Branched chain discotics Phase structure and orientation behaviour

Studies show that branching the side chains of hexakis(acoyloxy)-benzenes (HAB) and -cyclohexanes (HAChx) does not modify the structure of the discotic mesophase formed. Shear fields appear to act on entire columns, not on individual discs, thereby causing alignment of columns in the shear direction. X-ray diffraction patterns of samples at temperatures between 30°C and 40°C above the clearing temperature provide evidence for the presence of mesophase order.     

Molecular addressing? Studies on light-induced reorientation in liquid-crystalline side chain polymers

Polarized light leads to an effective reorientation of the optic axis in the glassy state of liquid-crystalline side chain polymers containing azobenzene mesogenic groups, via a trans-cis and cis-trans isomerization. Using a combination of U V and IR dichroitic studies it is shown for copolymers consisting of chromophores (azobenzene) and non-chromophores (phenylbenzoate) that only the chromophores are reoriented by light as far as the glassy state is concerned. Individual chromophores are thus addressed by photoselection. Photoselection in the fluid nematic state, on the other hand, leads also to a reorientation of the non-chromophores.     

New disc-shaped mesogens based on pentakis(phenylethynyl)benzene derivatives

First examples of amphiphilic alkyl pentakis(phenylethynyl)benzene ethers containing functional groups at the terminal position of their alkoxy chains were synthesized by etherification of pentabromophenol with 11-bromoundecan-1-ol and 11-bromoundecanoic acid ethyl ester, respectively, and subsequent palladium catalyzed, fivefold coupling reactions with the substituted phenylacetylene. Two undecanoic acid derivatives with different pentakis(phenylethynyl)phenoxy substituents in the ω-position were prepared by ester cleavage from the corresponding ethyl esters. The thermal behaviours of five penta-alkynes in their pure states, as well as of their charge transfer complexes formed from mixtures with 2,4,7-tri-nitrofluorenone, were examined.     

Isotope dilution mass spectrometry for micro- and trace-element determination

Isotope dilution mass spectrometry is an important method for accurate and precise determination of trace- and micro-amounts of the elements. Using different ionization techniques in the mass spectrometer most of the elements of the periodic table can be analysed.     

Methodische Hinweise und Fehlerm?glichkeiten bei der Untersuchung membranfiltrierter w?\riger L?sungen

Zusammenfassung Es wird auf eine bisher nicht beachtete Fehlermöglichkeit bei der analytischen Untersuchung und Weiterverwendung von membranfiltrierten Lösungen hingewiesen. Die üblichen Membranfilter enthalten zur Hydrophilisierung bestimmte Mengen anionaktiver Tenside, die sich nur in wechselndem Ausma\e vor dem Gebrauch eluieren lassen. Bei der Untersuchung von membranfiltrierten Flu\-, Grund- und Trinkwasserproben findet man dadurch zu hohe Tensidkonzentrationen und bei der Austestung und Verwendung sterilfiltrierter Wirkstofflösungen u. a. können betrÄchtliche Störungen eintreten. Von Fall zu Fall ist darum eine sorgfÄltige Versuchskontrolle hinsichtlich einer spezifischen Tensidwirkung nötig.

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Summary Reference is made to a source of error so far unknown in analytical examinations of aqueous membrane-filtered solutions. Membrane filters usually contain a certain amount of anionic surface-active substances for hydrophilizing purposes. These substances are only partly eliminated before the use of the filter. Therefore, in samples of membrane-filtered river, underground and tap water concentrations are found higher than the actual detergent content. There may also be interferences with the testing of bio-active substances, for instance of antibiotics. Advice is given to control carefully the possible specific effect of surface-active substances during these experiments.

     

Rates of base-catalysed cleavage of pyridyl-, quinolyl-, picolyl- and (quinolylmethyl)-trimethylsilanes

Rates of cleavage of some picoyl- and (quinolylmethyl)-trimethylsilanes (RSiMe₃, where R = PyCH₂ or QnCH₂SiMe₃) have been measured in “90%” aqueous methanolic sodium methoxide at 50°C. Relative reactivities are: 2-PyCH₂, 1.0; 3-PyCH₂, 0.030; 4-PyCH₂, 8.9; 2-QnCH₂, 41; 3-QnCH₂, 0.161; 4-QnCH₂, 37. The rates correlate well with those for base-catalysed hydrogen-exchange in the parent carbon acids RH. Approximate pK_a's (based on the scale of ion-pair acidities in CsNHC₆H₁₁H₂NC₆H₁₁, with pK_a of 9-phenylfluorene = 18.6) for the carbon acids, RH, can be derived as follows: 2-PyCH₃, 29.5; 3-PyCH₃, 34; 4-PyCH₃, 27; 2-QnCH₃, 25; 3-QnCH₃, 32; 4-QnCH₃, 25.Rates of cleavage of pyridyl- and quinolyl-trimethylsilanes (PySiMe₃ and QnSiMe₃) by sodium hydroxide in 4 : 1 v/v Me₂SO/H₂O at 50°C have also been measured; and the relative reactivities are: 2-Py, 1.0; 3-Py, 2.9; 4-Py, 8.4; 2-Qn, 15.9; 3-Qn, 12.7; 4-Qn, 184. The sequence of reactivity differes from that for base-catalysed hydrogen-exchange at the relevant positions of pyridine and quinoline, indicating that the reactivities are not determined in both cases (if in either) solely by the stabilities of the corresponding carbanions.     

Rhodopsin exhibits a preference for solvation by polyunsaturated docosohexaenoic acid

An all-atom molecular dynamics simulation of rhodopsin in a membrane environment has been carried out with lipid composition similar to that of the retinal membrane. The initial conformation of the protein was taken from the X-ray crystallographic structure (1F88), while those of the lipids came from a previous molecular dynamics simulation. During the course of the 12.5 ns simulation, the initially randomly placed lipids adopt an anisotropic solvation structure around the protein. The lipids, having one saturated stearic acid chain and one polyunsaturated docosohexaenoic acid chain with a zwitterionic phosphatidylcholine headgroup, arrange themselves to maximize contact between the polyunsaturated chain and the protein surface. This organization is driven by energetically favorable interactions between the transmembrance helices and the docosohexaenoyl chains that are largely of the van der Waals type. These observations are consistent with various experimental studies on rhodopsin and other G-protein coupled receptors and with the picture of extreme flexibility in polyunsaturated fatty acid chains that has arisen from recent NMR and computational work.