scholarly journals Mechanism of Base-Catalyzed Halogen Dance Reactions and the Role of Bromo-Bridged Transition States

2020 ◽  
Author(s):  
Nader Sakhaee ◽  
Yousef Fazaeli ◽  
Esmail Doustkhah ◽  
Sahar Sakhaee ◽  
Ahmad Takallou ◽  
...  

Base-catalyzed halogen dance reaction, has puzzled chemists ever since, to come up with new ideas regarding the mechanism of this beautiful chemical transformation. Series of fast metal-halogen exchanges are among the most recent mechanisms. Using DFT-Cam-B3LYP/ land2dz computations and focused on Halogen Dance (HD) reactions of bromobenzene derivatives, new bromo-bridged Transition States (TS) are proposed. These are then used to lay out 8 possible isomerization and 18 possible disproportionation paths. Mechanistic pathways were then analyzed based on TS’s energy and protonation/deprotonation steps to find the most suitable pathways. Overall pattern of these mechanisms draws for the first-time a cascade-like pattern for base-catalyzed halogen dance in its entirety. The present work shed light on a dynamic domino mechanism which dominates the realm of nonaqueous strongly basic medium reactions. Trends like these may well be a shared feature in base digestion of wood for its precious poly aromatic component like lignin.

2021 ◽  
Vol 15 ◽  
Author(s):  
Ya-Ting Huang ◽  
Fen-Fang Hong ◽  
Shu-Long Yang

Vascular dementia (VD), a cerebrovascular disease which causes cognitive impairment, is one of the significant factors that affects the quality of senectitude. Atherosclerosis (AS) is a chronic inflammatory syndrome and closely associated with VD. Analyzing the role of AS in VD contribute greatly to its early detection and prevention, but their relationship has not been integrated into a complete network. This review summarizes AS biomarkers as VD predictors for the first time and describes the direct mechanisms of AS causing VD from five aspects: vascular morphogenesis, hemodynamic change, neurovascular unit damage (NVU), oxidative stress, and microRNA (miRNA). Finally, it discriminates the relationship between AS and VD in common risk factors which can be disease or some molecules. In particular, these data imply that the role of AS in VD is not only a pathogenic factor but also a comorbidity in VD. This review aims to bring new ideas for the prediction and treatment of VD.


2021 ◽  
Vol 52 (1-2) ◽  
pp. 170-201
Author(s):  
Maria Swanson ◽  
Rebecca Ruth Gould

Abstract Drawing on archival research, this article introduces several Russian poems by the Arabic mahjar poet and writer Mikhail Naimy (Mīkhāʿīl Nu’aymah) (1889-1988) for the first time to scholarship. By examining the influence of Russian literature on Naimy’s literary output, we shed light on the role of multilingualism in generating literary identities and in shaping literary form. Naimy’s Russian poetry, we argue, furthers our understanding of the nahḍah as a multilingual movement that synthesized influences from many different languages. We also show how this multilingual orientation served as a bridge between the nahḍah and mahjar literature, by helping Arab writers craft a poetics of Arabic modernism in the diaspora. Alongside documenting an important archival discovery, this research contributes to our understanding of the temporality of Arabic modernism while illuminating its geographically and linguistically diverse substance.


2018 ◽  
Author(s):  
Pengcheng Gao ◽  
Qun Ma ◽  
Rui Liu ◽  
Xiaoding Lou ◽  
Yu Huang ◽  
...  

<p>Many researchers, however, found that the flow of both liquid and gas through nanoscale pores is one to even seven orders of magnitude faster than that would be predicted from the classic Newton’s mechanic theories, such as the Hagen-Poiseuille equation, the Bernoulli’s principle, the Knudsen theory. Here, for the first time, we propose a possible explanation for the ultra-fast flow of substance through the nano-confined pores based on the Wave-Particle Dualism. Since the mass of the substance is a constant, the velocity of the substance in the nanopores is very important. The molecule behaves like a particle above the critical velocity, while could reduce its velocity to the critical value in the nanopores, which, then, behaves like the wave inducing the tunneling transfer. The critical velocities in 18 different study cases from the literatures have been calculated. The role of quantum effect for ultrafast flow could possibly provide new ideas for studying the nature of the physiological processes with the ion and molecule channels, which are the backbones for the biology, and possibly promote the development of new method for energy conversion, desalination of sea water and even for information systems. </p>


2005 ◽  
Vol 30 (2) ◽  
pp. 57-64 ◽  
Author(s):  
S Manikutty

This paper argues that for effective development of managers, training programmes are far from sufficient. The major development of managerial capabilities, in fact, takes place not so much as a result of training programmes as on the job. But this development can be directed or undirected and one of the important tasks of a senior manager is to make sure this development is directed and effective. The development of junior managers by senior managers is a vital activity in a learning organization. In today�s fast changing environment, the only organizations that will survive will be learning organizations. Competitive advantage is not static. Organizations cannot place themselves in particular strategic postures in an industry and stay there for all time to come but have to evolve and adapt to new situations. This ability to adapt depends on the amount and kind of learning that takes place continuously in the organizations and how effectively managers can apply these learnings in their jobs. Formal training programmes can be useful and effective not by themselves but through effective coupling to organizational situations. This linkage is often lacking which is the prime reason for the apparent lack of effectiveness of such formal programmes. But building such linkages can hardly be done by academic institutions or consultants; they need to be ultimately done by the managers of the organizations themselves. As a general rule, most managers are aware of this role but have neither the time, energy nor incentive to do the development and training of their junior managers. They also lack a framework to do this systematically. This article suggests a possible framework. The role of senior managers as trainers varies with the stages the junior manager is in his career: as the first boss of a new manager, the senior managers have to shape the values and develop the ability in the new manager to prioritize and set goals for himself for the middle level managers, the senior managers have to act as trainers capitalizing on the experience the junior managers would have had thus far and integrating them with the training programmes they might have been deputed to for senior managers, they must act as disseminators and enablers of dissemination of new ideas for all levels, mentoring is very important. Not all managers can make effective mentors; and for those who have the aptitude, training programmes for mentorship can be useful. Ultimately, the role of the senior managers as trainers, coaches, and mentors is to enable the junior managers to learn effectively and help them in their self development.


Author(s):  
Volodymyr V. Manyuk

This article provides a concise description of chronological sequence of Rapids in the Dnipro within the area between the cities Dnipro and Zaporizhia, their role in the maritime transport of the Dnipro, and the relationship between humans and the river during a number of historical epochs; it presents the role of the Dnipro Rapids, also known as the Porohy of the Dnipro, as unique natural formations in the great River Dnipro, which flows through three countries and cuts through the Ukraininan Crystalline Shield. The article analyzes the sequence of measures taken by the supporters of conservation of nature along the Dnipro Rapids area, representatives of nature-conservation organizations and all people interested in Dnipro Rapids and conservation of its unique natural heritage - beginning with founding “Dniprovski Porohy” National Geological Reserve in Zaporizhia Oblast in 1974 to organizing “Dniprovi Porohy” Regional Landscape Park on the territory between Stari Kodaky village and the border of Zaporizhia Oblast. This paper highlights the diversity of geological processes which have taken place over a long and dynamic geological history, described in the stone chronicle or rocks and minerals, and which formed the Dnipro Rapids, an object of interest of many generations to come. This article emphasizes the fact that the geological component of a valuable natural phenomenon was described for the first time only in the results of particular studies by Valerian Domger, who conducted his research for the building of Katerynynska Railway upon instructions from the Geological Committee from 1881 to 1884. The pegmatite, diabase, granite, syenite with peculiarities of their mineral composition, elements of bedding, described by V Domger for the Nenasytetsky and Lohanivsky and other Rapids and islands, were not the only phenomena which have disappeared beneath the Dnipro waters forever. The small quarries, where the young geologist described the Sarmatian limestones, left no signs of their existence and not a single outcrop of the limestone survived. Therefore, the routes of V O Domger, the discoverer of the Nikopol manganese deposits, Tomakivska fauna of the Mediterranean type and Mandrykivska fauna, one of the best preserved in the world, are of great historical value. Likewise, his field studies have still not lost their scientific significance. This paper succinctly describes the geological history of the area of the Dnipro Rapids and the oldest crystalline rocks of the Aul series and non-stratified formations of the Dnipropetrovsk and other natural complexes, involved in the formation of certain rapids.


Author(s):  
Rana Jisr

The aim of this article is to shed light on the vital role of digital leaders in today’s businesses. Many firms have already grounded their partnership with digital transformation before the pandemic. Others sped up all efforts to implement digital capabilities due to COVID-19 for the first time for survival. So, we tried to show that a digital leader needs additional requirements to face the new challenges of working remotely. Furthermore, we think that good online communication skills with digital leaders draw a compelling composite picture of an effective working environment in a digital world.


2003 ◽  
Vol 68 (6) ◽  
pp. 1105-1118 ◽  
Author(s):  
Zdenek Chval ◽  
Miroslav Šíp

Fully optimised HF and DFT transition states of cisplatin binding to adenine and guanine are presented for the first time. They have similar structure as the recently published transition states for cisplatin hydrolysis with the angle of about 70° between entering and leaving ligands and corresponding bonds prolonged up to 0.5 Å. Calculated activation energies are in the range of 10.5-18 kcal/mol. The lowest activation energies were found for the binding of cis-Pt[(NH3)2(H2O)(OH)]+ to guanine. The role of hydrogen bonds in recognition of binding sites, stabilisation of reactants and final yields of individual cisplatin-DNA adducts is discussed.


2020 ◽  
Vol 3 (1) ◽  
pp. 46-50
Author(s):  
Khikmatul Islah ◽  
Juardi Juardi ◽  
Eman Sulaeman Nasim

The year 2019 was the year of the people's party in Indonesia, where every Indonesian citizen got their right to deliver their aspiration through the general election which would be held on April 17, 2019. This general election would be held simultaneously to elect the president and vice president and also the council members. Slightly different from the previous general election which had separated agenda between the president and vice president and the council members. The role of General Election Commission (KPU) in the general election was as an organizer that very important in succeeding the general election. As the organizer, KPU also had a big role in encouraging people to actively participate in casting their votes. One of the ways carried out by KPU Depok in order to encourage the voters of the Depok city to cast their votes was by conducting socialization. In the 2019 general election, one of the targets of the socialization conducted by KPU Depok was the first-time voters. Of the total number of 2,466 first-time voters registered as the Final Voters List (DPT), KPU Depok was targeting 100% of the first-time voters to participate in the April 17, 2019 general election. Various ways were made by KPU Depok to socialize and educate first-time voters all about the election. One of them was to collaborate with STIAMI Institute in order to socialize the 2019 general election for the first-time voters in Depok. The specific target to be achieved in the community service was to encourage the first-time voters to come to the polling stations (TPS) to cast their voting rights in the 2019 general election, also educate them the proper way to cast their votes in the 2019 general election. The method used in this community service was by socializing and conducting interview about the 2019 general election.


2019 ◽  
Vol 37 (2) ◽  
pp. 102-109
Author(s):  
Mike Mahoney

Abstract In this article, I share the story of my work with Brandon, a long-term patient who had a significant impact on my practice. Brandon was 8 when he was diagnosed with acute myeloid leukemia (AML), a form of childhood cancer that took his ability to walk. Beyond the hospital, family dynamics brought even more stressors to Brandon’s life. But even after his interest in my song- and instrument-based interventions dwindled, his drive toward creativity and connection with others made music therapy a vital resource for him. While I supported him, Brandon had a knack for helping me uncover new ideas, and then offering his patience as I developed them into interventions that I would use with patients in years to come. As a child, Brandon showed me how a patient’s play with toys could fit into music therapy. As an early adolescent, he set a path for my work using music technology with teens and young adults. And at the end of his life, Brandon’s family helped me understand the role of hope amidst tragedy. These three phases of music therapy are presented in detail and connected by the narrative thread of Brandon’s story. This article describes an adaptable approach to music therapy practice, helpful in strengthening relationships with patients not drawn to the clinician’s established interventions.


Author(s):  
Catherine Schifter

Imagine, as best you can, your Kindergarten classroom from way back when, or that of your children’s Kindergarten classroom, or perhaps one in which you teach or have taught. These are spacious rooms with tiny tables and chairs made especially for the small children who inhabit them during the school year. These small children are the future and their education in the early years is so important for establishing a set of skills and knowledge base to support their education for years to come. While all teachers are special, Kindergarten teachers take on the role of weaning children away from the home into the milieu of schooling. They often are a surrogate parent for these children who are away from home in a strange place without Mom or Grandmother or any other relative or familiar figure for the first time in their lives.


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