Density and Excess Molar Volume of the Protic Ionic Liquid Bis(2-hydroxyethyl)ammonium Acetate with Alcohols

Densities were determined for binary mixtures containing the protic ionic liquid bis(2-hydroxyethyl)ammonium acetate [BHEAA] and an alcohol (methanol, ethanol, and 1-propanol) at four different temperatures (293.15, 303.15, 313.15, and 323.15) K and ambient pressure. Coefficients of thermal expansion and excess molar volumes were calculated from the experimental densities. The excess molar volumes were fitted using the Redlich-Kister polynomial equation. Negative deviations from ideal behavior of the excess molar volume were observed for all systems investigated in this study. The results were interpreted in terms of ion-dipole interactions and structural factors of the ionic liquid and alcohol. It was observed that an increase of the alcohol carbon chain length led to lower interactions on mixing.     

Assessment of the integrity of poly(caprolactone)-b-poly(ethylene oxide) micelles under biological conditions: a fluorogenic-based approach

The integrity of block copolymer micelles is important for their effectiveness and successful delivery of the incorporated drugs. Here we evaluate the integrity of poly(caprolactone)-b-poly(ethylene oxide) micelles in media of varying chemical complexity and in cells by using fluorogenic micelles. Fluorogenic dye fluorescein-5-carbonyl azide diacetate was covalently attached to the micelle-core-forming part of the block copolymer, poly(caprolactone). The fluorescence was not detectable unless the poly(caprolactone)21-b-poly(ethylene oxide)45 micelles were destroyed and the fluorogenic dye was activated by deesterification. The fluorescence of the activated dye from destroyed micelles was easily detectable in various media and in cells. Micelles were stable in simple media such as phosphate-buffered saline but disassembled to varying extents with increasing chemical complexity of the media and addition of serum. The integrity of the internalized micelles within the cells showed a time-dependent decrease but remained largely preserved (80%) after 20 h of incubation with cells. A proof of principle was also demonstrated in vivo in mice. The fluorogenic approach to micelle integrity assessment presented herein should lend itself to other block copolymer micelles and assessments of their integrity in complex biological systems in vitro and in vivo.     

Proton diffusion across membranes of vesicles of poly(styrene-b-acrylic acid) diblock copolymers

A study of proton diffusion across membranes of block copolymer vesicles in dilute solution is described. The vesicles were formed by the self-assembly of a diblock copolymer of poly(styrene-b-acrylic acid) (PS(310)-b-PAA(36), where the numbers represent the degree of polymerization for individual blocks). A pH gradient was created across the vesicle membrane with the interior pH (pH(in)) of ca. 2.9 and the exterior pH (pH(out)) of ca. 8.5. The permeability of the polystyrene (PS) membrane was tuned by the addition of different amounts of dioxane (0-40 wt %) to the external aqueous solution. Proton concentrations in the solution outside of the vesicles were followed by monitoring the spectrum of a pH-sensitive fluorescent dye, namely 8-hydroxypyrene-1,3,6-trisulfonate. After the start of the experiment, the proton concentrations increase linearly with the square root of time, while the slopes of the lines increase with dioxane content. To calculate the diffusion coefficients of the protons across the vesicular membrane, the concentration data were fitted using a model, which describes the diffusion of species across the membrane of a reservoir. The apparent diffusion coefficient (D*, which equals the true diffusion coefficient multiplied by the partition coefficient of protons between PS and water) increases from 1.1 x 10(-18) cm(2)/s at 7 wt % dioxane in the external solution to 1.2 x 10(-14) cm(2)/s at 40 wt %. The increase of D* with dioxane content is related to its plasticization of the PS membrane, which can be used as a gating mechanism.     

Radiation damage to alkyl chain monolayers on semiconductor substrates investigated by electron spectroscopy

Monolayers of alkyl chains, attached through direct Si-C bonds to Si(111), via phosphonates to GaAs(100) surfaces, or deposited as alkyl-silane monolayers on SiO2, are investigated by ultraviolet and inverse photoemission spectroscopy and X-ray absorption spectroscopy. Exposure to ultraviolet radiation from a He discharge lamp, or to a beam of energetic electrons, leads to significant damage, presumably associated with radiation- or electron-induced H-abstraction leading to carbon-carbon double-bond formation in the alkyl monolayer. The damage results in an overall distortion of the valence spectrum, in the appearance of (occupied) states above the highest occupied molecular orbital of the alkyl molecule, and in a characteristic (unoccupied state) pi resonance at the edge of the carbon absorption peak. These distortions present a serious challenge for the interpretation of the electronic structure of the monolayer system. We show that extrapolation to zero damage at short exposure times eliminates extrinsic features and allows a meaningful extraction of the density of state of the pristine monolayer from spectroscopy measurements.     

Efficient Cache Attacks on AES, and Countermeasures

We describe several software side-channel attacks based on inter-process leakage through the state of the CPU’s memory cache. This leakage reveals memory access patterns, which can be used for cryptanalysis of cryptographic primitives that employ data-dependent table lookups. The attacks allow an unprivileged process to attack other processes running in parallel on the same processor, despite partitioning methods such as memory protection, sandboxing, and virtualization. Some of our methods require only the ability to trigger services that perform encryption or MAC using the unknown key, such as encrypted disk partitions or secure network links. Moreover, we demonstrate an extremely strong type of attack, which requires knowledge of neither the specific plaintexts nor ciphertexts and works by merely monitoring the effect of the cryptographic process on the cache. We discuss in detail several attacks on AES and experimentally demonstrate their applicability to real systems, such as OpenSSL and Linux’s dm-crypt encrypted partitions (in the latter case, the full key was recovered after just 800 writes to the partition, taking 65 milliseconds). Finally, we discuss a variety of countermeasures which can be used to mitigate such attacks.     

Catalytic effects of monolayers of metals deposited at underpotentials: Oxidation of formic acid on platinum

An independent potentiometric method is developed for the determination of autoprotolysis constants of nonaqueous amphiprotic solvents. The data of potentiometric titrations of a weak protolyte (base or acid) with a strong one are used for calculation of both autoprotolysis constant of the solvent and acid—base constant of the protolyte. The calculations are based on the method of least-squares in combination with the “pit-mapping” procedure developed by Sillén. The validity of the method was proved by the determination of the autoprotolysis constant of water. The method has no restriction concerning the strength of the weak protolyte, the latter being its main advantage. The autoprotolysis constants of methanol and ethylene glycol were determined by means of the proposed method too. The obtained values of pK_MeOH=17.00 and pK_EG=15.91 are in a good agreement with some recent data.     

Co-immobilization of transition-metal complexes and ionic liquids in a polymeric support for liquid-phase hydrogenations

A new recyclable heterogeneous system is reported for reactions with a transition-metal catalyst in ionic liquid medium. It consists of a polymeric phase in which both the ionic liquid and the transition-metal catalyst are incorporated. The system is readily prepared by simple mixing of the components. In hydrogenations, the polymeric system always outperformed the ‘classical’ biphasic systems with ionic liquids and it could be re-used successfully without loss of activity.