Magnetic Field-Sensitive Radical Pair Dynamics in Polymethylene Ether-Bridged Donor–Acceptor Systems

This is the final version of the article. Available from American Chemical Society via the DOI in this record.Donor–acceptor systems forming exciplexes are versatile models for the study of magnetic field effects (MFEs) on charge recombination reactions. The MFEs originate from singlet–triplet interconversion within transient radical ion pairs (RIPs), which exist in a dynamic equilibrium with the exciplexes. Here, we describe the synthesis and MFEs of the chain-linked N,N-dimethylaniline (DMA)/9-methylanthracene (MAnt) donor–acceptor system MAnt–(CH2)n–O–CH2–CH2–DMA for n = 6, 8, 10, and 16. The MFEs are found to increase with increasing chain length. Effects as large as 37.5% have been observed for the long-chain compound with n = 16. The solvent dependence of the MFEs at magnetic field intensity 75 mT is reported. For the range of solvent static dielectric constants εs = 6.0–36.0, the MFEs go through a maximum for intermediate polarities, for which the direct formation of RIPs prevails and their dissociation and reencounter are balanced. Field-resolved measurements (MARY spectra) are reported for solutions in butyronitrile. The MARY spectra reveal that for n = 8, 10, 16, the average exchange interaction is negligible during the coherent lifetime of the radical pair. However, singlet–triplet dephasing broadens the lineshape; the shorter the linker, the more pronounced this effect is. For n = 6, a dip in the fluorescence intensity reveals a nonzero average exchange coupling of the order of ±5 mT. We discuss the field-dependence in the framework of the semiclassical theory taking spin-selective recombination, singlet–triplet dephasing, and exchange coupling into account. Singlet recombination rates of the order of 0.1 ns–1 and various degrees of singlet–triplet dephasing govern the spin dynamics. In addition, because of a small free energy gap between the exciplex and the locally excited fluorophore quencher pair, a fully reversible interconversion between the RIP, exciplex, and locally excited fluorophore is revealed by spectrally resolved MFE measurements for the long-chain systems (n = 10, 16).The financial support from The Royal Society (RG170378), Ho Chi Minh City University of Technology and Education (T2018-36TD̵) and Austrian Science Fund (FWF-Project P ACS Omega Article DOI: 10.1021/acsomega.8b01232 ACS Omega 2018, 3, 10296−10305 10303 21518-N19) is gratefully acknowledged. D.R.K. is thankful NVIDIA for supporting this research through their GPU Grant Program

Painting the Nation:Examining the Intersection Between Politics and the Visual Arts Market in Emerging Economies

Politics and art have throughout history, intersected in diverse and complex ways. Ideologies and political systems have used the arts to create a certain image and, depending on the form of government this has varied from clear-cut state propaganda, to patronage, to more indirect arms-length funding procedures. Therefore, artists working within the macro-level socio-political context cannot help but be influenced, inspired and sometimes restricted by these policies and political influences. This article examines the contemporary art markets of two emerging, Socialist economies to investigate the relationship between state pol-itics and the contemporary visual arts market. We argue that the respective governments and art worlds are trying to construct a brand narrative for their nations, but that these discourses are often at cross-purposes. In doing so, we illustrate that it is impos-sible to separate a consideration of the artwork from the macro-level context in which it is produced, distributed, and consumed

Association of physical exercise and calcium intake with bone mass measured by quantitative ultrasound

<p>Abstract</p> <p>Background</p> <p>Interventions other than medications in the management of osteoporosis are often overlooked. The purpose of this study was to investigate the association of physical activity and calcium intake with bone parameters.</p> <p>Methods</p> <p>We measured the heel T-score and stiffness index (SI) in 1890 pre- and postmenopausal women by quantitative ultrasound (QUS) and assessed physical activity and dietary calcium intake by questionnaire. Participants were divided according to their weekly physical activity (sedentary, moderately active, systematically active) and daily calcium consumption (greater than or less than 800 mg/day).</p> <p>Results</p> <p>SI values were significantly different among premenopausal groups (p = 0.016) and between sedentary and systematically active postmenopausal women (p = 0.039). QUS T-scores in systematically active premenopausal women with daily calcium intake > 800 mg/day were significantly higher than those in all other activity groups (p < 0.05) independent of calcium consumption.</p> <p>Conclusions</p> <p>Systematic physical activity and adequate dietary calcium intake are indicated for women as a means to maximize bone status benefits.</p

Secure synthesis and activation of protocol translation agents

Protocol heterogeneity is pervasive and is a major obstacle to effective integration of services in large systems. However, standardization is not a complete answer. Standardized protocols must be general to prevent a proliferation of standards, and can therefore become complex and inefficient. Specialized protocols can be simple and efficient, since they can ignore situations that are precluded by application characteristics. One solution is to maintain agents for translating between protocols. However, n protocol types would require agents, since an agent must exist for a source - destination pair. A better solution is to create agents as needed. This paper examines the issues in the creation and management of protocol translation agents. We focus on the design of Nestor, an environment for synthesizing and managing RPC protocol translation agents. We provide rationale for the translation mechanism and the synthesis environment, with specific emphasis on the security issues arising in Nestor. Nestor has been implemented and manages heterogeneous RPC agents generated using the Cicero protocol construction language and the URPC toolkit.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/49229/2/ds7402.pd