Microwave‐Assisted Direct Esterification of Cyclic Phosphinic Acids

It is known that phosphinic acids do not undergo direct esterification under conventional conditions. However, the reaction may take place on microwave irradiation. 1‐Hydroxy‐3‐phospholene 1‐oxides, 1‐hydroxy‐phospholane 1‐oxides, and a 1‐hydroxy‐1,2,3,4,5,6‐hexahydrophosphinine 1‐oxide were esterified with n‐pentanol, i‐pentanol, n‐octanol, and i‐octanol(2‐ethylhexanol). The phosphinates prepared in 50%–94% yield are all new compounds, and a number of them are useful intermediates.     

Synchronization engineering: theoretical framework and application to dynamical clustering

A method for engineering the global behavior of populations of rhythmic elements is presented. The framework, which is based on phase models, allows a nonlinear time-delayed global feedback signal to be constructed which produces an interaction function corresponding to the desired behavior of the system. It is shown theoretically and confirmed in numerical simulations that a polynomial, delayed feedback is a versatile tool to tune synchronization patterns. Dynamical states consisting of one to four clusters were engineered to demonstrate the application of synchronization engineering in an experimental electrochemical system.     

Measurement of the 20 and 90 keV resonances in the 18O(p,alpha)15N reaction via the Trojan horse method

The 18O(p,alpha)15N reaction is of primary importance in several astrophysical scenarios, including fluorine nucleosynthesis inside asymptotic giant branch stars as well as oxygen and nitrogen isotopic ratios in meteorite grains. Thus the indirect measurement of the low energy region of the 18O(p,alpha)15N reaction has been performed to reduce the nuclear uncertainty on theoretical predictions. In particular the strength of the 20 and 90 keV resonances has been deduced and the change in the reaction rate evaluated.     

Activation mechanism of the human histamine H4 receptor--an explicit membrane molecular dynamics simulation study

Molecular dynamics (MD) simulations in a membrane-embedded environment were carried out on the homology model of the human histamine H4 receptor (hH4R) alone and in complex with its endogenous activator histamine and with the first reported selective hH4R antagonist JNJ7777120. During the simulation of the histamine-hH4R complex, considerable changes occurred in the hH4R structure as well as in the interaction pattern of histamine at the binding site. These changes are in agreement with experimental data published on GPCR activation. In particular, the intracellular side of TM helix VI moved significantly away from TM helices III and VII. Moreover, histamine formed an interaction with Asn147 (4.57) that was previously proved to be important in hH4R activation. Results of the MD simulations of the native hH4R and the JNJ7777120-hH4R complex suggest that these models represent an inactive conformation of hH4R. MD simulation in the presence of JNJ7777120 resulted in the movement of the intracellular side of TM helix VI in the direction of TM helix III. Snapshots of the simulations may serve as functionally relevant models in the development of novel hH4R ligands in the future.     

A new strategy for the preparation of heterocyclic β-amino esters: orthogonally protected β-amino esters with a piperidine skeleton

A simple strategy is presented for the introduction of a nitrogen atom into the carbocycle of an aminocyclopentenecarboxylic ester via dihydroxylation of the olefinic bond, followed by NaIO₄-mediated cleavage of the diol intermediate and ring expansion, resulting in new regioisomeric 3-amino-4-piperidinecarboxylic acid derivatives. This method permits the preparation of amino esters with a piperidine skeleton in enantiomerically pure form.     

Subtle interactions in silica-alumina mixtures

Object of the study in this paper was the mechanical mixtures of amorphous silica and α-Al₂O₃ with different precursors (gibbsite, boehmite, and γ-Al₂O₃). The results obtained revealed that measurable interactions exist in different binary systems without previous thermal treatment. These interactions could be explained by the existence of attractive and repulsive forces which appear between the OH⁻ groups present on the surfaces of alumina and silica constituents. In thermally treated samples, the interactions are not driven by intermolecular forces but rather by polymorphic transformations of alumina and silica, which are followed by sintering.     

Protein interaction with a Pluronic-modified poly(lactic acid) Langmuir monolayer

Interaction of bovine serum albumin (BSA) with poly(lactic acid) (PLA) layers mixed with poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers (Pluronic) at air/solution interfaces was studied by the Langmuir balance technique. Wettability of the mixed PLA-Pluronic system was characterized in the form of a transferred one-layer Langmuir-Blodgett film, and considerable hydrophilization was obtained for all of the Pluronics (6400, 6800, 10500, and 12700) applied here. The density of PEO chains in the monolayer and hence the coverage of PLA was controlled by the composition and the compression of the mixed monolayers. Tensiometric investigations revealed that a significant reduction of BSA adsorption/penetration was achieved by applying the Pluronic 6800 and 12700 with long PEO blocks for hydrophilization of PLA. Interaction of BSA with the modified PLA monolayer depended on the density and length of the PEO chains. The surface morphological characteristics of the films determined by atomic force microscopy were in good correlation with the results of BSA interaction. The average roughness of the polymer LB layer was high due to BSA penetration into the PLA film, while smooth surfaces with small roughness were obtained when the PLA layer was modified by Pluronic 6800.     

Complexes of Al(III) with d-gluconic acid

The complexation of Al(III) with d-gluconic acid was studied in solution by means of pH-potentiometry, ESI mass spectrometry and one- and two-dimensional NMR spectroscopy. Six complexes were found to form in solution from pH 2 to 10: [AlL]²⁺, [AlLH₋₁]⁺, [AlLH₋₂], [AlLH₋₃]⁻, [AlL₂H₋₁] and [AlL₂H₋₂]⁻. NMR spectroscopy indicated very complicated chemical exchange processes between the free ligand and gluconic acid molecules bound in the metal complexes, with different coordination modes resulting in changes both of the chemical shift and of the line shape of the signals. A solid complex [AlL₂H₋₁] · 2H₂O was isolated as a microcrystalline powder and characterized. The structures of the complexes are discussed on the basis of the spectroscopic results and MM force field calculations.