Empirical σ Molecular Orbital Parameters and their Correlation with Rates of Substitution Reactions in Quadrate Cr(III) and Co(III) Complexes

1971 ◽  
Vol 49 (9) ◽  
pp. 1497-1501 ◽  
Author(s):  
C. H. Langford
Keyword(s):  
Field Theories ◽  
Complete Analysis ◽  
Substitution Reactions ◽  
Spectral Parameters ◽  
Empirical Measures ◽  
Orbital Parameters ◽  
Spectral Bands ◽  
Leaving Group ◽  
The Relationship

Empirical measures of σ bonding involving metal 3d orbitals are derived from Perumareddi's (4) complete analysis of the quartet spectral bands of quadrate complexes in the families Cr(NH3)5Xn+ and Cr(OH2)5Xn+. These are shown to correlate with lability of X in the Cr(III) complexes and in Co(NH3)5Xn+ complexes in a sense indicating that relative reactivity is controlled by variation of ligand metal 3d σ interaction. The relationship between the two Cr(III) series implies that the non-labile ligands can labilize the leaving group in proportion to their σ donor capacities. This observation bears on some well-known difficulties in crystal field theories of reactivity. In evaluating the correlation of spectral parameters with reactivity, the role of solvation in reactivity of Cr(III) and Co(III) complexes is discussed with emphasis on the surprisingly small solvent effects that have been observed.

SN2 Substitution Reactions at the Amide Nitrogen in the Anomeric Mutagens, N-Acyloxy-N-alkoxyamides

2009 ◽  
Vol 62 (7) ◽  
pp. 700 ◽  
Author(s):  
Katie L. Cavanagh ◽  
Stephen A. Glover ◽  
Helen L. Price ◽  
Rhiannon R. Schumacher
Keyword(s):  
Kinetic Studies ◽  
Model Reaction ◽  
Side Chain ◽  
Carboxylate Group ◽  
Amide Nitrogen ◽  
Substitution Reactions ◽  
Sn2 Reactions ◽  
Leaving Group ◽  
Rate Of Substitution

N-Acyloxy-N-alkoxyamides 1a are unusual anomeric amides that are pyramidal at the nitrogen because of bis oxyl substitution. Through this configuration, they lose most of their amide character and resemble α-haloketones in reactivity. They are susceptible to SN2 reactions at nitrogen, a process that is responsible for their mutagenic behaviour. Kinetic studies have been carried out with the nucleophile N-methylaniline that show that, like SN2 reactions at carbon centres, the rate constant for SN2 displacement of carboxylate is lowered by branching β to the nitrogen centre, or bulky groups on the alkoxyl side chain. Branching or bulky groups on the carboxylate leaving group, however, do not impact on the rate of substitution, which is mostly controlled by the pKA of the departing carboxylate group. These results are in line with computed properties for the model reaction of ammonia with N-acetoxy-N-methoxyacetamide but are in contrast to the role of steric effects on their mutagenicity.

scholarly journals Music Against the Challenges of Digital Society

2021 ◽  
pp. 810-821
Author(s):  
Boris V. Markov ◽  
Dmitriy A. Yarochkin
Keyword(s):  
Modern Society ◽  
Theoretical Explanation ◽  
Complete Analysis ◽  
Starting Point ◽  
Definition Of ◽  
Political Technology ◽  
The Relationship ◽  
Networked Society ◽  
Anthropology Of Music

The aim of the article is to separate the concepts of musicology, music anthropology, music, and instrumentalism. This very division and reflection of the interrelations of concepts provide a starting point for a detailed study of the problems of musical instrumentalism. The article is methodological in nature. It contains a number of important settings that are necessary for the anthropological analysis of music. The Central theoretical explanation of the article is the separation of musical anthropology and the anthropology of music. For this purpose, a number of tasks, namely, the definition of the theoretical fields of musical anthropology and the anthropology of music, and the disclosure of the role of music in traditional and modern society are proposed. The concept of musical action is introduced. Solving these problems allows to give a more complete analysis of the relationship between a person and music. It is this problem that becomes the main problem in the music media mainstream, where popular music is used as a way of producing moods and experiences. Music becomes a particularly valuable commodity in a networked society, which is made not so much for the purpose of incorporating into the values of high culture but to control the behavior of people in the music market. In addition to commercialization, music is becoming an effective political technology that provides consensus among voters. In this regard, there is a cultural problem, how high art in general and music, in particular, can preserve its traditional purpose – to promote humanization

Basicity, nucleophilicity, and nucleofugality in the elimination–substitution reactions of β-phenylmercaptoethyl phenolates in DMSO–ethanol media

1994 ◽  
Vol 72 (2) ◽  
pp. 448-453 ◽  
Author(s):  
Hai-Qi Xie ◽  
Nguyen Truong ◽  
Erwin Buncel ◽  
J. Garfield Purdon
Keyword(s):  
Reaction Rate ◽  
Phenyl Group ◽  
Kinetic Studies ◽  
Substitution Reactions ◽  
Leaving Group ◽  
Partial Completion ◽  
Comparison Of The Results ◽  
Pure Dmso ◽  
Phenyl Vinyl

Kinetic studies have been performed on the base-promoted 1,2-elmination reactions of a series of β-phenylmercaptoethyl phenolates with potassium ethoxide in EtOH–DMSO media, yielding phenyl vinyl sulfide. The E2 mechanism was indicated by the absence of H/D exchange in the substrate when the reaction in EtOD–DMSO-d6 containing EtO− was carried to partial completion. The Brønsted coefficient values (βLG, effect of nucleofugality on reaction rate) of ca• 0.30 and ca• 0.98 were estimated for the reaction in pure DMSO and ethanol, respectively. Comparison of the results with reported reactions of substrates of similar structure revealed the important role of the phenyl group on sulfur, the leaving-group nucleofugality, and the medium basicity, in controlling the reaction pathways (elimination versus substitution).

Choosing a Markov blanket

2020 ◽  
Vol 43 ◽  
Author(s):  
Thomas Parr
Keyword(s):  
Markov Blanket ◽  
Target Article ◽  
The Relationship

Abstract This commentary focuses upon the relationship between two themes in the target article: the ways in which a Markov blanket may be defined and the role of precision and salience in mediating the interactions between what is internal and external to a system. These each rest upon the different perspectives we might take while “choosing” a Markov blanket.

Staring Down Death

Crisis ◽  
2016 ◽  
Vol 37 (3) ◽  
pp. 212-217 ◽  
Author(s):  
Thomas E. Joiner ◽  
Melanie A. Hom ◽  
Megan L. Rogers ◽  
Carol Chu ◽  
Ian H. Stanley ◽  
...  
Keyword(s):  
Suicide Risk ◽  
Clinical Utility ◽  
Blink Rate ◽  
Specific Task ◽  
Careful Planning ◽  
Eye Blink ◽  
Eye Blinks ◽  
Potential Clinical Utility ◽  
The Relationship

Abstract. Background: Lowered eye blink rate may be a clinically useful indicator of acute, imminent, and severe suicide risk. Diminished eye blink rates are often seen among individuals engaged in heightened concentration on a specific task that requires careful planning and attention. Indeed, overcoming one’s biological instinct for survival through suicide necessitates premeditation and concentration; thus, a diminished eye blink rate may signal imminent suicidality. Aims: This article aims to spur research and clinical inquiry into the role of eye blinks as an indicator of acute suicide risk. Method: Literature relevant to the potential connection between eye blink rate and suicidality was reviewed and synthesized. Results: Anecdotal, cognitive, neurological, and conceptual support for the relationship between decreased blink rate and suicide risk is outlined. Conclusion: Given that eye blinks are a highly observable behavior, the potential clinical utility of using eye blink rate as a marker of suicide risk is immense. Research is warranted to explore the association between eye blink rate and acute suicide risk.

Parenting Behaviors and Anxiety in Young Adults

2015 ◽  
Vol 36 (3) ◽  
pp. 170-176 ◽  
Author(s):  
Erin N. Stevens ◽  
Joseph R. Bardeen ◽  
Kyle W. Murdock
Keyword(s):  
Effortful Control ◽  
Parenting Behaviors ◽  
Protective Role ◽  
Anxiety Symptoms ◽  
Interactive Effects ◽  
Parental Overprotection ◽  
High Control ◽  
Development Of Anxiety ◽  
The Relationship

Parenting behaviors – specifically behaviors characterized by high control, intrusiveness, rejection, and overprotection – and effortful control have each been implicated in the development of anxiety pathology. However, little research has examined the protective role of effortful control in the relation between parenting and anxiety symptoms, specifically among adults. Thus, we sought to explore the unique and interactive effects of parenting and effortful control on anxiety among adults (N = 162). Results suggest that effortful control uniquely contributes to anxiety symptoms above and beyond that of any parenting behavior. Furthermore, effortful control acted as a moderator of the relationship between parental overprotection and anxiety, such that overprotection is associated with anxiety only in individuals with lower levels of effortful control. Implications for potential prevention and intervention efforts which specifically target effortful control are discussed. These findings underscore the importance of considering individual differences in self-regulatory abilities when examining associations between putative early-life risk factors, such as parenting, and anxiety symptoms.

Social Support, Emotional Intelligence, and Posttraumatic Stress Disorder Symptoms

2016 ◽  
Vol 37 (1) ◽  
pp. 31-39 ◽  
Author(s):  
Nicole L. Hofman ◽  
Austin M. Hahn ◽  
Christine K. Tirabassi ◽  
Raluca M. Gaher
Keyword(s):  
Social Support ◽  
Posttraumatic Stress Disorder ◽  
Emotional Intelligence ◽  
Protective Factors ◽  
Posttraumatic Stress ◽  
Stress Disorder ◽  
Traumatic Events ◽  
Ptsd Symptoms ◽  
The Relationship

Abstract. Exposure to traumatic events and the associated risk of developing Posttraumatic stress disorder (PTSD) symptoms is a significant and overlooked concern in the college population. It is important for current research to identify potential protective factors associated with the development and maintenance of PTSD symptoms unique to this population. Emotional intelligence and perceived social support are two identified protective factors that influence the association between exposure to traumatic events and PTSD symptomology. The current study examined the mediating role of social support in the relationship between emotional intelligence and PTSD symptoms. Participants included 443 trauma-exposed university students who completed online questionnaires. The results of this study indicated that social support mediates the relationship between emotional intelligence and reported PTSD symptoms. Thus, emotional intelligence is significantly associated with PTSD symptoms and social support may play an integral role in the relationship between emotional intelligence and PTSD. The current study is the first to investigate the role of social support in the relationship between emotional intelligence and PTSD symptoms. These findings have important treatment and prevention implications with regard to PTSD.

Coping Humor as a Mediator Between Emotional Intelligence and Job Satisfaction

2017 ◽  
Vol 16 (3) ◽  
pp. 155-159 ◽  
Author(s):  
Peizhen Sun ◽  
Jennifer J. Chen ◽  
Hongyan Jiang
Keyword(s):  
Job Satisfaction ◽  
Emotional Intelligence ◽  
Future Research ◽  
Satisfaction Scale ◽  
Primary School Teachers ◽  
Mediating Role ◽  
Regulation Of Emotion ◽  
The Relationship ◽  
Overall Job Satisfaction

Abstract. This study investigated the mediating role of coping humor in the relationship between emotional intelligence (EI) and job satisfaction. Participants were 398 primary school teachers in China, who completed the Wong Law Emotional Intelligence Scale, Coping Humor Scale, and Overall Job Satisfaction Scale. Results showed that coping humor was a significant mediator between EI and job satisfaction. A further examination revealed, however, that coping humor only mediated two sub-dimensions of EI (use of emotion and regulation of emotion) and job satisfaction. Implications for future research and limitations of the study are discussed.

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