Wound Closure After Port Implantation-A Randomized Controlled Trial Comparing Tissue Adhesive and Intracutaneous Suturing.

BACKGROUND: Wound healing after pectoral port implantation is a major factor determining the success or failure of the procedure. Infection and wound dehiscence can endanger the functionality of the port system and impede chemotherapy. The cosmetic result is important for patient satisfaction as well. METHODS: From August 2015 to July 2017, adult patients with an indication for port implantation were entered into a prospective, randomized and controlled single-center study. The skin incision was closed either with tissue adhesive or with an intracutaneous suture. The primary endpoints were the total score of the scar evaluated by the patient and the investigator on the POSAS scale (Patient and Observer Scar Assessment Scale: 6 [normal skin] to 60 points), blinded assessment of photographic documentation by ten evaluating physicians, and the patient's reported quality of life. The calculation of case numbers was based only on the patients' overall POSAS assessment, which was tested for non-inferiority. The secondary endpoints were other complications (infection, dehiscence) and the duration of wound closure (trial registration number NCT02551510). RESULTS: 156 patients (60 ± 13 years, 64% women) participated in the study. The patient-assessed total POSAS score of tissue adhesive revealed non-inferiority to suturing (adhesive 11.7 ± 5.8 vs. suture 10.1 ± 4.0, p for non-inferiority <0.001). Both the investigators in their POSAS assessments and the blinded physician evaluators in their assessment of photographically documented wounds rated wound closure by suturing better than closure with tissue adhesive. No significant differences were found between groups with respect to quality of life or the frequency of wound infection or dehiscence. CONCLUSION: Closure of the upper cutaneous layer with tissue adhesive is a suitable and safe method of wound closure after port implantation.

Communication: Probing the absolute configuration of chiral molecules at aqueous interfaces.

We demonstrate that the enantiomers of chiral macromolecules at an aqueous interface can be distinguished with monolayer sensitivity using heterodyne-detected vibrational sum-frequency generation (VSFG). We perform VSFG spectroscopy with a polarization combination that selectively probes chiral molecular structures. By using frequencies far detuned from electronic resonances, we probe the chiral macromolecular structures with high surface specificity. The phase of the sum-frequency light generated by the chiral molecules is determined using heterodyne detection. With this approach, we can distinguish right-handed and left-handed helical peptides at a water-air interface. We thus show that heterodyne-detected VSFG is sensitive to the absolute configuration of complex, interfacial macromolecules and has the potential to determine the absolute configuration of enantiomers at interfaces.

Investigation of the Ice-Binding Site of an Insect Antifreeze Protein Using Sum-Frequency Generation Spectroscopy.

We study the ice-binding site (IBS) of a hyperactive antifreeze protein from the beetle Dendroides canadensis (DAFP-1) using vibrational sum-frequency generation spectroscopy. We find that DAFP-1 accumulates at the air-water interface due to the hydrophobic character of its threonine-rich IBS while retaining its highly regular ß-helical fold. We observe a narrow band at 3485 cm(-1) that we assign to the O-H stretch vibration of threonine hydroxyl groups of the IBS. The narrow character of the 3485 cm(-1) band suggests that the hydrogen bonds between the threonine residues at the IBS and adjacent water molecules are quite similar in strength, indicating that the IBS of DAFP-1 is extremely well-ordered, with the threonine side chains showing identical rotameric confirmations. The hydrogen-bonded water molecules do not form an ordered ice-like layer, as was recently observed for the moderate antifreeze protein type III. It thus appears that the antifreeze action of DAFP-1 does not require the presence of ordered water but likely results from the direct binding of its highly ordered array of threonine residues to the ice surface.

Observation of ice-like water layers at an aqueous protein surface.

We study the properties of water at the surface of an antifreeze protein with femtosecond surface sum frequency generation spectroscopy. We find clear evidence for the presence of ice-like water layers at the ice-binding site of the protein in aqueous solution at temperatures above the freezing point. Decreasing the temperature to the biological working temperature of the protein (0 °C to -2 °C) increases the amount of ice-like water, while a single point mutation in the ice-binding site is observed to completely disrupt the ice-like character and to eliminate antifreeze activity. Our observations indicate that not the protein itself but ordered ice-like water layers are responsible for the recognition and binding to ice.

Structure and dynamics of water in nanoscopic spheres and tubes.

We study the reorientation dynamics of liquid water confined in nanometer-sized reverse micelles of spherical and cylindrical shape. The size and shape of the micelles are characterized in detail using small-angle x-ray scattering, and the reorientation dynamics of the water within the micelles is investigated using GHz dielectric relaxation spectroscopy and polarization-resolved infrared pump-probe spectroscopy on the OD-stretch mode of dilute HDO:H2O mixtures. We find that the GHz dielectric response of both the spherical and cylindrical reverse micelles can be well described as a sum of contributions from the surfactant, the water at the inner surface of the reversed micelles, and the water in the core of the micelles. The Debye relaxation time of the core water increases from the bulk value τ(H2O) of 8.2 ± 0.1 ps for the largest reverse micelles with a radius of 3.2 nm to 16.0 ± 0.4 ps for the smallest micelles with a radius of 0.7 nm. For the nano-spheres the dielectric response of the water is approximately ∼6 times smaller than expected from the water volume fraction and the bulk dielectric relaxation of water. We find that the dielectric response of nano-spheres is more attenuated than that of nano-tubes of identical composition (water-surfactant ratio), whereas the reorientation dynamics of the water hydroxyl groups is identical for the two geometries. We attribute the attenuation of the dielectric response compared to bulk water to a local anti-parallel ordering of the molecular dipole moments. The difference in attenuation between nano-spheres and nano-cylinders indicates that the anti-parallel ordering of the water dipoles is more pronounced upon spherical than upon cylindrical nanoconfinement.

Influence of Förster-type energy transfer on the vibrational relaxation of anionic hydration shells.

We study the influence of Förster energy transfer on the vibrational relaxation dynamics of anionic hydration shells by performing time-resolved mid-infrared spectroscopy on the OH-stretch vibration of water molecules in aqueous solutions of sodium iodide. We observe that the Förster energy transfer leads to a pronounced acceleration of the vibrational relaxation. We describe the observed dynamics with a model in which we include the Förster vibrational energy transfer between the different hydroxyl groups in solution. With this model we can quantitatively describe the experimental data over a wide range of isotopic compositions and salt concentrations. Our results show that resonant energy transfer is an efficient mechanism assisting in the vibrational relaxation of anionic hydration shells.

Structure and dynamics of water in nonionic reverse micelles: a combined time-resolved infrared and small angle x-ray scattering study.

We study the structure and reorientation dynamics of nanometer-sized water droplets inside nonionic reverse micelles (water/Igepal-CO-520/cyclohexane) with time-resolved mid-infrared pump-probe spectroscopy and small angle x-ray scattering. In the time-resolved experiments, we probe the vibrational and orientational dynamics of the O-D bonds of dilute HDO:H(2)O mixtures in Igepal reverse micelles as a function of temperature and micelle size. We find that even small micelles contain a large fraction of water that reorients at the same rate as water in the bulk, which indicates that the polyethylene oxide chains of the surfactant do not penetrate into the water volume. We also observe that the confinement affects the reorientation dynamics of only the first hydration layer. From the temperature dependent surface-water dynamics, we estimate an activation enthalpy for reorientation of 45 ± 9 kJ mol(-1) (11 ± 2 kcal mol(-1)), which is close to the activation energy of the reorientation of water molecules in ice.