Stability of the magnetic Schr\"odinger operator in a waveguide

The spectrum of the Schr\"odinger operator in a quantum waveguide is known to be unstable in two and three dimensions. Any enlargement of the waveguide produces eigenvalues beneath the continuous spectrum. Also if the waveguide is bent eigenvalues will arise below the continuous spectrum. In this paper a magnetic field is added into the system. The spectrum of the magnetic Schr\"odinger operator is proved to be stable under small local deformations and also under small bending of the waveguide. The proof includes a magnetic Hardy-type inequality in the waveguide, which is interesting in its own

On the semi-classical analysis of the groundstate energy of the Dirichlet Pauli operator in non-simply connected domains

We consider the Dirichlet Pauli operator in bounded connected domains in the plane, with a semi-classical parameter. We show, in particular, that the ground state energy of this Pauli operator will be exponentially small as the semi-classical parameter tends to zero and estimate this decay rate. This extends our results, discussing the results of a recent paper by Ekholm--Kova\v{r}\'ik--Portmann, to include also non-simply connected domains.Comment: 15 pages, 4 figure

New insight on the structural features of the cytotoxic auristatins MMAE and MMAF revealed by combined NMR spectroscopy and quantum chemical modelling

Antibody-drug conjugates (ADCs) are emerging as a promising class of selective drug delivery systems in the battle against cancer and other diseases. The auristatins monomethyl auristatin E (MMAE) and monomethyl auristatin F (MMAF) appear as the cytotoxic drug in almost half of the state-of-the-art ADCs on the market or in late stage clinical trials. Here, we present the first complete NMR spectroscopic characterisation of these challenging molecules, and investigate their structural properties by a combined NMR and quantum chemical modelling approach. We find that in solution, half of the drug molecules are locked in an inactive conformation, severely decreasing their efficiency, and potentially increasing the risk of side-effects. Furthermore, we identify sites susceptible to future modification, in order to potentially improve the performance of these drugs.Peer reviewe

Erythrocyte antioxidant protection of rose hips (Rosa spp.)

Rose hips are popular in health promoting products as the fruits contain high content of bioactive compounds. The aim of this study was to investigate whether health benefits are attributable to ascorbic acid, phenols, or other rose-hip-derived compounds. Freeze-dried powder of rose hips was preextracted with metaphosphoric acid and the sample was then sequentially eluted on a C18 column. The degree of amelioration of oxidative damage was determined in an erythrocyte in vitro bioassay by comparing the effects of a reducing agent on erythrocytes alone or on erythrocytes pretreated with berry extracts. The maximum protection against oxidative stress, 59.4 ± 4.0% (mean standard deviation), was achieved when incubating the cells with the first eluted meta-phosphoric extract. Removal of ascorbic acid from this extract increased the protection against oxidative stress to 67.9 ± 1.9% . The protection from the 20% and 100% methanol extracts was 20.8 ± 8.2% and 5.0 ± 3.2% , respectively. Antioxidant uptake was confirmed by measurement of catechin by HPLC-ESI-MS in the 20% methanol extract. The fact that all sequentially eluted extracts studied contributed to protective effects on the erythrocytes indicates that rose hips contain a promising level of clinically relevant antioxidant protection

Mechanisms of Stereodirecting Participation and Ester Migration from Near and Far in Glycosylation and Related Reactions

This review is the counterpart of a 2018 Chemical Reviews article (Adero, P. O.; Amarasekara, H.; Wen, P.; Bohe, L.; Crich, D. Chem. Rev. 2018, 118, 8242-8284) that examined the mechanisms of chemical glycosylation in the absence of stereodirecting participation. Attention is now turned to a critical review of the evidence in support of stereodirecting participation in glycosylation reactions by esters from either the vicinal or more remote positions. As participation by esters is often accompanied by ester migration, the mechanism(s) of migration are also reviewed. Esters are central to the entire review, which accordingly opens with an overview of their structure and their influence on the conformations of six-membered rings. Next the structure and relative energetics of dioxacarbeniun ions are covered with emphasis on the influence of ring size. The existing kinetic evidence for participation is then presented followed by an overview of the various intermediates either isolated or characterized spectroscopically. The evidence supporting participation from remote or distal positions is critically examined, and alternative hypotheses for the stereodirecting effect of such esters are presented. The mechanisms of ester migration are first examined from the perspective of glycosylation reactions and then more broadly in the context of partially acylated polyols.Peer reviewe

The Properties and Role of O-Acyl-omega-hydroxy Fatty Acids and Type I-St and Type II Diesters in the Tear Film Lipid Layer Revealed by a Combined Chemistry and Biophysics Approach

Correction: 10.1021/acs.joc.1c02513.The tear film lipid layer (TFLL) that covers the ocular surface contains several unique lipid classes, including O-acyl-omega-hydroxy fatty acids, type I-St diesters, and type II diesters. While the TFLL represents a unique biological barrier that plays a central role in stabilizing the entire tear film, little is known about the properties and roles of individual lipid species. This is because their isolation from tear samples in sufficient quantities is a tedious task. To provide access to these species in their pure form, and to shed light on their properties, we here report a general strategy for the synthesis and structural characterization of these lipid classes. In addition, we study the organization and behavior of the lipids at the air-tear interface. Through these studies, new insights on the relationship between structural features, such as number of double bonds and the chain length, and film properties, such as spreading and evaporation resistance, were uncovered.Peer reviewe

Tear Film Lipid Layer Structure : Self-Assembly of O-Acyl-omega-hydroxy Fatty Acids and Wax Esters into Evaporation-Resistant Monolayers

In healthy eyes, the tear film lipid layer (TFLL) is considered to act as an evaporation resistant barrier, which prevents eyes from drying. Seeking to understand the mechanisms behind the evaporation resistance of the TFLL, we studied mixtures of lipid layer wax esters and O-acyl-omega-hydroxy fatty acids. Analyzing their self-assembly and biophysical properties led to new discoveries concerning the structure and function of the TFLL. We discovered how these lipids self-assemble at the air-water interface and form an efficient antievaporative barrier, demonstrating for the first time how the interaction of different tear film lipid species can improve the evaporation resistance compared with individual lipid classes on their own. These results provide a potential mechanism for the evaporation resistance of the lipid layer. In addition, the results serve as a base for the future development of improved dry eye treatments and other applications where the evaporation of water represents a significant challenge.Peer reviewe

Dark energy and key physical parameters of clusters of galaxies

We study physics of clusters of galaxies embedded in the cosmic dark energy background. Under the assumption that dark energy is described by the cosmological constant, we show that the dynamical effects of dark energy are strong in clusters like the Virgo cluster. Specifically, the key physical parameters of the dark mater halos in clusters are determined by dark energy: 1) the halo cut-off radius is practically, if not exactly, equal to the zero-gravity radius at which the dark matter gravity is balanced by the dark energy antigravity; 2) the halo averaged density is equal to two densities of dark energy; 3) the halo edge (cut-off) density is the dark energy density with a numerical factor of the unity order slightly depending on the halo profile. The cluster gravitational potential well in which the particles of the dark halo (as well as galaxies and intracluster plasma) move is strongly affected by dark energy: the maximum of the potential is located at the zero-gravity radius of the cluster.Comment: 8 pages, 1 figur

Interactions of polar lipids with cholesteryl ester multilayers elucidate tear film lipid layer structure

Purpose: The tear film lipid layer (TFLL) covers the tear film, stabilizing it and providing a protective barrier against the environment. The TFLL is divided into polar and non-polar sublayers, but the interplay between lipid classes in these sublayers and the structure-function relationship of the TFLL remains poorly characterized. This study aims to provide insight into TFLL function by elucidating the interactions between polar and non-polar TFLL lipids at the molecular level. Methods: Mixed films of polar O-acyl-omega-hydroxy fatty acids (OAHFA) or phospholipids and non-polar cholesteryl esters (CE) were used as a model of the TFLL. The organization of the films was studied by using a combination of Brewster angle and fluorescence microscopy in a Langmuir trough system. In addition, the evaporation resistance of the lipid films was evaluated. Results: Phospholipids and OAHFAs induced the formation of a stable multilamellar CE film. The formation of this film was driven by the interdigitation of acyl chains between the monolayer of polar lipids and the CE multilayer lamellae. Surprisingly, the multilayer structure was destabilized by both low and high concentrations of polar lipids. In addition, the CE multilayer was no more effective in resisting the evaporation of water than a polar lipid monolayer. Conclusions: Formation of multilamellar films by major tear film lipids suggest that the TFLL may have a similar structure. Moreover, in contrast to the current understanding, polar TFLL lipids may not mainly act by stabilizing the non-polar TFLL sublayer, but through a direct evaporation resistant effect.Peer reviewe

Women\u27s Lacrosse Players’ perceptions of teammate leadership: Examining athlete leadership behaviors, attributes, and interactions

Athletes fulfill both on the field (task) and off the field (social) team roles. For this reason, recent research on athlete leadership has concluded there is no one best type of athlete leader. In the current study, role differentiation theory was applied to investigate how peers perceive teammate leadership roles and behaviors within a women’s lacrosse program at a NCAA Division I university. Each player (N = 30) participated in a survey in which they were tasked with rating every teammate on the following leadership behaviors: technical, interpersonal, and contagious energy. Individual player attributes of were also considered in the analysis of a cross-classified nested model that resulted in 870 total ratings that predicted overall athlete leadership. Results suggest behaviors of technical, interpersonal, and contagious energy all impact the perception of teammates’ overall leadership. Coaches and athletes can use these results to be reassured that both on field and off field leadership behaviors are important for athlete leadership development. Furthermore, a discussion of how behaviors of social roles and leadership behaviors can be transferable for athletes’ in life after sport is discussed