Pharmaceutical formulations utilizing protein drugs as powders can be used as drug delivery systems in various ways. Besides powders for inhalation, another promising approach is their use as suspensions in non-aqueous liquids for subcutaneous administration providing high protein stability and good injectability. In this study protein powder suspensions were prepared using a swing-mill.
View Article and Find Full Text PDFThe nanofiber formation in aqueous suspension of two classes of symmetric single-chain bolaamphiphiles with different polar headgroups and a diacetylene-modified alkyl chain with a length of 32, 34, and 36 C atoms was investigated by differential scanning calorimetry, transmission electron microscopy, and small-angle neutron scattering. As observed before for other bolalipids with phosphocholine (PC) and dimethyl-phosphoethanolamine (MePE) headgroups, the molecules form fibers when suspended in water at low temperatures but disassemble into micellar-like aggregates upon heating. The introduction of a diacetylene group in the middle of the long chain leads to a perturbation of chain packing so that this fiber-micelle transition occurs at lower temperature compared to the other bolalipids having unmodified alkyl chains.
View Article and Find Full Text PDFA variety of bolalipids with a single long alkyl chain and two identical headgroups self-assemble in aqueous solutions into helical entangled nanofibers leading to the formation of a hydrogel. An increase in temperature usually leads to the break-up of the fiber structure into micellar aggregates. In this paper the question is addressed whether bolalipids of different lengths or different headgroup structures can form mixed fibers.
View Article and Find Full Text PDFThe self-assembly process in aqueous suspension of two new asymmetrical single-chain bolaamphiphiles, namely 32-{[hydroxy(2-hydroxyethoxy)phosphinyl]oxy}dotriacontane-1-yl-{2-[N-(3-dimethylaminopropyl)-N,N-dimethylammonio]ethylphosphate} (DMAPPC-C32-POH) and 32-hydroxydotriacontane-1-yl-{2-[N-(3-dimethylaminopropyl)-N,N-dimethylammonio]ethylphosphate} (DMAPPC-C32-OH), was studied as a function of temperature using transmission electron microscopy, differential scanning calorimetry, FT-IR-spectroscopy, small angle neutron and small angle X-ray scattering to determine whether the asymmetry of the molecule induces the formation of types of aggregates other than the well characterized helical nanofibres of structurally similar symmetrical single-chain bolaamphiphiles with identical headgroups. DMAPPC-C32-POH in acetate buffer at pH 5 can still form nanofibres, i.e.
View Article and Find Full Text PDFThe high-resolution humidity scanning QCM-D technique enables investigation of hydration of soft matter films using a quartz crystal microbalance with dissipation monitoring (QCM-D) equipped with a humidity module. Based on a continuous increase of relative humidity, properties of soft matter films can be investigated depending on the water content of the surrounding atmosphere. Determination of complete water sorption isotherms is possible via analysis of the overtone dependence of the resonance frequencies.
View Article and Find Full Text PDFThe aggregation behaviour in aqueous suspensions of symmetrical bipolar phospholipids (bolalipids) composed of one long alkyl chain and two polar headgroups were studied as a function of their chemical structure, i.e. the length of their chain, the modification of the chain by introduction of hetero-atoms, triple bonds, or phenyl rings, and the size of the headgroups.
View Article and Find Full Text PDFThe aggregation behavior in aqueous suspension of two symmetrical single-chain bolaamphiphiles, namely 12,21-dithiadotriacontane-1,32-diyl-bis [2-(tri-methylammonio)ethylphosphate] (PC-C32SS-PC) and 12,21-dithiadotriacontane-1,32-diyl-bis[2-(dimethylammonio)ethylphosphate] (Me(2)PE-C32SS-Me(2)PE), containing sulfur as heteroatoms in the chains, was studied using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), small angle neutron scattering (SANS), and transmission electron microscopy (TEM). The rheological properties of hydrogels formed by the aggregation into nanofibers were studied by oscillatory rheology. Based on the well-characterized behavior of bolalipids with long alkyl chains which at room temperature can form a network of nanofibers leading to the formation of a hydrogel, we investigated whether the incorporation of two heteroatoms of sulfur into the spacer chain of the molecules has an influence on the aggregation properties.
View Article and Find Full Text PDFThe aggregation behavior and rheological properties of aqueous suspensions of the bolaamphiphile dotriacontane-1,32-diyl-bis[2-(dimethylammonio)ethylphosphate] (Me(2)PE-C32-Me(2)PE) were investigated depending on the pH value and the salinity by means of differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and oscillatory rheology. This bolaamphiphile self-assembles into helical fibers of approximately 5 nm thickness with an all-trans conformation of the alkyl chains. These nanofibers can gel water very effectively by forming a three-dimensional network.
View Article and Find Full Text PDFHerein, we report the synthesis of two novel, amino-functionalized single-chain bolalipids and, based on those, a general synthetic approach for the insertion of various carboxylic acids into the bolalipid headgroups, e.g. alpha-lipoic acid for one-dimensional fixation of gold nanoparticles, sorbic acid for polymerization experiments, or lysine for the use in gene delivery systems.
View Article and Find Full Text PDFThe chemical structures of polymethylene-1,omega-bis(phosphocholines) that self-assemble into nanofibres was modified on the one hand in the hydrophobic chain region, by introduction of sulfur and oxygen atoms, and on the other hand by variation of the polar headgroup structure with functionalised tertiary amines. The temperature-dependent self-assembly of these novel bolaphospholipids into nanofibres and spherical micelles was investigated by differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). The thermal stabilities of the nanofibres strongly depend on the chemical compositions of the headgroups and of the hydrophobic chains.
View Article and Find Full Text PDFThe temperature-dependent self-assembly and the mixing behavior of symmetrical single-chain bolaamphiphiles with different polymethylene chain lengths and different headgroup structures were investigated in water by differential scanning calorimetry (DSC), cryo transmission electron microscopy (cryo-TEM), and small angle neutron scattering (SANS). The even-numbered polymethylene-1,omega-bis(phosphocholines) (PC-C n-PC) are known to form nanofibers composed of stretched molecules with an all- trans alkyl chain conformation (Drescher, S.; Meister, A.
View Article and Find Full Text PDFBipolar phospholipids (bolalipids) represent an exciting class of amphiphilic molecules as they self-assemble in water to distinct structures of nanoscopic dimensions. Reported here are structural details of helical nanofibers, composed of achiral, symmetrical single-chain bolalipids with phosphocholine headgroups. These nanofibers are used as template for the fixation of gold nanoparticles (AuNPs) without prior functionalization.
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