General Synthesis and Physicochemical Characterisation of a Series of Peptide‐Mimic Lysine‐Based Amino‐Functionalised Lipids

A series of novel malonic acid diamides (second generation) with two long hydrophobic alkyl chains and an alkaline polar head group was synthesised and characterised as a new class of amino‐functionalised lipids. These peptide‐mimic lipids are suitable for polynucleotide transfer. The lipids bear a novel backbone consisting of a lysine unit and a malonic acid unit. Six different head‐group structures, which vary in size and number of amino groups that can be protonated, were attached to the backbone structure. Furthermore, different alkyl chains were used to build the lipophilic part (namely tetradecyl, hexadecyl, and oleyl). Phase transitions of the new compounds in aqueous dispersions at pH 10 were analysed and discussed in terms of head group and alkyl chain variations. The shape and size of the formed aggregates of selected lipid dispersions were investigated by dynamic light scattering and transmission electron microscopy.     

Atomic Layer Deposition of Cobalt Phosphide for Efficient Water Splitting

Transition‐metal phosphides (TMP) prepared by atomic layer deposition (ALD) are reported for the first time. Ultrathin Co‐P films were deposited by using PH₃ plasma as the phosphorus source and an extra H₂ plasma step to remove excess P in the growing films. The optimized ALD process proceeded by self‐limited layer‐by‐layer growth, and the deposited Co‐P films were highly pure and smooth. The Co‐P films deposited via ALD exhibited better electrochemical and photoelectrochemical hydrogen evolution reaction (HER) activities than similar Co‐P films prepared by the traditional post‐phosphorization method. Moreover, the deposition of ultrathin Co‐P films on periodic trenches was demonstrated, which highlights the broad and promising potential application of this ALD process for a conformal coating of TMP films on complex three‐dimensional (3D) architectures.     

Structure–Function Relationships of New Lipids Designed for DNA Transfection

Cationic liposome/DNA complexes can be used as nonviral vectors for direct delivery of DNA‐based biopharmaceuticals to damaged cells and tissues. To obtain more effective and safer liposome‐based gene transfection systems, two cationic lipids with identical head groups but different chain structures are investigated with respect to their in vitro gene‐transfer activity, their cell‐damaging characteristics, and their physicochemical properties. The gene‐transfer activities of the two lipids are very different. Differential scanning calorimetry and synchrotron small‐ and wide‐angle X‐ray scattering give valuable structural insight. A subgel‐like structure with high packing density and high phase‐transition temperature from gel to liquid‐crystalline state are found for lipid 7 (N′‐2‐[(2,6‐diamino‐1‐oxohexyl)amino]ethyl‐2,N‐bis(hexadecyl)propanediamide) containing two saturated chains. Additionally, an ordered head‐group lattice based on formation of a hydrogen‐bond network is present. In contrast, lipid 8 (N′‐2‐[(2,6‐diamino‐1‐oxohexyl)amino]ethyl‐2‐hexadecyl‐N‐[(9Z)‐octadec‐9‐enyl]propanediamide) with one unsaturated and one saturated chain shows a lower phase‐transition temperature and a reduced packing density. These properties enhance incorporation of the helper lipid cholesterol needed for gene transfection. Both lipids, either pure or in mixtures with cholesterol, form lamellar phases, which are preserved after addition of DNA. However, the system separates into phases containing DNA and phases without DNA. On increasing the temperature, DNA is released and only a lipid phase without intercalated DNA strands is observed. The conversion temperatures are very different in the two systems studied. The important parameter seems to be the charge density of the lipid membranes, which is a result of different solubility of cholesterol in the two lipid membranes. Therefore, different binding affinities of the DNA to the lipid mixtures are achieved.     

Studies on pre-hump and main fractions of cellulose-2,5-acetate in acetone

Technical cellulose-2.5-acetates (CA 2.5) were characterized regarding their carbohydrate composition in comparison to the raw material. The association of the CA 2.5 samples in acetone was studied by size exclusion chromatography (SEC) using various acetone grades and styrene divinylbenzene copolymer columns. In HPLC grade acetone with and without addition of 1% water up to three different pre-humps eluted in front of the main fraction of the polymer. The evaluation of the main peak by light scattering measurements resulted in high molar masses indicating that for these technical CA 2.5 samples even the main fraction is not dissolved without association. No pre-humps or association phenomena were observed after addition of 1 ppm LiBr to HPLC grade acetone or with p.a. grade acetone. In addition pre-hump enriched and pre-hump free fractions were isolated by fractionated precipitation. The carbohydrate composition of these fractions was determined and correlated with their association pattern in SEC investigations.     

Continuous bordering of matrices and continuous matrix decompositions

Summary. Let be the set of all real -matrices of rank . We prove that for there are no continuous vector fields such that the bordered matrix is regular for all . This result has some relevance for the numerical analysis of steady state bifurcation. As a by-product we show that there is no nonvanishing continuous vector field with for all , where is the set of all matrices of rank deficiency one. This implies that there is no singular value decomposition of depending continuously on in any matrix set which contains . As another application we prove that in general there is no global analytic singular value decomposition for analytic matrix valued functions of more than one real variable. Received October 6, 1993 / Revised version received July 18, 1994     

Selective nucleophilic replacement of the benzylsulfanyl group in 2,4‐disulfanyl‐substituted thieno[2,3‐d]pyrimidin‐6‐carboxylic acid derivatives by secondary amines

Thieno[2,3‐d]pyrimidines with benzylsulfanyl and allylsulfanyl group in the presence of other alkylsul‐fanyl substituents react selectively under mild conditions with secondary amines under replacement of the benzyl or allyl residue whereas the other substituents remain intact. This enables the synthesis of different basic substituted derivatives with potentially biologically activity.