Ligand Substitution Dynamics

Substitution of a ligand in an inner sphere complex by an outside group is the most fundamental reaction in metal ion chemistr

Ligand Substitution Processes

From the preface: The subject of the mechanistic study of ligand substitution reactions is currently undergoing an exciting growth. New fast-reaction techniques have removed the upper limit on rates that can be measured, and extension to less familiar central metal atoms has begun in earnest. This might seem the wrong moment for review of the field. As yet, definitive treatment is possible only for those complexes involving monodentate ligands with cobalt(III) and platinurn(II). But, because information is so extensive for these systems, it is clear that they are functioning as models from which concepts and experiments are generated for application over the fast-growing range of the subject. We believe that this is an important moment to reopen debate on fundamentals so that concepts will be most felicitously formulated to aid growth of understanding. This monograph is centrally concerned with three aspects of those fundamentals. We have attempted to develop an approach to classification of ligand substitution reactions that is adapted to what seem to have emerged as the characteristic features of these reactions and is susceptible to operational tests. (We do recognize that any such scheme of ideas is necessarily obsolescent once it is formulated since new experiments will certainly follow immediately.) We have tried to evaluate the basis for making generalizations about ligand substitution processes and to formulate tests to show whether new reactions fall within familiar patterns. Finally, we have sought to base the models of ligand substitution processes in the language of molecular-orbital theory. We believe that MO theory is most useful, because it may be used to correlate rate data on complexes with the extensive information available from spectral and magnetic studies, yet differs from crystal-field theory in providing a natural place for consideration of the bonding electrons, which must be a principal determinant of reaction processes. To keep this essay within bounds, we assume familiarity with the elements of experimental kinetics, transition-state theory, and the simple molecular-orbital theory of complexes. Introductory physical chemistry, some familiarity with the study of reaction mechanisms, and mastery of one of the qualitative treatments of MO theory as applied to transition-metal complexes should provide sufficient background. Thus, we hope that this book will be useful to students, relatively early in their careers, who wish to explore this field. Our debts to very many workers will be obvious throughout. We want to record here our special personal debt to Professors Ralph G. Pearson and Fred Basolo and to Dr. Martin Tobe. We particularly thank Professor George S. Hammond for his interest and enthusiasm in this project. Professor Hammond carefully read and criticized the entire manuscript in the final drafts. We received many other valuable criticisms at various stages of this project from Professors R. D. Archer, F. Basolo, J. O. Edwards, J. Finholt, P. Haake, J. Halpern, A. Kropf, R. G. Pearson, S. I. Shupack, M. S. Silver, and C. Walling, and Dr. U. Belluco and Dr. L. Cattalini. We very much appreciate their help and probably should have followed their suggestions more closely. We warmly acknowledge expert assistance from Mrs. Madeline deFriesse, Miss Jan Denby, and Mrs. Diane Celeste in preparation of the manuscript. COOPER H. LANGFORD HARRY B. GRAY Amherst, Massachusetts New York, New York October 196

Drainage network reorganization affecting the Nene and Welland catchments of eastern England as a result of a late Middle Pleistocene glacial advance

Cycladic Archaeology and Research: New approaches and discoveries reflects the present exciting times in Cycladic archaeology. New excavations are bringing to light sanctuaries unmentioned by literary sources and inscriptions (e.g., Kythnos, Despotiko); new theoretical approaches to insularity and networks are radically changing our views of the Cyclades as geographic and cultural unit(s). Furthermore, the restoration and restudy of older sites (e.g., Delos, Paros, Naxos) are challenging old truths, updating chronologies and contexts throughout the Mediterranean and beyond. This volume is intended to share these recent developments with a broader, international audience. The essays have been carefully selected as representing some of the most important recent work and include significant previously-unpublished material. Individually, they cover archaeological sites and materials from across the Cycladic islands, and illustrate the diversity of the islands’ material culture across the Geometric, Archaic, Classical, Hellenistic, Roman, and Late Antique periods. Together, they share common themes such as the importance of connectivity, and the role of each island’s individual landscape and its resources in shaping human activity. The work they represent attests the ongoing appeal of the islands and of the islanders in the collective imagination, and demonstrates the scope for still further innovative work in the years ahead

A spatial investigation of the environmental controls over cryoconite aggregation on Longyearbreen glacier, Svalbard.

A cryoconite granule is a near-spherical aggregation of biota and abiotic particles found upon glacier surfaces. Recently, microstructural studies have revealed that photosynthetic microorganisms and extracellular polymeric substances (EPS) are omnipresent within cryoconite granules and have suggested their importance as biological "forming factors". To assess these forming factors, and their biological control over aggregate size and stability, across a typical Arctic valley glacier surface, a suite of rapid, spectrophotometric, microplate methods were utilised. Subsequent spatial mapping of these data revealed distinct patterns. Labile carbohydrates were found to increase up-glacier, suggestive of EPS production for cryoprotection and nutrient assimilation. Conversely, pigment concentrations were found to increase towards the glacier terminus and valley sides, suggestive of allochthonous input, a general reduction in physical disturbance and of the build-up of photosynthetic pigments and less labile cyanobacterial sheath material. Aggregate size was found to increase towards the glacier edges, linked to the input of particulate matter from the valley sides, and to broadly increase down-glacier, in the same way as pigment concentrations. Statistical analyses of transect data revealed that the photoautotrophic count and carbohydrate–chlorophyll ratio of the cryoconite sampled could explain 83% of the measured variation in aggregate size and stability. Considering solely aggregate size, the number and length of photoautotrophic filaments could explain 92% of the variation in this parameter. These findings demonstrate the two-dimensional distribution of key biological controls upon cryoconite aggregation for the first time, and highlight the importance of filamentous cyanobacteria and EPS production to the development of stable cryoconite granules

Le FORUM, Vol. 36 No. 3

https://digitalcommons.library.umaine.edu/francoamericain_forum/1034/thumbnail.jp

Le FORUM, Vol. 37 No. 1

https://digitalcommons.library.umaine.edu/francoamericain_forum/1036/thumbnail.jp

Demystifying academics to enhance university-business collaborations in environmental science

In countries globally there is intense political interest in fostering effective university-business collaborations, but there has been scant attention devoted to exactly how an individual scientist's workload (i.e. specified tasks) and incentive structures (i.e. assessment criteria) may act as a key barrier to this. To investigate this an original, empirical dataset is derived from UK job specifications and promotion criteria, which distil universities' varied drivers into requirements upon academics. This work reveals the nature of the severe challenge posed by a heavily time-constrained culture; specifically, tension exists between opportunities presented by working with business and non-optional duties (e.g. administration and teaching). Thus, to justify the time to work with business, such work must inspire curiosity and facilitate future novel science in order to mitigate its conflict with the overriding imperative for academics to publish. It must also provide evidence of real-world changes (i.e. impact), and ideally other reportable outcomes (e.g. official status as a business' advisor), to feed back into the scientist's performance appraisals. Indicatively, amid 20-50 key duties, typical full-time scientists may be able to free up to 0.5 day per week for work with business. Thus specific, pragmatic actions, including short-term and time-efficient steps, are proposed in a "user guide"to help initiate and nurture a long-term collaboration between an early- to mid-career environmental scientist and a practitioner in the insurance sector. These actions are mapped back to a tailored typology of impact and a newly created representative set of appraisal criteria to explain how they may be effective, mutually beneficial and overcome barriers. Throughout, the focus is on environmental science, with illustrative detail provided through the example of natural hazard risk modelling in the insurance sector. However, a new conceptual model of academics' behaviour is developed, fusing perspectives from literature on academics' motivations and performance assessment, which we propose is internationally applicable and transferable between sectors. Sector-specific details (e.g. list of relevant impacts and user guide) may serve as templates for how people may act differently to work more effectively together

Uridine Metabolism in the Goldfish Retina During Optic Nerve Regeneration: Whole Retina Studies

Accumulation of radioactivity from [ 3 H]uridine in incubations of whole goldfish retinas is increased in the ipsilateral retina during a period of regeneration that follows unilateral optic nerve crush. Brief incubations to investigate the nature of enhanced labeling of the acid-soluble fraction showed a peak uptake 4 days following crush, with a gradual decrease to control levels by 21 days following crush. That nucleoside uptake may not mediate the effect is supported by the observation that the rate of uptake of 5′-deoxyadenosine, a nonmetabolizable nucleoside analog, is the same in post-crush (PC) and normal (N) retinal incubations. Following brief incubations of PC and N retinas with [ 3 H]uridine, there is enhanced labeling in PC retinas relative to N retinas of recovered UMP, UDP, UTP, and uridine nucleotide sugars, whereas recovery of labeled uridine itself is slightly decreased. The results suggest that the increased accumulation of radioactivity in PC retinas following incubation with uridine reflects an increase in the activities of retinal uridine kinase and uridine nucleotide kinases.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/65630/1/j.1471-4159.1981.tb01713.x.pd

Perspectives by patients and physicians on outcomes of mid-urethral sling surgery

Introduction and hypothesis: The aim of this study is to determine patient expectations regarding wanted and unwanted sequels of mid-urethral sling (MUS) procedures and to identify mismatches during the physician-patient information exchange prior to MUS procedures. Methods: A patient preference study (40 patients) and a questionnaire study with 20 experts as control group were conducted. Seventeen different sequels, defined by an expert team, were evaluated. Results: Both patients and expert physicians ranked cure and improvement of stress urinary incontinence as the most important goals of treatment. De novo urge urinary incontinence, requiring post-operative intermittent self-catheterisation and dyspareunia were considered to be the most important complications by patients. Time to resume work after the operation and dyspareunia were among the highest rated sequels in the patient group compared to re-operation and intra-operative complications in the expert group. Conclusions: No differences were found in the five most important outcome parameters. In pre-operative counselling and future clinical trials, time to resume work and dyspareunia should be given more consideration by clinicians

New metrics for the Lancet Standing Commission on Liver Disease in the UK

Health Polic