopolymers (lipids) composed of 1,2-dimyristoyl-rac-glycerol-3-dodecaethylene glycol (GDM-12), 1,2-dioleoyl-rac-glycerol-3-dodecaethylene glycol (GDO-12) and 1,2-distearoyl-rac-glycerol-3-triicosaethylene glycol (GDS-23) in the spectral range of 4000-500 cm(-1) have been acquired by using a thin layered FT-IR spectrometer in conjunction with a custom built temperature-controlled demountable liquid cell having a pathlength of ∼15 µm. The lipids under consideration have long hydrophobic acyl chains and contain various units of hydrophilic polyethylene glycol (PEG) headgroups. In contrast to conventional phospholipids, this new kind of lipids forms liposomes or nanovesicles spontaneously upon hydration, without requiring external activation energy. We have found that the thermal stability of the PEGylated lipids differs greatly depending upon the acyl chain-lengths as well as the nature of the associated bonds and the number of PEG headgroup units. In particular, GDM-12 (saturated 14 hydrocarbon chains with 12 units of PEG headgroup) exhibits one sharp order-disorder phase transition over a temperature range increasing from 3°C to 5°C. Similarly, GDS-23 (saturated 18 hydrocarbon chains with 23 units of PEG headgroup) displays comparatively broad order-disorder phase transition profiles between temperature 17°C and 22°C. In contrast, GDO-12 (monounsaturated 18 hydrocarbon chains with 12 units of PEG headgroup) does not reveal any order-disorder transition phenomena demonstrating a highly disordered behavior for the entire temperature range. To confirm these observations, differential scanning calorimetry (DSC) was applied to the samples and revealed good agreement with the infrared spectroscopy results. Finally, the investigation of thermal properties of lipids is extremely critical for numerous purposes and the result obtained in this work may find application in various studies including the development of PEGylated lipid based novel drug and substances delivery vehicles.


Assuntos
Biopolímeros/química , Temperatura , Biopolímeros/biossíntese , Varredura Diferencial de Calorimetria , Lipídeos/química , Modelos Biológicos , Transição de Fase , Polietilenoglicóis/química , Espectrofotometria Infravermelho/instrumentação , Espectrofotometria Infravermelho/métodos , Espectroscopia de Infravermelho com Transformada de Fourier , Termodinâmica
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