Mutual Relationships of Nanoconfined Hexoses: Impacts on Hydrodynamic Radius and Anomeric Ratios.

Although all hexose sugars share the same chemical formula, CHO, subtle differences in their stereochemical structures lead to their various biological roles. Due to their prominent role in metabolism, hexose sugars are commonly found in nanoconfined environments. The complexity of authentic nanoconfined biological environments makes it challenging to study how confinement affects their behavior.

Shape of AOT Reverse Micelles: The Mesoscopic Assembly Is More Than the Sum of the Parts.

AOT reverse micelles are a common and convenient model system for studying the effects of nanoconfinement on aqueous solutions. The reverse micelle shape is important to understanding how the constituent components come together to form the coherent whole and the unique properties observed there. The shape of reverse micelles impacts the amount of interface present and the distance of the solute from the interface and is therefore vital to understanding interfacial properties and the behavior of solutes in the polar core.

Direct evidence that cryoprotectant mixtures facilitate individual component permeation into living plant cells.

The fundamental interactions between plant cells and cryoprotectants during vitrification are understudied in the field of plant cryopreservation. Within this area of research, real time cryoprotectant permeation into plant cells is even less documented. In this study, we monitor the real time permeation of individual cryoprotectants into rice callus cells when in mixtures with other cryoprotectants.

Predicting the Geometry of Core-Shell Structures: How a Shape Changes with Constant Added Thickness.

The core-shell assembly motif is ubiquitous in chemistry. While the most obvious examples are core/shell-type nanoparticles, many other examples exist. The shape of the core/shell constructs is poorly understood, making it impossible to separate chemical effects from geometric effects.

Tracking Permeation of Dimethyl Sulfoxide (DMSO) in Shoot Tips Using Coherent Raman Microscopy.

Cryopreservation has emerged as a low-maintenance, cost-effective solution for the long-term preservation of vegetatively propagated crops. Shoot tip cryopreservation often makes use of vitrification methods that employ highly concentrated mixtures of cryoprotecting agents; however, little is understood as to how these cryoprotecting agents protect cells and tissues from freezing. In this study, we use coherent anti-Stokes Raman scattering microscopy to directly visualize where dimethyl sulfoxide (DMSO) localizes within shoot tips.

Where Are Sodium Ions in AOT Reverse Micelles? Fluoride Anion Probes Nanoconfined Ions by F Nuclear Magnetic Resonance Spectroscopy.

Confining water to nanosized spaces creates a unique environment that can change water's structural and dynamic properties. When ions are present in these nanoscopic spaces, the limited number of water molecules and short screening length can dramatically affect how ions are distributed compared to the homogeneous distribution assumed in bulk aqueous solution. Here, we demonstrate that the chemical shift observed in F NMR spectroscopy of fluoride anion, F, probes the location of sodium ions, Na, confined in reverse micelles prepared from AOT (sodium dioctyl sulfosuccinate) surfactants.

Urea Disrupts the AOT Reverse Micelle Structure at Low Temperatures.

Aside from its prominent role in the excretory system, urea is also a known protein denaturant. Here, we characterize urea as it behaves in confined spaces of AOT (sodium bis(2-ethylhexyl) sulfosuccinate) reverse micelles as a model of tight, confined spaces found at the subcellular level. Dynamic light scattering revealed that low temperatures (275 K) caused the smallest of the reverse micelle sizes, = 10, to destabilize and dramatically increase in apparent hydrodynamic diameter.

How to Characterize Amorphous Shapes: The Tale of a Reverse Micelle.

Aerosol-OT reverse micelles represent a chemical construct where surfactant molecules self-assemble to stabilize water nanodroplets 1-10 nm in diameter. Although commonly assumed to adopt a spherical shape, all-atom molecular dynamics simulations and some experimental studies predict a nonspherical shape. If these aggregates are not spherical, then what shape do they take? Because the tools needed to evaluate the shape of something that lacks regular structure, order, or symmetry are not well developed, we present a set of three intuitive metrics─coordinate-pair eccentricity, convexity, and the curvature distribution─that estimate the shape of an amorphous object, and we demonstrate their use on a simulated aerosol-OT reverse micelle.

Non-Uniform Distribution of Cryoprotecting Agents in Rice Culture Cells Measured by CARS Microscopy.

Cryoprotectants allow cells to be frozen in liquid nitrogen and cryopreserved for years by minimizing the damage that occurs in cooling and warming processes. Unfortunately, how the specific cryoprotectants keep the cells viable through the cryopreservation process is not entirely evident. This contributes to the arduous process of optimizing cryoprotectant formulations for each new cell line or species that is conserved.

Nanoconfinement Raises the Energy Barrier to Hydrogen Atom Exchange between Water and Glucose.

In bulk aqueous environments, the exchange of protons between labile hydroxyl groups typically occurs easily and quickly. Nanoconfinement can dramatically change this normally facile process. Through exchange spectroscopy (EXSY) NMR measurements, we observe that nanoconfinement of glucose and water within AOT (sodium bis(2-ethylhexyl) sulfosuccinate) reverse micelles raises the energy barrier to labile hydrogen exchange, which suggests a disruption of the hydrogen bond network.

Coordination Chemistry of a Controlled Burst of Zn in Bulk Aqueous and Nanosized Water Droplets with a Zincon Chelator.

The light-induced photolysis of [Zn(NTAdeCage)] generates a temporally controlled burst of Zn, which is rapidly chelated by the free ligand Zincon. The [Zn(Zincon)] coordination progress is monitored using absorption spectroscopy in bulk aqueous buffer and reverse micelle environments. The [Zn(NTAdeCage)] photocage and free ligand Zincon have different reverse micelle locations that affect the [Zn(Zincon)] formation at the nanoscale compared to the bulk aqueous buffer.

Sweet Confinement: Glucose and Carbohydrate Osmolytes in Reverse Micelles.

The research presented here reports the surprising observation that adding glucose and other carbohydrate osmolytes to the polar phase of water-containing reverse micelles causes the particles to shrink. This apparent change in reverse micelle size is attributed to two factors: an increase in the surface area per surfactant molecule induced by the presence of carbohydrate and changes in the particle shape eccentricity. The studies reported here not only focus on glucose but also explore other carbohydrate osmolytes, specifically ethylene glycol, glycerol, erythritol, xylitol, sorbitol, myo-inositol, and trehalose, in the nanoconfined environments of reverse micelles.

Nanoconfinement's Dramatic Impact on Proton Exchange between Glucose and Water.

Glucose nanoconfined by solubilization in water-containing AOT (sodium bis(2-ethylhexyl) sulfosuccinate) reverse micelles has been investigated using H NMR. NMR spectra reveal well-defined signals for the glucose hydroxyl groups that suggest slow chemical exchange between them and the water hydroxyl groups. Using the EXSY (ZZ-exchange) method, the chemical exchange rate from water to glucose hydroxyl groups was measured for glucose in reverse micelles as a function of size (water pool diameter of ∼1-5 nm) at 25 °C.

Correlation of insulin-enhancing properties of vanadium-dipicolinate complexes in model membrane systems: phospholipid langmuir monolayers and AOT reverse micelles.

We explore the interactions of V(III) -, V(IV) -, and V(V) -2,6-pyridinedicarboxylic acid (dipic) complexes with model membrane systems and whether these interactions correlate with the blood-glucose-lowering effects of these compounds on STZ-induced diabetic rats. Two model systems, dipalmitoylphosphatidylcholine (DPPC) Langmuir monolayers and AOT (sodium bis(2-ethylhexyl)sulfosuccinate) reverse micelles present controlled environments for the systematic study of these vanadium complexes interacting with self-assembled lipids. Results from the Langmuir monolayer studies show that vanadium complexes in all three oxidation states interact with the DPPC monolayer; the V(III) -phospholipid interactions result in a slight decrease in DPPC molecular area, whereas V(IV) and V(V) -phospholipid interactions appear to increase the DPPC molecular area, an observation consistent with penetration into the interface of this complex.

The conundrum of pH in water nanodroplets: sensing pH in reverse micelle water pools.

In aqueous environments, acidity is arguably the most important property dictating the chemical, physical, and biological processes that can occur. However, in a variety of environments where the minuscule size limits the number of water molecules, the conventional macroscopic description of pH is no longer valid. This situation arises for any and all nanoscopically confined water including cavities in minerals, porous solids, zeolites, atmospheric aerosols, enzyme active sites, membrane channels, and biological cells and organelles.

Correlating proton transfer dynamics to probe location in confined environments.

The dramatic impact of differing environments on proton transfer dynamics of the photoacid HPTS prompted us to investigate these systems with two highly complementary methods: ultrafast time-resolved transient absorption and two-dimensional NMR spectroscopies. Both ultrafast time-resolved transient absorption spectroscopy and time-resolved anisotropy decays demonstrate the proton transfer dynamics depend intimately on the specific reverse micellar system. For w(0) = 10 reverse micelles formed with anionic AOT surfactant, the HPTS proton transfer dynamics are similar to dynamics in bulk aqueous solution, and the corresponding (1)H 2D NOESY NMR spectra display no cross peaks between HPTS and AOT consistent with the HPTS residing well hydrated by water in the interior of the reverse micelle water pool.

Ultrafast vibrational dynamics of water confined in phospholipid reverse micelles.

Ultrafast dynamics of OH stretching excitations of H2O confined in dioleoylphosphatidylcholine (DOPC) reverse micelles, a phospholipid model system, are studied in femtosecond pump-probe experiments. Measurements in a wide range of hydration show that spectral diffusion within the OH stretching band accelerates substantially with increasing water content. Concomitantly, the OH stretching lifetime decreases from approximately 500 fs at a 1:1 ratio of water and DOPC molecules (w0 = 1) to 300 fs for large water pools (ratio 16:1, w0 = 16).

Ultrafast energy migration pathways in self-assembled phospholipids interacting with confined water.

Phospholipids self-assembled into reverse micelles in benzene are introduced as a new model system to study elementary processes relevant for energy transport in hydrated biological membranes. Femtosecond vibrational spectroscopy gives insight into the dynamics of the antisymmetric phosphate stretching vibration ν(AS)(PO(2))(-), a sensitive probe of local phosphate-water interactions and energy transport. The decay of the ν(AS)(PO(2))(-) mode with a 300-fs lifetime transfers excess energy to a subgroup of phospholipid low-frequency modes, followed by redistribution among phospholipid vibrations within a few picoseconds.

Cy3 in AOT reverse micelles II. Probing intermicellar interactions using fluorescence correlation spectroscopy.

Cyanine-3 (Cy3) fluorescent dye molecules confined in sodium di-2-ethylhexyl sulfosuccinate (AOT) reverse micelles were examined using dynamic light scattering and fluorescence correlation spectroscopy to probe the kinetics of Cy3 dye and reverse micelle aggregation. This study explored a range of reverse micelle sizes, defined as w(0) = [H(2)O]/[AOT], in which the occupation number ranged from one Cy3 molecule per ∼10(5) to ∼10(6) reverse micelles. These measurements reveal that in the smallest reverse micelle, w(0) = 1, the Cy3 molecules aggregate to form H-aggregate dimers, and the Cy3 dimerization is accompanied by the formation of a transient dimer between reverse micelles.