Metal-Organic Frameworks: Photophysics, Energy Transfer, and Electronic Structure

The current landscape of technological and industrial related fields is looking for novel materials with enhanced performances, which will not only improve various fields in science, but also can ensure increased environmental safety. Recently, metal-organic frameworks (MOFs) have been shown as a promising type of material for a wide range of applications including gas storage and separation, sensing, and heterogeneous catalysis. The main advantages of MOFs rely on their modular structures as well as their porosity. For instance, the modular nature of MOFs provides a control over chromophore arrangement, systematic tuning of ligand design and synthetic conditions allowing one to systematically tune photophysical or electronic properties. Thus, these materials could be utilized as a tool to address the current need in enhancement of material performance. This work presented within the following nine chapters is focused on the design, synthesis, and characterization of MOFs that target fundamental understanding of photophysical properties, energy transfer processes, and the ability to tune electronic structures of these materials. The first chapter reviews MOF applications in areas for which development is highly dependent on fundamental studies of MOF photophysics. Next four chapters discuss a utilization of MOF as an efficient replica of a protein β- barrel to maintain chromophore emission. The major principles governing chromophore photophysical response inside a confined environment are examined. Chapters six and seven describe the key factors responsible for tunability of MOF electronic structure as a function of second metal or mixed valence sites incorporation. Chapter eight demonstrates the unprecedented role of MOF modularity necessary for engineering of radionuclide containing materials. Finally, chapter nine reveals the possibility of MOF electronic structure modulation as a function of external light stimuli. Overall, this work shows the possibility of MOF engineering towards various applications ranging from photocatalysts to optoelectronic devices

Sources of fluids and metals and evolution models of skarn deposits in the Qimantagh metallogenic belt: A case study from the Weibao deposit, East Kunlun Mountains, northern Tibetan Plateau.

This is the author accepted manuscript. The final version is available from Elsevier via the DOI in this record.The Weibao Cu-Pb-Zn deposit is typical of skarn deposits in the Qimantagh metallogenic belt (QMB), EastKunlun Mountains, northern Tibetan Plateau. It comprises three ore blocks from west to east, known as Weixi,Main and Weidong. Mineralization in the Weibao deposit is intimately related to Late Triassic intrusions oc-curring at Weixi and Weidong, and orebodies are predominantly hosted by the Langyashan Formation (marinecarbonate rocks), and to a lesser extent the Devonian volcanic rocks. Skarns from Weixi and Weidong arecharacterized by a high garnet/pyroxene ratio and diopside- and andradite-rich composition of pyroxenes andgarnets, indicating a proximal, oxidized type. In contrast, skarn mineralogy of Main indicates a slightly reducedcondition, typical of Pb-Zn skarn deposits. At least five hydrothermal mineralization stages can be identified andthe microthermometric study indicates a general trend of cooling and dilution of the magmatic-hydrothermalfluids. Significant precipitation of Cu-Fe sulfides commenced from the fluid with the temperature of 340–448 °Cand the salinity of 2.1–15.0 wt% NaCl equiv. Pb-Zn sulfides however mainly precipitated when the temperaturesdeclined to < 370 °C and the salinity declined to < 7.6 wt% NaCl equiv. Carbon, hydrogen and oxygen isotopiccomposition of the fluids suggests a predominantly igneous source for the initial fluids, which were modifiedoutward by fluid-rock interaction and mixing with meteoric waters. Both sulfur and lead isotope composition ofsulfides supports a mixed sulfur and metal reservoir consisting of Triassic intrusive rocks and wall rocks.Compared to early skarn-forming and late quartz-carbonate stages, two ore-forming stages show clear evidenceof fluid boiling and fluid-rock interaction. Combined with microthermometric data of ore-forming stages, it canbe deduced that fluid cooling, boiling and fluid-rock interaction were responsible for the significant metalprecipitation. The Weibao deposit shows many similarities with skarn deposits in the QMB, and its genetic modeltherefore can be extrapolated to other skarn deposits in this region.This study was financially supported by the Geological Survey Program (Grant 1212011085528) of the China Geological Survey; the Program of High-level Geological Talents (201309) and Youth Geological Talents (201112) of the China Geological Survey; and the IGCP–592 project sponsored by IUGS–UNESCO. SZ appreciates the co-operation with the Natural History Museum (RS, AD) and the Camborne School of Mines, University of Exeter (JA) for hosting his skarn re-search. This is a contribution to their research on mineralized skarn systems funded by the EU Horizon 2020 project “FAME” (grant# 641650) and the Chinese Scholarship Council (fellowship to SZ). Dr. Hongying Qu, Jiannan Liu, Hui Wang and Jianhou Zhou from the CAGSare acknowledged for their assistance during the fieldwork

10.術後逆流性食道炎の検討(第2報)(第526回千葉医学会例会・第9回佐藤外科例会)

Engineering of novel systems capable of efficient energy capture and transfer in a predesigned pathway could potentially boost applications varying from organic photovoltaics to catalytic platforms and have implications for energy sustainability and green chemistry. While light-harvesting properties of different materials have been studied for decades, recently, there has been great progress in the understanding and modeling of short- and long-range energy transfer processes through utilization of metal–organic frameworks (MOFs). In this Forum Article, the recent advances in efficient multiple-chromophore coupling in well-defined metal–organic materials through mimicking a protein system possessing near 100% energy transfer are discussed. Utilization of a MOF as an efficient replica of a protein β-barrel to maintain chromophore emission was also demonstrated. Furthermore, we established a novel dependence of a photophysical response on an electronic configuration for chromophores with the benzylidene imidazolinone core. For that, we prepared 16 chromophores, in which the benzylidene imidazolinone core was modified with electron-donating and electron-withdrawing substituents. To establish the structure-dependent photophysical properties of the prepared chromophores, 11 novel molecular structures were determined by single-crystal X-ray diffraction. These findings allow one to predict the chromophore emission profile inside a rigid framework as a function of the substituent, a key parameter for achieving the spectral overlap necessary to study and increase resonance energy transfer efficiency in MOF-based materials

Морфометрическое проявление признаков у инбредных линий раздельноплодной свеклы столовой (Beta vulgaris L)

Relevance. Inbreeding is the most widespread method of obtaining starting breeding material and plays a central role in heterosis breeding programs of most crops. Beetroot inbred lines possessing economically valuable characteristics require constant maintenance via self-pollination. However, self-pollination leads to depression of a number of traits. Thorough theoretical studies and practical developments are needed to preserve valuable beetroot lines. We aimed to study the root and leaf rosette variability resulting from beetroot self-pollination. We also investigated the inheritance of monogermity in beetroots.Materials and methods. Experimental work was carried out at the All-Russian Research Institute of Vegetable Growing – branch of the Federal State Budgetary Scientific Institution "Federal Scientific Vegetable Center" (FSBSI FSVC), 2011-202], Moscow Region. The object of the study was inbred beetroot lines originated from beetroots of foreign selection. The research data were obtained via field observations and measurements.Results. It has been experimentally shown that the constant signs of self-pollinated beet lines of 1 year of life are the position and height of the leaf rosette. Stabilization and maintenance of separate fertility at a high level is carried out by selection. A negative correlation was noted between the signs of the degree of separateness and the height of the leaf rosette of the plant, the proportion of the neck of the root crop in its diameter, the mass of the root crop and the proportion of the root crop in the biomass of the plant in the offspring of the fourth generation of the inbreeding. The decrease in the productivity of the seed plant occurs at the beginning of the process of creating self-pollinated lines – in the first generation.Актуальность. Инбридинг, как наиболее широко распространенный метод получения исходного материала, занимает ведущее место в селекционных программах по гетерозису у большинства сельскохозяйственных культур. Поддержание линейного материала свеклы столовой по хозяйственно ценным признакам, требует глубоких теоретических и практических разработок. У самоопыленных растений по ряду признаков возникает депрессия. Целью исследования явилось изучение изменчивости признаков корнеплода и листовой розетки в процессе самоопыления и наследование признака раздельноплодность у свеклы столовой.Материалы и методы. Экспериментальная работа проведена во Всероссийском Научно-исследовательском институте овощеводства – филиале ФГБНУ ФНЦО в 2011-2020 годах, Московская область. Исходным материалом послужили образцы зарубежной селекции. Объектом исследования служили инцухт-линии свеклы столовой. Материалом для исследований послужили данные полевых измерений и учетов.Результаты. Экспериментально показано, что константными признаками самоопыленных линий свеклы столовой 1 года жизни являются положение и высота листовой розетки. Стабилизация и поддержание раздельноплодности на высоком уровне осуществляется отбором. Отмечена отрицательная корреляционная связь между признаками степень раздельноплодности и высота листовой розетки растения, доля шейки корнеплода в его диаметре, масса корнеплода и доля корнеплода в биомассе растения у потомства четвертого поколения инцухта. Снижение продуктивности семенного растения происходит в начале процесса создания самоопыленных линий – в первом поколении

Mineralogical study of the Gonçalo Li-pegmatite deposit, Portugal

Beside the Scandinavian countries and Serbia, Portugal is among the European countries with the most significant lithium resources. The Li-rich occurrences in Portugal are mainly associated with aplite-pegmatite dykes and sills intruded in granitic and metasedimentary rocks of the Central Iberian and Galicia – Trás-os-Montes geotectonic zones (Carvalho & Farinha, 2004). The Gonçalo Li-pegmatites in the Guarda district (currently only used as decorative stone) have significant economic importance. Among other deposits, Gonçalo is a reference site in the focus of the EU FAME project (www.fame-project.eu) that aims to unlock the development potential of the most promising European Sn-W-Li ore types. Results of optical microscopy, QEMSCAN©, Raman and electron-probe microanalysis of the Gonçalo Li-pegmatite deposit have been employed to determine the mineralogical variability of the pegmatites with the aim to determine the deportment of lithium and potential rare-metal by-products and to guide enhanced mineral processing technologies.Available to download freely and reproduced here with permission of the publisher. The attached file is the published pdf

Fulleretic well-defined scaffolds: Donor–fullerene alignment through metal coordination and its effect on photophysics

Herein, we report the first example of a crystalline metal–donor–fullerene framework, in which control of the donor–fullerene mutual orientation was achieved through chemical bond formation, in particular, by metal coordination. The 13C cross‐polarization magic‐angle spinning NMR spectroscopy, X‐ray diffraction, and time‐resolved fluorescence spectroscopy were performed for comprehensive structural analysis and energy‐transfer (ET) studies of the fulleretic donor–acceptor scaffold. Furthermore, in combination with photoluminescence measurements, the theoretical calculations of the spectral overlap function, Förster radius, excitation energies, and band structure were employed to elucidate the photophysical and ET processes in the prepared fulleretic material. We envision that the well‐defined fulleretic donor–acceptor materials could contribute not only to the basic science of fullerene chemistry but would also be used towards effective development of organic photovoltaics and molecular electronics

Hierarchical Corannulene‐Based Materials: Energy Transfer and Solid‐State Photophysics

We report the first example of a donor–acceptor corannulene-containing hybrid material with rapid ligand-to-ligand energy transfer (ET). Additionally, we provide the first time-resolved photoluminescence (PL) data for any corannulene-based compounds in the solid state. Comprehensive analysis of PL data in combination with theoretical calculations of donor–acceptor exciton coupling was employed to estimate ET rate and efficiency in the prepared material. The ligand-to-ligand ET rate calculated using two models is comparable with that observed in fullerene-containing materials, which are generally considered for molecular electronics development. Thus, the presented studies not only demonstrate the possibility of merging the intrinsic properties of π-bowls, specifically corannulene derivatives, with the versatility of crystalline hybrid scaffolds, but could also foreshadow the engineering of a novel class of hierarchical corannulene-based hybrid materials for optoelectronic devices

Проблематика и методология языковой локализации продукта

This article is devoted to reviewing important components of globalization such as localization and internationalization. The article presents the main concepts of these processes and establishes the basic differences between language localization and translation. The text also concerns the systematization of problems in the process of working on the localization of a product, methods of performing localization, theoretical methods of internationalization and localization.Данная статья посвящена ознакомлению с такими важными составляющими глобализации как локализация и интернационализация. В статье приведены основные понятия данных процессов и установлены базовые различия между языковой локализацией и переводом. Так же текст касается систематизации проблематик в процессе работы над локализацией продукта, способах выполнения локализации и теоретических методах интернационализации и локализации

Modification of the structure of risk factors in women with ectopic pregnancy

The article considers the structure of risk factors for ectopic pregnancy. 40 patients were divided into two study groups: retrospective, which included 18 patients with blood loss of more than 500 ml and confirmed ectopic pregnancy, and prospective, which included 30 patients, with average blood loss of less than 150 ml, and with a confirmed diagnosis of ectopic pregnancy.В статье рассмотрены структура факторов риска эктопической беременности. 48 пациенток, были разделены на две исследуемые группы: 1-ая, в которую вошли 18 пациенток с кровопотерей более 500 мл и подтверждённой внематочной беременностью, и 2-ая, в которую вошли 30 пациенток, со средней кровопотерей менее 150 мл, и с подтвержденным диагнозом внематочная беременность

Thermochronological constraints on the exhumation history of the Carboniferous Katebasu gold deposit, western Tianshan Gold Belt, NW China

This is the author accepted manuscript. The final version is available from the Geological Society of London via the DOI in this recordThe western Tianshan Gold Belt hosts numerous giant and large gold deposits that have been formed during the late Paleozoic amalgamation of the Tianshan orogen. However, little is known about their exhumation histories during the Mesozoic to Cenozoic intracontinental evolution of the orogen. The Carboniferous Katebasu orogenic gold deposit in northwestern China is a new gold discovery within the western Tianshan Gold Belt, and it shares many similarities with other orogenic gold deposits in the belt. In this contribution, new 40Ar/39Ar and (U-Th)/He ages were combined with previous geochronology and numerical modeling to quantify its post-Carboniferous cooling and exhumation history. The results revealed a three-phase cooling history and two phases of post-mineralization exhumation. We suggest that a large volume (∼0.8 km) of the mineralized roof parts of the Katebasu deposit might have been removed during uplift and erosion, whereas significant ore reserves could still exist at depth. The large erosion depth of the Katebasu gold deposit in the Nalati Range of the Chinese western Tianshan also signifies that shallow-emplaced porphyry and epithermal systems that formed prior to Permo-Triassic uplift might have been largely eroded.Natural Environment Research Council (NERC