Theoretical investigation of the scope of sequential ligand tuning using a bifunctional scorpionate tris(1,2,4-triazolyl)borate-based architecture

The donor properties of a series of tripodal mixed N-donor/carbene ligands derived through sequential alkylation of hydrotris(1,2,4-triazolyl)borate have been investigated by density functional theory (DFT) methods. The structures of complexes of the form [Mo(L)(CO)3]- were optimized (L = [HB(1,2,4-triazolyl)n(1,2,4-triazol-5-ylidene)3-n]- (n = 0 – 3), hydrotris(pyrazolyl)borate, hydrotris(3,5-dimethylpyrazolyl)borate and hydrotris(imidazol-2-ylidene)borate) and nuCO frequencies for these complexes and partial charges of their Mo(CO)3 fragments were determined. Results show that ligand donation is highly tunable when compared to similar experimentally known ligands with a shift in the symmetric nuCO stretching mode of -39 cm -1 on going from the tris(1,2,4-triazolyl)borate complexes to that of the triscarbene hydrotris(1,2,4-triazol-5-ylidene) and an increase in partial charge (distributed multipole analysis) of the Mo(CO)3 fragment from -0.23 to -0.48

Assessing Globalization's Critics: "Talkers Are No Good Doers???"

This paper is about the critics of the "doers" of globalization. It describes who they are, where they came from, what they want, how economists, policymakers, and others might understand them better, and where globalization might head from here. Many critics are themselves strongly internationalist and want to see globalization proceed, but under different rules. Some, particularly the protesters in the streets, focus mainly on what is wrong with the world. But some of them put forward broad alternative visions and others offer detailed recommendations for alleviating the problems they see arising from status quo globalization. Most of them have roots in long-standing transnational advocacy efforts to protect human rights and the environment and reduce poverty around the world. What brings them together today is their shared concern that the process by which globalization's rules are being written and implemented is undermining democracy and failing to spread the benefits broadly. This paper sketches the key issues and concerns that motivate the critics in a way that is broadly representative and intelligible to economists. It finds more resonance for the critics' agenda in economics than they commonly recognize. And it attempts to capture the concerns of Southern as well as Northern critics and to analyze the issues that divide as well as bring them together. Finally, it evaluates those issues and alternative proposals on which even globalization enthusiasts and the critics might come together cooperatively.globalization

Advancing imaging technologies for patients with spinal pain : with a focus on whiplash injury

Background: Radiological observations of soft-tissue changes that may relate to clinical symptoms in patients with traumatic and non-traumatic spinal disorders are highly controversial. Studies are often of poor quality and findings are inconsistent. A plethora of evidence suggests some pathoanatomical findings from traditional imaging applications are common in asymptomatic participants across the life span, which further questions the diagnostic, prognostic, and theranostic value of traditional imaging. Although we do not dispute the limited evidence for the clinical importance of most imaging findings, we contend that the disparate findings across studies may in part be due to limitations in the approaches used in assessment and analysis of imaging findings. Purpose: This clinical commentary aimed to (1) briefly detail available imaging guidelines, (2) detail research-based evidence around the clinical use of findings from advanced, but available, imaging applications (eg, fat and water magnetic resonance imaging and magnetization transfer imaging), and (3) introduce how evolving imaging technologies may improve our mechanistic understanding of pain and disability, leading to improved treatments and outcomes. Study Design/Setting: A non-systematic review of the literature is carried out. Methods: A narrative summary (including studies from the authors' own work in whiplash injuries) of the available literature is provided. Results: An emerging body of evidence suggests that the combination of existing imaging sequences or the use of developing imaging technologies in tandem with a good clinical assessment of modifiable risk factors may provide important diagnostic information toward the exploration and development of more informed and effective treatment options for some patients with traumatic neck pain. Conclusions: Advancing imaging technologies may help to explain the seemingly disconnected spectrum of biopsychosocial signs and symptoms of traumatic neck pain

Adaptive gait changes due to spectacle magnification and dioptric blur in older people

YesPurpose. A recent study suggested that updated spectacles could increase falls rate in older people. We hypothesized that this may be due to changes in spectacle magnification and this study assessed the effects of spectacle magnification on adaptive gait. Methods. Adaptive gait and visual function was measured in 10 older adults (mean age 77.1 ¿ 4.3 years) with the participants¿ optimal refractive correction and when blurred with +1.00DS, +2.00DS, -1.00DS and -2.00DS lenses. Adaptive gait measurements for the lead and trail foot included foot position before the step, toe clearance of the step edge and foot position on the step. Vision measurements included visual acuity, contrast sensitivity and stereoacuity. Results. The blur lenses led to equal decrements in visual acuity and stereoacuity for the +1.00DS and -1.00DS and the +2.00DS and -2.00DS lenses. However, they had very different effects on adaptive gait compared to the optimal correction: Positive blur lenses led to an increased distance of the feet from the step, increased vertical toe clearance and reduced distance of the lead heel position on the step. Negative lenses led to the opposite of these changes. Conclusion. The adaptive gait changes did not mirror the effects of blur on vision, but were driven by the magnification changes of the lenses. Steps appear closer and larger with positive lenses and further away and smaller with negative ones. Magnification likely explains the mobility problems some older adults have with updated spectacles and after cataract surgery.Federation of Ophthalmic and Dispensing Optician