Unveiling Eco-Friendly Reverse Micelle Systems: Dimethyl Carbonate as a Novel Biocompatible Solvent.

In this study, we systematically explored the characteristics of dimethyl carbonate (DMC)/sodium 1,4-bis-2-ethylhexylsulfosuccinate (AOT) reverse micelles (RMs) in the presence of water using dynamic light scattering (DLS), proton nuclear magnetic resonance (H NMR), and molecular probes. DMC, a biocompatible solvent, enables the formulation of AOT RMs without the need for a co-surfactant. DLS revealed that as the water content increased, the droplet sizes grew larger.

Electrochemical and Spectroscopic Studies Performed for Indomethacin and 1-Naphthol Incorporated in 1-Butyl-3-methyl-imidazolium Bis(2-ethylhexyl) Sulfosuccinate Vesicles to Investigate Them as a Potentially pH-Sensitive Nanocarrier.

Characterization studies of 1-butyl-3-methyl-imidazolium bis(2-ethylhexyl) sulfosuccinate vesicles at different pH values have been carried out by using liquid surface tension, transmission electron microscopy, and dynamic light scattering. The results show that there are no vesicle changes in its size and negative Z potential at pH 3, 6, and 10. Furthermore, indomethacin and 1-naphthol, both pH-dependent, electroactive, and fluorescence probes, were used to further characterize the bilayer employing electrochemical and emission techniques.

PRODAN Photophysics as a Tool to Determine the Bilayer Properties of Different Unilamellar Vesicles Composed of Phospholipids.

Vesicles formed by phospholipids are promising candidates for drug delivery. It is known that the lipid composition affects properties such as the rigidity-fluidity of the membrane and that it influences the bilayer permeability, but sometimes sophisticated techniques are selected to monitor them. In this work, we study the bilayer of different unilamellar vesicles composed of different lipids (1,2-dioleoyl--glycero-3-phosphocholine, DOPC, and lecithin) and diverse techniques such as extruder and electrospun templates and using 6-propionyl-2-(,-dimethyl) aminonaphthalene (PRODAN) and its photophysics.

Green AOT reverse micelles as nanoreactors for alkaline phosphatase. The hydrogen bond "dances" between water and the enzyme, the reaction product, and the reverse micelles interface.

In this work, we present an investigation of the influence of water encapsulated in 1,4-bis-2-ethylhexylsulfosuccinate/methyl laurate and 1,4-bis-2-ethylhexylsulfosuccinate/isopropyl myristate reverse micelles on the enzymatic hydrolysis of 1-naphthyl phosphate by alkaline phosphatase. Our results show that the enzyme is active in the biocompatible reverse micelles studied and that the Michaelis-Menten kinetic model is valid in all systems. We found that both micellar systems studied have a particular behavior toward pH and that the penetration of external solvents into the interfaces is crucial to understanding the effect.

Temperature thresholds of ecosystem respiration at a global scale.

Ecosystem respiration is a major component of the global terrestrial carbon cycle and is strongly influenced by temperature. The global extent of the temperature-ecosystem respiration relationship, however, has not been fully explored. Here, we test linear and threshold models of ecosystem respiration across 210 globally distributed eddy covariance sites over an extensive temperature range.

Ensemble modelling, uncertainty and robust predictions of organic carbon in long-term bare-fallow soils.

Simulation models represent soil organic carbon (SOC) dynamics in global carbon (C) cycle scenarios to support climate-change studies. It is imperative to increase confidence in long-term predictions of SOC dynamics by reducing the uncertainty in model estimates. We evaluated SOC simulated from an ensemble of 26 process-based C models by comparing simulations to experimental data from seven long-term bare-fallow (vegetation-free) plots at six sites: Denmark (two sites), France, Russia, Sweden and the United Kingdom.

SoilTemp: A global database of near-surface temperature.

Current analyses and predictions of spatially explicit patterns and processes in ecology most often rely on climate data interpolated from standardized weather stations. This interpolated climate data represents long-term average thermal conditions at coarse spatial resolutions only. Hence, many climate-forcing factors that operate at fine spatiotemporal resolutions are overlooked.

Water-soluble gold nanoparticles: recyclable catalysts for the reduction of aromatic nitro compounds in water.

A structure/catalytic activity study of water-soluble gold nanoparticles, stabilized by zwitterionic ligands derived from imidazolium salts, in the reduction of aromatic nitro compounds in pure water at different temperature, as well as their recyclability, was performed. Our studies indicate that the nanoparticles synthesized by an easy, fast and reproducible process, need a short characteristic induction time to restructure the surfaces and make them active. The differences observed in the catalytic activity of the nanoparticles, determined by using the typical Langmuir-Hinshelwood model, are strongly based on the degree of coverage and spatial arrangement of the imidazolium salts on them.

Generic parameters of first-order kinetics accurately describe soil organic matter decay in bare fallow soils over a wide edaphic and climatic range.

The conventional soil organic matter (SOM) decay paradigm considers the intrinsic quality of SOM as the dominant decay limitation with the result that it is modelled using simple first-order decay kinetics. This view and modelling approach is often criticized for being too simplistic and unreliable for predictive purposes. It is still under debate if first-order models can correctly capture the variability in temporal SOM decay observed between different agroecosystems and climates.

Study of lipid peroxidation and ascorbic acid protective role in large unilamellar vesicles from a new electrochemical performance.

In this contribution an electrochemical study is described for the first time of lipid peroxidation and the role of antioxidant on lipid protection using large unilamellar vesicles (LUVs). In order to simulate the cell membrane, LUVs composed of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) were used. A vesicle-modified electrode was constructed by immobilizing DOPC LUVs onto carbon paste electrodes (CPEs).

Gold nanoparticles stabilized with sulphonated imidazolium salts in water and reverse micelles.

Herein we describe the synthesis of gold nanoparticles (Au-NPs) in presence of sulphonated imidazolium salts [1,3-bis(2,6-diisopropyl-4-sodiumsulfonatophenyl)imidazolium (), 1-mesityl-3-(3-sulfonatopropyl)imidazolium () and 1-(3-sulfonatopropyl)imidazolium ()] in water and in a confinement environment created by reverse micelles (RMs). The Au-NPs were characterized-with an excellent agreement between different techniques-by UV-vis spectroscopy, transmission electron microscopy (TEM), dynamic light scattering (DLS) and zeta potential. In homogeneous media, the Au-NPs interact with the imidazolium ring and the sulphonate groups were directed away from the NPs' surface.

Effect of climate warming on the annual terrestrial net ecosystem CO exchange globally in the boreal and temperate regions.

The net ecosystem CO exchange is the result of the imbalance between the assimilation process (gross primary production, GPP) and ecosystem respiration (RE). The aim of this study was to investigate temperature sensitivities of these processes and the effect of climate warming on the annual terrestrial net ecosystem CO exchange globally in the boreal and temperate regions. A database of 403 site-years of ecosystem flux data at 101 sites in the world was collected and analyzed.

Gold nanoparticles covalently assembled onto vesicle structures as possible biosensing platform.

In this contribution a strategy is shown to covalently immobilize gold nanoparticles (AuNPs) onto vesicle bilayers with the aim of using this nanomaterial as platform for the future design of immunosensors. A novel methodology for the self-assembly of AuNPs onto large unilamellar vesicle structures is described. The vesicles were formed with 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and 1-undecanethiol (SH).

Singularities in the physicochemical properties of spontaneous AOT-BHD unilamellar vesicles in comparison with DOPC vesicles.

In the present work, we study different physicochemical properties of the spontaneous unilamellar vesicles created by the catanionic ionic liquid-like surfactant benzyl-n-hexadecyldimethylammonium 1,4-bis-2-ethylhexylsulfosuccinate (AOT-BHD), using two different fluorescent probes: 6-propionyl-2-(dimethylaminonaphthalene), PRODAN and trans-4-[4-(dimethylamino)-styryl]-1-methylpyridinium iodide, HC. Steady-state and time resolved fluorescence emission spectroscopy allowed us to find the unique properties of the AOT-BHD bilayer in comparison with vesicles formed using the traditional phospholipid 1,2-di-oleoyl-sn-glycero-3-phosphatidylcholine, DOPC. From the emission results, we observed that the region of the bilayer close to the polar head of AOT-BHD is a powerful electron donor environment, even larger than DOPC.

On the characterization of NaDEHP/n-heptane nonaqueous reverse micelles: the effect of the polar solvent.

The behavior of two polar solvents, ethylene glycol (EG) and dimethylformamide (DMF), entrapped in sodium bis-(2-ethylhexyl) phosphate (NaDEHP)/n-heptane reverse micelles (RMs) was investigated using dynamic light scattering (DLS), molecular probe absorption and FT-IR spectroscopy. DLS results reveal the formation of RMs containing EG and DMF as a polar component. To the best of our knowledge this is the first report where both polar solvents are entrapped by the NaDEHP surfactant to effectively create RMs.

Higher temperature sensitivity for stable than for labile soil organic carbon--evidence from incubations of long-term bare fallow soils.

The impact of climate change on the stability of soil organic carbon (SOC) remains a major source of uncertainty in predicting future changes in atmospheric CO2 levels. One unsettled issue is whether the mineralization response to temperature depends on SOC mineralization rate. Long-term (>25 years) bare fallow experiments (LTBF) in which the soil is kept free of any vegetation and organic inputs, and their associated archives of soil samples represent a unique research platform to examine this issue as with increasing duration of fallow, the lability of remaining total SOC decreases.

Enzymatic hydrolysis of N-benzoyl-L-tyrosine p-nitroanilide by α-chymotrypsin in DMSO-water/AOT/n-heptane reverse micelles. A unique interfacial effect on the enzymatic activity.

The reverse micelle (RM) media are very good as nanoreactors because they can create a unique microenvironment for carrying out a variety of chemical and biochemical reactions. The aim of the present work is to determine the influence of different water-dimethyl sulfoxide (DMSO) mixtures encapsulated in 1,4-bis-2-ethylhexylsulfosuccinate (AOT)/n-heptane RMs on the enzymatic hydrolysis of N-benzoyl-L-tyrosine p-nitroanilide (Bz-Try-pNA) by α-chymotrypsin (α-CT). The reaction was first studied in homogeneous media at different DMSO-water mixture compositions and in DMSO-water/AOT/n-heptane RMs.

A unique ionic liquid with amphiphilic properties that can form reverse micelles and spontaneous unilamellar vesicles.

Catanionic surfactants: the synthesis of a new surfactant ionic liquid with unique properties is described. The formation of reverse micelles in benzene and large unilamellar vesicles, formed spontaneously without the help of any mechanical of chemistry methods, in water is demonstrated by using dynamic light scattering and small-angle X-ray scattering techniques.

Cationic reverse micelles create water with super hydrogen-bond-donor capacity for enzymatic catalysis: hydrolysis of 2-naphthyl acetate by alpha-chymotrypsin.

Reverse micelles (RMs) are very good nanoreactors because they can create a unique microenvironment for carrying out a variety of chemical and biochemical reactions. The aim of the present work is to determine the influence of different RM interfaces on the hydrolysis of 2-naphthyl acetate (2-NA) by alpha-chymotrypsin (alpha-CT). The reaction was studied in water/benzyl-n-hexadecyldimethylammonium chloride (BHDC)/benzene RMs and, its efficiency compared with that observed in pure water and in sodium 1,4-bis-2-ethylhexylsulfosuccinate (AOT) RMs.

An alternative approach to quantify partition processes in confined environments: the electrochemical behavior of PRODAN in unilamellar vesicles.

Herein, we investigate the behavior of the electroactive molecular probe 6-propionyl-2-dimethyl amino naphthalene (PRODAN) in large unilamellar vesicles (LUV) formed with the phospholipid 1,2-di-oleoyl-sn-glycero-3-phosphatidylcholine (DOPC) by using cyclic voltammetry (CV). The CV studies in pure water confirm our previous spectroscopic results that PRODAN self-aggregates due to its low water solubility. Moreover, the electrochemical results also reveal that the PRODAN aggregated species are non-electroactive within the studied electrochemical potential region.

Characterization of multifunctional reverse micelles' interfaces using hemicyanines as molecular probes. II: Effect of the surfactant.

In this work, we have investigated the behavior of the cationic hemicyanine trans-4-[4-(dimethylamino)-styryl]-N-methylpyridinium iodide (HC) in benzene/benzyl-n-hexadecyl dimethylammonium chloride (BHDC)/water reverse micelle media using absorption and emission spectroscopy in addition to the steady-state and time-resolved fluorescence emission techniques and compare the results to those obtained in benzene/sodium 1,4-bis-2-ethylhexylsulfosuccinate (AOT)/water reverse micelle media (Moyano, F.; et al. J.

Characterization of multifunctional reverse micelles' interfaces using hemicyanines as molecular probes. I. Effect of the hemicyanines' structure.

In this work, we report the behavior of two different hemicyanines, trans-4-[4-(dimethylamino)styryl]-N-methylpyridinium iodide (HC) and 4-[4-(dihexadecylamino)styryl]-N-methylpyridinium iodide (DIA), in water/sodium 1,4-bis-2-ethylhexylsulfosuccinate (AOT)/benzene reverse micelles media using absorption and emission spectroscopy in addition to the steady-state and time-resolved fluorescence emission techniques. Our results show that the AOT reverse micelles interface has the nontrivial deaggregation property, a result that may have potential application for the preparation of dye lasers, which require a noninteracting monomeric form of the dye. Also, we show that the water interacts with a different region of the AOT moiety depending on the external organic solvent used and, in addition, we also present a nice, simple, and noteworthy method that helps to examine the presence or the absence of organized media.

An example of how to use AOT reverse micelle interfaces to control a photoinduced intramolecular charge-transfer process.

6-Propionyl-2-(N,N-dimethyl)aminonaphtahalene, PRODAN, is widely used as a fluorescent molecular probe due to its significant Stokes shift in polar solvents. It is an aromatic compound with intramolecular charge-transfer (ICT) states which can be particularly useful as sensors. In this work, we performed absorption, steady-state, time-resolved fluorescence (TRES), and time-resolved area normalized emission (TRANES) spectroscopies on PRODAN dissolved in nonaqueous reverse micelles.

On the investigation of the bilayer functionalities of 1,2-di-oleoyl-sn-glycero-3-phosphatidylcholine (DOPC) large unilamellar vesicles using cationic hemicyanines as optical probes: a wavelength-selective fluorescence approach.

The behavior of the cationic hemicyanines trans-4-[4-(dimethylamino)-styryl]-1-methylpyridinium iodide (HC) and 4,(4-(dihexadecylamino)styryl-N-methyl-pyridinium iodide (DIA) were studied in large unilamellar vesicles (LUV) of 1,2-di-oleoyl-sn-glycero-3-phosphatidylcholine (DOPC) using absorption, emission, depolarization and time resolved spectroscopies. Also, thorough spectroscopic studies were performed in homogeneous media to investigate the different interactions that the dyes can experience with its microenvironment. These results help us to comprehend the dye performance under different media and, consequently find interesting features of the DOPC membrane properties.

New insights on the behavior of PRODAN in homogeneous media and in large unilamellar vesicles.

The behavior of 6-propionyl-2-dimethylaminonaphthalene (PRODAN) was studied in homogeneous media and in large unilamellar vesicles (LUVs) of the phospholipid 1,2-di-oleoyl-sn-glycero-3-phosphatidylcholine (DOPC), using absorption, emission, depolarization, and time-resolved spectroscopies. In homogeneous media, the Kamlet and Taft solvatochromic comparison method quantified solute-solvent interactions from the absorption and emission PRODAN bands. These studies demonstrate that the absorption band is sensitive to the polarity-polarizability (pi) and the hydrogen bond donor ability (alpha) parameters of the media.