Relationship between ozone and biologically relevant UV at 4 NDACC sites.

Clouds and aerosols, as well as overhead ozone, can have large effects on ultraviolet (UV) irradiances. We use statistical methods to remove cloud effects and mean aerosol effects from spectral UV irradiance measurements to investigate the relationship between UV and total column ozone. We show that for fixed solar zenith angles (SZA), seasonal changes in ozone lead to marked changes in clear-sky UV irradiances. Such effects are larger at mid-latitudes than in the tropics. At mid-latitudes, the minimum ozone amount over the course of a year can be about 50 percent of its maximum, with the lowest values in autumn and the highest values in spring. These seasonal ozone changes lead to UV Index (UVI) values in autumn that can exceed those in spring at the same SZA by nearly a factor of two. Differences are even larger for UV spectra weighted by the action spectra for DNA-damaging UV, and for cutaneous previtamin D production. In some cases, the seasonal increase exceeds a factor of 4. The analysis experimentally demonstrates the limits of applicability of the concept of constant Radiative Amplification Factors (RAFs) for estimating effects of changes in ozone for some weighting functions. Changes in DNA-weighted UV and erythemally weighted UV are well represented by the published RAFs. However, there are large SZA dependencies in the case of UVB and vitamin D-weighted UV. For all weightings considered, RAFs calculated from the observations as a function of SZA show similar dependencies between sites, in good agreement with published values, independently of the ozone data source. High quality measurements show that natural variations in ozone are responsible for huge variations in biologically damaging UV, with seasonal changes at fixed solar zenith angles sometimes exceeding a factor of four. The measured changes from thousands of spectra agree well with calculations over a wide range of solar zenith angles.

Excision of Extensive Orbitozygomaticomaxillary Complex Tumors Combining an Intra- and Extraoral Approach With Transpalpebral Orbital Exenteration.

The junction of the bones of the orbit, caudal maxilla and zygoma intersect to form an anatomically intricate region known as the orbitozygomaticomaxillary complex (OZMC). Given the critical role of the OZMC in the structure, function and esthetics of the skull and midface, tumors in this region present unique challenges to the oromaxillofacial surgeon. Attempts to achieve histologically clean tumor margins in a cosmetically pleasing manner requires excellent intra-operative visualization. Additionally, minimized intra-operative and post-opertive complications is of paramount importance. In this manuscript we describe a combined intra- and extraoral approach to extensive tumors of the OZMC that incorporates orbital exenteration as a technique, which allows for excellent intra-operative visualization and mitigate intra- and post-operative complications. In addition, we describe our experience utilizing the technique in five clinical cases.

Biomechanical Testing of a Calcium Phosphate-Phosphoserine-Based Mineral-Organic Adhesive for Non-invasive Fracture Repair of Mandibular Fractures in Dogs.

Mandibular fracture repair is complicated by limited availability of bone as well as the presence of the neurovascular bundle and an abundance of tooth roots. Fractures at the location of the mandibular first molar teeth are common and it can be particularly challenging to apply stable fixation. Non-invasive fracture repair techniques utilize intraoral placement of fixation devices typically involving polymerized composites and/or interdental wiring. A novel calcium phosphate-phosphoserine-based mineral-organic adhesive was tested ex vivo to determine its effects on augmenting strength of different non-invasive fracture fixation techniques. This study both tested the use of mineral-organic adhesive for the purpose of stabilizing currently used non-invasive fracture repair constructs (intraoral composite splinting ± interdental wiring) and evaluated adhesive alone or with subperiosteally placed plates on buccal cortical bone surface. Aside from controls, not receiving an osteotomy along the mesial root of the mandibular first molar tooth, six treatment groups were tested to evaluate ultimate strength, stiffness, angular displacement, bending moment, and application time. All forms of fixation were found to be significantly weaker than control (p < 0.001). Only the control (p < 0.001) and mineral-organic adhesive and composite (P = 0.002) groups were found to be significantly stronger than wire and composite. No difference was noted in stiffness between any groups with control or wire and composite. Application times varied from the mineral-organic adhesive group (mean = 206 s) to mineral-organic adhesive and composite (mean = 1,281 s). Twenty-three fixation devices exhibited adhesive failure, 20 demonstrated cohesive failure, and 5 failed by cohesive and adhesive failure. When evaluating the ultimate strength of the fixation device groups, mineral-organic adhesive, and composite was shown to be the strongest construct. The use of resorbable bone adhesive and composite may provide a stronger fixation construct over interdental wire and composite for mandibular fracture repair in dogs.

Python-based dynamic scheduling assistant for atmospheric measurements by Bruker instruments using OPUS.

Atmospheric remote sensing by instruments such as spectrometers and interferometers often requires scheduling that is dependent on external factors, for example; time and solar (or lunar) zenith angle. Such instruments manufactured by Bruker often use the software package OPUS, which, while useful, is not flexible enough for automatic, repeated, atmospheric measurements of this nature. In this brief paper, we describe ASAP, a Python tool developed to run our network of Fourier transform interferometers in New Zealand and Antarctica. It allows the automated scheduling of measurements by time, lunar, or solar zenith angle while accounting for weather or other external parameters. There is a wide range of useful functions, all packaged in a simple graphical user interface; it is available on request.

Donor-Acceptor Distance Sampling Enhances the Performance of "Better than Nature" Nicotinamide Coenzyme Biomimetics.

Understanding the mechanisms of enzymatic hydride transfer with nicotinamide coenzyme biomimetics (NCBs) is critical to enhancing the performance of nicotinamide coenzyme-dependent biocatalysts. Here the temperature dependence of kinetic isotope effects (KIEs) for hydride transfer between "better than nature" NCBs and several ene reductase biocatalysts is used to indicate transfer by quantum mechanical tunneling. A strong correlation between rate constants and temperature dependence of the KIE (ΔΔH(⧧)) for H/D transfer implies that faster reactions with NCBs are associated with enhanced donor-acceptor distance sampling. Our analysis provides the first mechanistic insight into how NCBs can outperform their natural counterparts and emphasizes the need to optimize donor-acceptor distance sampling to obtain high catalytic performance from H-transfer enzymes.