Strategy for Engineering High Photolysis Efficiency of Photocleavable Protecting Groups through Cation Stabilization

Photolabile protecting groups (PPGs) enable the precise activation of molecular function with light in many research areas, such as photopharmacology, where remote spatiotemporal control over the release of a molecule is needed. The design and application of PPGs in recent years have particularly focused on the development of molecules with high molar absorptivity at long irradiation wavelengths. However, a crucial parameter, which is pivotal to the efficiency of uncaging and which has until now proven highly challenging to improve, is the photolysis quantum yield (QY). Here, we describe a novel and general approach to greatly increase the photolysis QY of heterolytic PPGs through stabilization of an intermediate chromophore cation. When applied to coumarin PPGs, our strategy resulted in systems possessing an up to a 35-fold increase in QY and a convenient fluorescent readout during their uncaging, all while requiring the same number of synthetic steps for their preparation as the usual coumarin systems. We demonstrate that the same QY engineering strategy applies to different photolysis payloads and even different classes of PPGs. Furthermore, analysis of the DFT-calculated energy barriers in the first singlet excited state reveals valuable insights into the important factors that determine photolysis efficiency. The strategy reported herein will enable the development of efficient PPGs tailored for many applications

Enantiomerically pure β-phenylalanine analogues from α–β-phenylalanine mixtures in a single reactive extraction step

An efficient and selective method for the extraction of α-amino acids in preference over their β-isomers using PdCl2(PPh3)2 was discovered, which enables the separation of product mixtures obtained in the enantioselective enzymatic formation of β-amino acids.

One pot ‘click’ reactions: tandem enantioselective biocatalytic epoxide ring opening and [3+2] azide alkyne cycloaddition

Halohydrin dehalogenase (HheC) can perform enantioselective azidolysis of aromatic epoxides to 1,2-azido alcohols which are subsequently ligated to alkynes producing chiral hydroxy triazoles in a one-pot procedure with excellent enantiomeric excess.

Phenylimino Indolinone:A Green-Light-Responsive T-Type Photoswitch Exhibiting Negative Photochromism

Imines are photoaddressable motifs useful in the development of new generations of molecular switches, but their operation with low-energy photons and control over isomer stability remain challenging. Based on a computational design, we developed phenylimino indolinone (PIO), a green-light-addressable T-type photoswitch showing negative photochromism. The isomerization behavior of this photoactuator of the iminothioindoxyl (ITI) class was studied using time-resolved spectroscopies on time scales from femtoseconds to the steady state and by quantum-chemical analyses. The understanding of the isomerization properties and substituent effects governing these photoswitches opens new avenues for the development of novel T-type visible-light-addressable photoactuators based on C=N bonds

Geomatyka w nauczaniu leśników na uczelniach rolniczych

The idea for this publication was barn in June 2015, during a meeting of Polish teachers involved with Geographic lnformation Systems. The meeting was initiated by the Department of Geoinformation, Faculty of Geographical Sciences, University of Łódź, which received a grant to organize it. The discussion and presentations from academic teachers representing various universities in Poland were very interesting and sometimes heated. it would be advisable for other educators to familiarise themselves with the aspects of GIS education among Polish geographers, foresters, surveyors and other users. The experience of Geoinformation education in Poland is still modest, so the views of people who have been involved at Polish universities with it since the 1990s should be interesting to readers. Geographic lnformation Systems (GIS) – the integration of environmental and climate issues as an important factor for economic development and quality of life – an innovative second-degree studies. Akronim GIS-E-QL: GIS for environment and quality of life. Project objectives: The main aim of the project is to start-up attractive and innovative second­ degree studies – geoinformation in mutual cooperation of the FGS and the FMCS, students education, improving the competence of academic teachers, conference organization, publishing, cooperation with practitioners and establishing contacts with partners from Norway. This aim is consistent with the “Ana lysis of the economy's demand for graduates in key field of strategy in the context of the Europe 2020” 2012 and “Strategy for development of higher education in Poland 2020”, in the field of promoting innovative courses, formed collectively with practitioners, raising awareness of the environment. Joint actions of educators and practitioners, supported the by the strengthening of university's hardware, software and spatial data, will ensure a high quality project. The existing cooperation with practitioners indicate that further training is necessary and they would like to see postgraduates in their institutions. The final beneficiaries of the project will be the students and the academical teaching staff and indirectly the economy of the region. Students who graduate will be the main recipient of the project, the next will be teaching staff who will have contact with the practices and Norwegian partners with similar interests. In broad terms the project will benefit Polish and European economy and environment.This book has been prepared within the project „Geographic Information Systems (GIS) – the integration of environmental and climate issues as an important factor of economic development and quality of life – an innovative second-degree studies” supported by a grant from Norway through the Norway Grants and co-financed by the Polish funds. (Agreement No FSS/2014/HEI/W/0114/U/0013)

GIS w polskiej edukacji wyższej – dyskusja

The idea for this publication was barn in June 2015, during a meeting of Polish teachers involved with Geographic lnformation Systems. The meeting was initiated by the Department of Geoinformation, Faculty of Geographical Sciences, University of Łódź, which received a grant to organize it. The discussion and presentations from academic teachers representing various universities in Poland were very interesting and sometimes heated. it would be advisable for other educators to familiarise themselves with the aspects of GIS education among Polish geographers, foresters, surveyors and other users. The experience of Geoinformation education in Poland is still modest, so the views of people who have been involved at Polish universities with it since the 1990s should be interesting to readers. Geographic lnformation Systems (GIS) – the integration of environmental and climate issues as an important factor for economic development and quality of life – an innovative second-degree studies. Akronim GIS-E-QL: GIS for environment and quality of life. Project objectives: The main aim of the project is to start-up attractive and innovative second­ degree studies – geoinformation in mutual cooperation of the FGS and the FMCS, students education, improving the competence of academic teachers, conference organization, publishing, cooperation with practitioners and establishing contacts with partners from Norway. This aim is consistent with the “Ana lysis of the economy's demand for graduates in key field of strategy in the context of the Europe 2020” 2012 and “Strategy for development of higher education in Poland 2020”, in the field of promoting innovative courses, formed collectively with practitioners, raising awareness of the environment. Joint actions of educators and practitioners, supported the by the strengthening of university's hardware, software and spatial data, will ensure a high quality project. The existing cooperation with practitioners indicate that further training is necessary and they would like to see postgraduates in their institutions. The final beneficiaries of the project will be the students and the academical teaching staff and indirectly the economy of the region. Students who graduate will be the main recipient of the project, the next will be teaching staff who will have contact with the practices and Norwegian partners with similar interests. In broad terms the project will benefit Polish and European economy and environment.The experience of Polish scientists and educators in the GIS has not been as long as mentioned by Michael F. Goodchild who jointly with Ross Newkirk (Goodchild 2006) started the fi rst GIS training course at the University of Western Ontario in Canada in 1975. Discussions on the scope of knowledge included in the GIS have continued at most universities that have offered such classes. In 1988/89, owing to the National Centre for Geographic Information and Analysis (NCGIA), the 3-volume document of over 1000 pages was put together to include curriculums, student materials and other teaching aids. We have good models and we can use them. Meetings and discussions about the GIS education have been and still are regularly held all over the world (Forer P., Unwin D. 1999). When employees of Polish universities were starting to learn the GIS software and possibilities, Morgan J. M., Fleury B., Becker R. A. (1996) had already identifi ed over 800 higher education institutions all over the world that had offered at least one GIS course. The rapid development of new technologies, methods, the creation of new labour markets has arisen discussions on the contents GIS training in various centres of higher education, e.g. in the Netherlands, the US, and those have been similar to the ones presented in this article (Toppen F. J. 1992) and some issues needed to be resolved in court (DiBiase, D. 2008). You can see how important these meetings of educators are for exchanging opinions and experience. They have allowed to meed people representing various fi elds involved in the geoinformation, which may result in co-operation and new educational initiatives, and sometimes, competition. Finally, we should agree with prof. J. Gaździcki (2009 p. 12) that “It is obvious that the success of any measures to modernise education in the area under consideration depends on the interest of academic communities, involvement of research and academic staff in these endeavours, their will, ambition and willingness to co-operate”.This book has been prepared within the project „Geographic Information Systems (GIS) – the integration of environmental and climate issues as an important factor of economic development and quality of life – an innovative second-degree studies” supported by a grant from Norway through the Norway Grants and co-financed by the Polish funds. (Agreement No FSS/2014/HEI/W/0114/U/0013)

Bright Ion Channels and Lipid Bilayers

<p>If we look at a simple organism such as a zebrafish under a microscope, we would see many cells working in harmony. If we zoomed in, we would observe each unit performing its own tasks in a special aqueous environment isolated from the other units by a lipid bilayer approximately 5 nm thick. These confined units are soda!: they communicate with one another by sensing and responding to the chemical changes in their environment through receptors and ion channels. These channels control the highly specific and selective passage of ions from one side of the cell to the other and are embedded in lipid bilayers. The movement of ions through ion channels supports excitation and electrical signaling in the nervous system.</p><p>Ion channels have fascinated scientists not only because of their specificity and selectivity, but also for their functions, the serious consequences when they malfunction, and the other potential applications of these molecules. Light is a useful trigger to control and manipulate ion channels externally. With the many state-of-the-art optical technologies available, light offers a high degree of spatial and temporal control, millisecond precision, and noninvasive intervention and does not change the chemical environment of the system of interest.</p><p>In this Account, we discuss research toward the dynamic control of lipid bilayer assembly and channel function, particularly the transport across the lipid bilayer-ion channel barrier of cells using light. We first summarize the manipulation of ion channel activity with light to modulate the channel's natural activity. Based on the type of photoswitch employed, we can achieve novel functionalities with these channels, and control neural activity. Then we discuss the recent developments in light-induced transport through lipid bilayers. We focus on three different approaches: the incorporation of photoswitchable copolymers into the lipids, the doping of the lipid bilayer with photosensitive amphiphiles and the preparation of the lipid bilayers solely from photoswitchable lipids.</p><p>These examples reflect the versatility of what we can achieve by manipulating biological systems with light, from triggering the permeability of a specific area of a lipid bilayer to controlling the behavior of a whole organism.</p>

Aminomutases: mechanistic diversity, biotechnological applications and future perspectives

Aminomutases carry out the chemically challenging exchange of a hydrogen atom and an amine substituent present on neighboring carbon atoms. In recent years, aminomutases have been intensively investigated for their biophysical, structural and mechanistic characteristics. The reactions catalyzed by these enzymes have considerable potential for biotechnological applications. Here, we present an overview of this diverse group of enzymes, with a focus on enzymatic mechanisms and recent developments in their use in applied biocatalysis.

Haloalkane dehalogenase catalysed desymmetrisation and tandem kinetic resolution for the preparation of chiral haloalcohols

Six different bacterial haloalkane dehalogenases were recombinantly produced in Escherichia coli, purified, and used to catalyse the conversion of prochiral short-chain dihaloalkanes and a meso dihaloalkane, yielding enantioenriched haloalcohols. A two-reaction one-enzyme process was established in which the desymmetrisation of a dihaloalkane is followed by kinetic resolution of the chiral haloalcohol that is produced in the first step. In case of 1,3-dibromo-2-methylpropane and 1,3-dibromo-2-phenylpropane, an increase of the enantiomeric excess of the respective haloalcohol was observed in time, leading to ee values of >97%, with analytical yields of 24 and 52%, respectively. The results show that haloalkane dehalogenases can be used for the production of highly enantioenriched haloalcohols and that in some cases product enantiopurity can be improved by allowing a two-step one-enzyme tandem reaction.