Molecular Organization of Various Collagen Fragments as Revealed by Atomic Force Microscopy and Diffusion‐Ordered NMR Spectroscopy

Heterogeneous mixtures of collagen fragments can be used as nutrition supplement or as key ingredients for ointments with therapeutic relevance in wound healing. Some mixtures of collagen fragments are referred to as collagen hydrolysates owing to the production process with hydrolytic enzymes. Since the precise composition of collagen hydrolysates is generally unknown, it is of interest to analyze samples containing various collagen fragments with appropriate biophysical methods. Any product optimization without a profound knowledge concerning the size and the molecular weight distribution of its components is nearly impossible. It turned out that a combination of AFM methods with NMR techniques is exceptionally suited to examine the size range and the aggregation behavior of the collagen fragments in the hydrolysates of fish, jellyfish, chicken, porcine and bovine collagen. Supported by molecular modeling calculations, the AFM and NMR experiments provide a detailed knowledge about the composition of collagen hydrolysates and collagen ointments. Furthermore, the data allow a correlation between the size of the fragments and their potential bioactivity.     

Phase effects in masking by harmonic complexes in birds

Masking by harmonic complexes depends on the frequency content of the masker and its phase spectrum. Harmonic complexes created with negative Schroeder phases (component phases decreasing with increasing frequency) produce more masking than those with positive Schroeder phases (increasing phase) in humans, but not in birds. The masking differences in humans have been attributed to interactions between the masker phase spectrum and the phase characteristic of the basilar membrane. In birds, the similarity in masking by positive and negative Schroeder maskers, and reduced masking by cosine-phase maskers (constant phase), suggests a phase characteristic that does not change much along the basilar papilla. To evaluate this possibility, the rate of phase change across masker bandwidth was varied by systematically altering the Schroeder algorithm. Humans and three species of birds detected tones added in phase to a single component of a harmonic complex. As observed in earlier studies, the minimum amount of masking in humans occurred for positive phase gradients. However, minimum masking in birds occurred for a shallow negative phase gradient. These results suggest a cochlear delay in birds that is reduced compared to that found in humans, probably related to the shorter avian basilar epithelia.     

Control of branching ratios in the dissociative ionization of deuterium chloride

The dissociative ionization of deuterium chloride (DCl) has been investigated by employing femtosecond laser pulses at 805 nm. The product branching ratio D(+)/Cl(+) of the fragments D(+) and Cl(+) is strongly affected by the chirp alpha of the laser pulses. The ratio can be controlled by a factor of 3 ranging from D(+)/Cl(+) = 0.7 at alpha = -800 fs(2) to D(+)/Cl(+) = 1.9 at alpha = +150 fs(2). The observation can be rationalized by a model where negative chirp favors intra-electronic state excitation, and positive chirp favors inter-electronic state excitation in the dissociation of the molecular ion. Complementary experiments on hydrogen chloride (HCl) are discussed.     

Synthesis of key fragments of leiodelide A

The synthesis of all key fragments of the marine macrolide leiodelide A is described. The polyoxygenated northern subunit is derived from d-xylose, while the southern subunit is rapidly assembled via an aldol reaction and Horner-Wadsworth-Emmons olefination. This highly convergent approach will allow for rapid modification and assembly of several isomers of leiodelide A, which may be necessary considering the assignment of leiodelide B has been previously shown to be incorrect.     

Rigid Lipid Membranes and Nanometer Clefts: Motifs for the Creation of Molecular Landscapes

Amphiphilic lipids associate in water spontaneously to form micelles, vesicles, monolayers, or biological membranes. These aggregates are soft and their shape can be changed easily. They behave like complex fluids because they are merely held together by weak, nondirected forces. The most important characteristic of these monolayers is their ability to dissolve hydrophobic molecules in the form of freely movable monomers. The fluid molecular layers are not suitable to anchor the components of chain reactions. However, if the alkyl chains are replaced by rigid skeletons or if the head groups are connected through intermolecular interactions, the aggregates become rigid and their fluid solvent character is lost. The construction of chiral surfaces by synkinesis (synthesis of noncovalent compounds) and of enzyme‐type surface clefts of defined size can now be carried out by using rigid lipid membranes. Monolayers and nanometer pores on solid substrates attain sharp edges, and upright nanometer columns on smooth surfaces no longer dissipate. Five examples illustrate the advantages of using rigid molecular assemblies: 1) Cationic domains of rigid edge amphiphiles in fluid membranes act as manipulable ion channels. 2) Spherical micelles, micellar helical fibers, and vesicular tubes can be dried and stored as stable material. Molecular landscapes form on smooth surfaces. 3) α,ω‐Diamide bolaamphiphiles form rigid nanometer‐thick walls on smooth surfaces and these barriers cannot be penetrated by amines. Around steroids and porphyrins, they form rigid nanometer clefts whose walls and water‐filled centers can be functionalized. 4) The structure of rigid oligophenylene‐ and quinone monolayers on electrodes can be changed drastically and reversibly by changing the potential. 5) 10¹⁰ Porphyrin cones on a 1‐cm² gold electrode can be controlled individually by AFM‐ and STM‐tips and investigated by electrochemical, photochemical, and mechanical means. In summary, rigid monolayers and bilayers allow the formation of a great variety of membrane structures that cannot be obtained from classical fluid alkyl amphiphiles.     

Design and performance of an X‐ray scanning microscope at the Hard X‐ray Nanoprobe beamline of NSLS‐II

A hard X‐ray scanning microscope installed at the Hard X‐ray Nanoprobe beamline of the National Synchrotron Light Source II has been designed, constructed and commissioned. The microscope relies on a compact, high stiffness, low heat dissipation approach and utilizes two types of nanofocusing optics. It is capable of imaging with ～15 nm × 15 nm spatial resolution using multilayer Laue lenses and 25 nm × 26 nm resolution using zone plates. Fluorescence, diffraction, absorption, differential phase contrast, ptychography and tomography are available as experimental techniques. The microscope is also equipped with a temperature regulation system which allows the temperature of a sample to be varied in the range between 90 K and 1000 K. The constructed instrument is open for general users and offers its capabilities to the material science, battery research and bioscience communities.     

Neutron velocity distribution from a superthermal solid 2H2 ultracold neutron source

We have determined for the first time the velocity distribution of neutrons from a solid ²H₂ ultracold neutron (UCN) source. The spectrum rises sharply above 4.5m/s and has a maximum around 7m/s after transport in an 8m long guide. The number of neutrons in the UCN velocity range (< 7m/s) may be increased by a factor of two by placing the experiment 1m above the UCN source level.