Rankings as a comprehensive model to assess innovation and investment development of mesolevel economic systems (case of Tomsk region)

Актуальность определяется растущим интересом зарубежных и отечественных исследователей и практиков к рейтингам как комплексному методу оценки инновационно‐инвестиционого развития регионов. При этом нет единства мнений по методикам формирования рейтингов, отбора показателей и методов расчета. Цель работы: исследование и анализ рейтингов как модели комплексной оценки инновационного и инвестиционного развития экономических систем мезоуровня. Методы исследования: методы сравнительного, логического анализа, анализ и синтез, системный подход. Результаты. Представлен сравни‐ тельный анализ российских инновационно‐инвестиционных рейтингов; рассмотрены методики их составления и используемые системы показателей. Сформулированы ограничения рейтинга как модели комплексной оценки в целом, дана характеристика каждого отдельного рейтинга. В качестве примеров приведены позиции регионов Сибирского федерального округа в пяти российских рейтингах.The relevance of the topic is determined by the growing interest of foreign and domestic researchers and practitioners in ratings as a comprehensive method for assessing the innovative and investment development of the regions. At the same time there is no unity of opinion on the methods of rating formation, selection of indicators and calculation methods. The aim of the study is to research and analyze ratings as a model for integrated assessment of innovation and investment development of meso‐level economic systems. Methods of research: methods of comparative, logical analysis, analysis and synthesis, systematic approach. Results. The paper introduces the comparative analysis of Russian innovation and investment ratings, considers the methods of their compilation and the system of indicators. The rating constraints are formulated as a model of integrated assessment in general, and the characteristics of each individual rating are given. The authors give the positions of the regions of the Siberian Federal District in five Russian rankings as an example

Neue Wege zur Analyse der Elektronendichteverteilung in Molekuelen Ein Beitrag zum Verstaendnis chemischer Bindungen und molekularer Struktur

With app.SIGLECopy held by FIZ Karlsruhe; available from UB/TIB Hannover / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekDEGerman

Docking, triggering, and biological activity of dynemicin A in DNA: a computational study

The triggering and biological activity of the naturally occurring enediyne dynemicin A (1) was investigated, both inside and outside the minor groove of the duplex 10-mer B-DNA sequence d(CTACTACTGG)·d(CCAGTAGTAG), using density functional theory (B3LYP with the 3-21G and 6-31G(d) basis set), BD(T)/cc-pVDZ (Brueckner doubles with a perturbative treatment of triple excitations), and the ONIOM approach. Enediyne 1 is triggered by NADPH in a strongly exothermic reaction (−88 kcal/mol), which involves a number of intermediate steps. Untriggered 1 has a high barrier for the Bergman cyclization (52 kcal/mol) that is lowered after triggering to 16.7 kcal/mol due to an epoxide opening and the accompanying strain relief. The Bergman reaction of triggered 1 is slightly exothermic by 2.8 kcal/mol. The singlet biradical formed in this reaction is kinetically stable (activation enthalpies of 19.5 and 21.8 kcal/mol for retro-Bergman reactions) and is as reactive as para-benzyne. The activity-relevant docking mode is an edge-on insertion into the minor groove, whereas the intercalation between base pairs, although leading to larger binding energies, excludes a triggering of 1 and the development of its biological activity. Therefore, an insertion−intercalation model is developed, which can explain all known experimental observations made for 1. On the basis of the insertion−intercalation model it is explained why large intercalation energies suppress the biological activity of dynemicin and why double-strand scission can be achieved only in a two-step mechanism that involves two enediyne molecules, explaining thus the high ratio of single-strand to double-strand scission observed for 1

Investigation of the NMR spin-spin coupling constants across the hydrogen bonds in ubiquitin: the nature of the hydrogen bond as reflected by the coupling mechanism

The indirect scalar NMR spin−spin coupling constants across the H-bonds of the protein ubiquitin were calculated, including the Fermi contact, the diamagnetic spin−orbit, the paramagnetic spin−orbit, and the spin dipole term, employing coupled perturbed density functional theory in combination with the B3LYP functional and different basis sets:  (9s,5p,1d/5s,1p)[6s,4p,1d/3s,1p] and (11s,7p,2d/5s,1p)[7s,6p,2d/4s,2p]. Four different models based on either the crystal or the aqueous solution structure of ubiquitin were used to describe H-bonding for selected residue pairs of ubiquitin. Calculated and measured 3hJ(NC‘) coupling constants differ depending on the model used, which is due to the fact that the geometry of ubiquitin is different in the solid state and in aqueous solution. Also, conformational averaging leads to a decrease of the magnitude of the measured 3hJ(NC‘) constants, which varies locally (larger for β-sheets, smaller for α-helix). Two different spin−spin coupling mechanisms were identified. While mechanism I transmits spin polarization via an electric field effect, mechanism II involves also electron delocalization from the lone pair of the carbonyl oxygen to the antibonding orbital of the N−H bond. Mechanism I is more important in the crystal structure of ubiquitin, while in aqueous solution, mechanism II plays a larger role. It is possible to set up simple relationships between the spin−spin coupling constants associated with the H bond in proteins and the geometrical features of these bonds. The importance of the 3hJ(NC‘) and 1J(N−H) constants as descriptors for the H-bond is emphasized

Comparison of Ni, Pd, Pt complexes of N,N-bis(dialkylphosphinomethyl)aminomethane: A DFT study

In this work, [MX2(R2PCH2)2NMe] complexes have been modeled and studied by density functional theory (DFT). The metal M (M = Ni, Pt, Pd), the halogen X (X = Cl, Br, I) and the substituent R (R = Me, Cy, Ph) on the phosphorus atoms were systematically combined to 27 different complexes. Replacing the nitrogen atom on the ligand with a methylene group and the methyl group on the nitrogen atom with a phenyl group were two additional variations considered in this work. Electronic and structural properties of each complex were examined and general trends were derived. Pd-P bond lengths were found to be longer than Pt-P bond lengths reflecting the well-known Lanthanide contraction. The modification of the amino part turned out to be most sensitive with regard to changes in the geometry and the electronic structure of the complexes. Therefore, it may serve as a sensitive tool for the design and synthesis of new catalysts as well as antibiotics based on aminomethylphosphine complexes. © 2008 Elsevier B.V.06B507This work is funded by the Bogazici University Research Funds, project 06B507