Dependence on Oil Chain‐Length of the Curvature Elastic Properties of Nonionic Surfactant Films: Droplet Growth from Spheres to a Bicontinuous Network

Using NMR self‐diffusion and ²H‐NMR relaxation experiments, we have investigated growth of oil‐in‐water microemulsion droplets when spontaneous curvature is lowered, starting at emulsification failure boundary. We compare two ternary nonionic microemulsion systems, containing penta‐ethylene glycol dodecyl ether (C₁₂E₅), and decane or hexadecane, at same surfactant‐to‐oil ratio and approximately the same spontaneous curvature. Droplet growth in microemulsions appears in general to be only minor. Quantitative differences between the two systems indicate differences in the curvature elastic constants.     

On modeling the dissolution of sedimentary rocks in acidic environments. An overview of selected mathematical methods with presentation of a case study

Different environmental processes utilize calcium carbonate and sedimentary rocks, for instance sedimentary rocks are used for water purification as filters and utilized also for acid remediation of process waters before being discarded. Additionally sedimentary rocks are used in another very important environmental process, wet Flue Gas Desulfurization. In this process, limestone and carbonates in general play one important role because of their dissolution and provision of the necessary amount of calcium ions used for the precipitation of gypsum. The objective of this study is to present in a first place an overview of a reduced number of specific theoretical and empirical mathematical models applied to the dissolution of carbonates in acidic environments with provision of additional developments and details, secondly a case study was presented where a suitable time of exposure and surface diffusivity obtained analytically by different methods well describe the experimental results. There were justifications for this choice. The experimental data and the related mathematical modeling were performed considering transient conditions. In the present work diverse raw materials were tested in order to reveal their suitability for wet Flue Gas Desulfurization. The research was focused on products from $\text{ CO }_{2}$ CO 2 fixation processes materials as well as other types of limestone samples. In this way it was found that also waste materials from different environmental processes, like $\text{ CO }_{2}$ CO 2 fixation can be used for Flue Gas Desulfurization.     

Energetics and mechanisms for the unimolecular dissociation of protonated trioses and relationship to proton-mediated formaldehyde polymerization to carbohydrates in interstellar environments

We report the unimolecular decomposition of protonated glyceraldehyde, [HOCH(2)CH(OH)CHO]H(+), and protonated dihydroxyacetone, [HOCH(2)C(O)CH(2)OH]H(+). On the basis of mass spectrometric experiments and computational quantum chemistry, we have found that these isomeric ions interconvert freely at energies below that required for their unimolecular decompositions. The losses of formaldehyde and water (the latter also followed by CO loss) are the dominating processes, with formaldehyde loss having the lower energetic threshold. The reverse of the formaldehyde loss, namely, the addition of formaldehyde to protonated glycolaldehyde, appears to be an inefficient reaction at low temperature and pressure in the gas phase, leading to dissociation products. The relevance of these findings to interstellar chemistry and prebiotic chemistry is discussed, and it is concluded that the suggestion made in the literature that successive addition of formaldehyde by proton-assisted reactions should account for interstellar carbohydrates most likely is incorrect.     

Temperature dependence of charge separation and recombination in porphyrin oligomer-fullerene donor-acceptor systems

Electron-transfer reactions are fundamental to many practical devices, but because of their complexity, it is often very difficult to interpret measurements done on the complete device. Therefore, studies of model systems are crucial. Here the rates of charge separation and recombination in donor-acceptor systems consisting of a series of butadiyne-linked porphyrin oligomers (n = 1-4, 6) appended to C(60) were investigated. At room temperature, excitation of the porphyrin oligomer led to fast (5-25 ps) electron transfer to C(60) followed by slower (200-650 ps) recombination. The temperature dependence of the charge-separation reaction revealed a complex process for the longer oligomers, in which a combination of (i) direct charge separation and (ii) migration of excitation energy along the oligomer followed by charge separation explained the observed fluorescence decay kinetics. The energy migration is controlled by the temperature-dependent conformational dynamics of the longer oligomers and thereby limits the quantum yield for charge separation. Charge recombination was also studied as a function of temperature through measurements of femtosecond transient absorption. The temperature dependence of the electron-transfer reactions could be successfully modeled using the Marcus equation through optimization of the electronic coupling (V) and the reorganization energy (λ). For the charge-separation rate, all of the donor-acceptor systems could be successfully described by a common electronic coupling, supporting a model in which energy migration is followed by charge separation. In this respect, the C(60)-appended porphyrin oligomers are suitable model systems for practical charge-separation devices such as bulk-heterojunction solar cells, where conformational disorder strongly influences the electron-transfer reactions and performance of the device.     

An all-photonic molecule-based D flip-flop

The photochromic fluorescence switching of a fulgimide derivative was used to implement the first molecule-based D (delay) flip-flop device, which works based on the principles of sequential logic. The device operates exclusively with photonic signals and can be conveniently switched in repeated cycles.     

Application and Structural Analysis of Triazole‐Bridged Disulfide Mimetics in Cyclic Peptides

Ruthenium‐catalysed azide–alkyne cycloaddition (RuAAC) provides access to 1,5‐disubstituted 1,2,3‐triazole motifs in peptide engineering applications. However, investigation of this motif as a disulfide mimetic in cyclic peptides has been limited, and the structural consequences remain to be studied. We report synthetic strategies to install various triazole linkages into cyclic peptides through backbone cyclisation and RuAAC cross‐linking reactions. These linkages were evaluated in four serine protease inhibitors based on sunflower trypsin inhibitor‐1. NMR and X‐ray crystallography revealed exceptional consensus of bridging distance and backbone conformations (RMSD<0.5 Å) of the triazole linkages compared to the parent disulfide molecules. The triazole‐bridged peptides also displayed superior half‐lives in liver S9 stability assays compared to disulfide‐bridged peptides. This work establishes a foundation for the application of 1,5‐disubstituted 1,2,3‐triazoles as disulfide mimetics.     

DNA‐Binding Properties of Amidine‐Substituted Spiropyran Photoswitches

Two amidine‐substituted spiropyran derivatives have been characterized with respect to the DNA‐binding properties over a broad pH interval. The two derivatives differ in the number of positive charges. By varying the pH, the protonation state of the derivatives is also changed, allowing for additional variations in the charge distribution. We show that the closed spiro isomer does not bind for either of the two derivatives, whereas the open merocyanine forms bind both in the protonated and in the nonprotonated state, but with dramatically different binding constants. Flow‐oriented linear dichroism (LD) measurements also show that there are differences in the binding modes between the various forms. We rationalize these differences in terms of structure and charge distribution.     

Acid/Base Switching of the Tautomerism and Conformation of a Dioxoporphyrin for Integrated Binary Subtraction

Compared with most of the reported logic devices based on the supramolecular approach, systems based on individual molecules can avoid challenging construction requirements. Herein, a novel dioxoporphyrin DPH₂₂ was synthesized and two of its tautomers were characterized by single‐crystal X‐ray diffraction studies. Compound DPH₂₂ exhibits multichannel controllable stepwise tautomerization, protonation, and deprotonation processes through interactions with H⁺ and F^? ions. By using the addition of H⁺ and F^? ions as inputs and UV/Vis absorption values at λ=412, 510, 562, and 603 nm as outputs, the controlled tautomerism of DPH₂₂ has been successfully used for the construction of an integrated molecular level half‐subtractor and comparator. In addition, this acid/base‐switched tautomerism is reversible, thus endowing the system with ease of reset and recycling; consequently, there is no need to modulate complicated intermolecular interactions and electron‐/charge‐transfer processes.     

Synthesis of 1-Bromo-3-butyn-2-one and 1,3-Dibromo-3-buten-2-one

Synthetic procedures for the preparation of 1-bromo-3-butyn-2-one and 1,3-dibromo-3-buten-2-one are given. These compounds are prepared from 2-bromomethyl-2-vinyl-1,3-dioxolane, which can readily be prepared from 2-ethyl- 2-methyl-1,3-dioxolane. The synthetic routes are as follows: 2-bromomethyl-2-vinyl-1,3-dioxolane is converted to 2-(1,2-dibromoethyl)-2-bromomethyl-1,3-dioxolane. Double dehydrobromination with ^tBuOK affords 2-ethynyl-2-bromomethyl-1,3-dioxolane. Formolysis with formic acid gives 1-bromo-3-butyn-2-one. Deacetalized 2-bromoethyl-2-vinyl-1,3-dioxolane was treated with Br₂ and Li₂CO₃/12-crown-4 in tetrahydrofuran to give 1,3-dibrom-3-buten-2-one in moderate yield.     

Determination of phosphonoformate (foscarnet) in biological fluids by ion-pair reversed-phase liquid chromatography

Bioanalytical liquid chromatographic methods for the determination of phosphonoformate (foscarnet) have been developed. Biological fluids, after simple pre-treatment (ultrafiltration and/or treatment with charcoal), were injected into a reversed-phase liquid chromatographic system with electrochemical detection. Foscarnet was retained as an ion pair with tetrahexylammonium; addition of pyrophosphate was necessary in order to obtain an acceptable peak. This additive could also be used for the fine regulation of the retention to achieve the necessary selectivity.