Porphyrin-polymer nanocompartments: singlet oxygen generation and antimicrobial activity

A new water-soluble photocatalyst for singlet oxygen generation is presented. Its absorption extends to the red part of the spectrum, showing activity up to irradiation at 660 nm. Its efficiency has been compared to that of a commercial analogue (Rose Bengal) for the oxidation of L-methionine. The quantitative and selective oxidation was promising enough to encapsulate the photocatalyst in polymersomes. The singlet oxygen generated in this way can diffuse and remain active for the oxidation of L-methionine outside the polymeric compartment. These results made us consider the use of these polymersomes for antimicrobial applications. E. Coli colonies were subjected to oxidative stress using the photocatalyst-polymersome conjugates and nearly all the colonies were damaged upon extensive irradiation while under the same red LED light irradiation, liquid cultures in the absence of porphyrin or porphyrin-loaded polymersomes were unharme

Brushing the surface: cascade reactions between immobilized nanoreactors

Functionalization of hard or soft surfaces with, for example, ligands, enzymes or proteins, is an effective and practical methodology for the development of new applications. We report the assembly of two types of nanoreactors based upon poly(dimethylsiloxane)-block-poly(2-methyl-2-oxazoline) (PDMS-b-PMOXA) diblock copolymers as scaffold, uricase and lactoperoxidase as bio-catalysts located within the nanoreactors, and melittin as the biopores inserted into the hydrophobic shell. The nanoreactors were immobilized on poly(2-hydroxyethyl methacrylate)-co-poly(2-aminoethyl methacrylate hydrochloride) (PHEMA-co-P(2-AEMA·HCl) brushes-grafted wafer surfaces by utilizing the strong supramolecular interactions between biotin and streptavidin. The (PHEMA-co-P(2-AEMA·HCl) brushes on silicon surfaces were prepared by a surface initiating atom transfer radical polymerization (ATRP) "graft-from" technique. Cascade reactions between different surface-anchored nanoreactors were demonstrated by converting Amplex Red to the fluorescent probe resorufin by using the H2O2 produced from uric acid and H2O. The detailed properties of the nanoreactors on the functionalized surface including the binding behaviours and cascade reactions were investigated using emission spectroscopy, transmission electron microscopy (TEM), light scattering (LS), atomic force microscopy (AFM) and a quartz crystal microbalance (QCM-D). The results are proof-of-principle for the preparation of catalytically functional engineered surface materials and lay the foundation for applying this advanced functional surface material in biosensing, implanting and antimicrobial materials preparation

Porphyrin Containing Polymersomes with Enhanced ROS Generation Efficiency: in vitro evaluation

Abstract Porphyrins are molecules possessing unique photophysical properties making them suitable for application in photodynamic therapy. The incorporation of porphyrins into natural or synthetic nano-assemblies such as polymersomes is a strategy to improve and prolong their therapeutic capacities and to overcome their limitations as therapeutic and diagnostic agents. Here, 5,10,15,20-tetrakis(1-(6-ethoxy-6-oxohexyl)-4-pyridin-1-io)-21H,23H-porphyrin tetrabromide porphyrin is inserted into polymersomes in order to demonstrate that the encapsulation enhances its ability to generate highly reactive singlet oxygen (1O2) upon irradiation in vitro. The photoactivation of the free and polymersome-encapsulated porphyrin is evaluated by electron spin resonance and cell viability assays on three different mammalian cell lines. The results indicate that by encapsulating the porphyrin, a controlled ROS delivery within the cells is achieved, at the same time avoiding side effects such as dark toxicity, non-specific porphyrin release and over time decreased activity in vitro. This work focuses on showing a not-toxic model system for modern therapeutic nanomedicine, which works under mild irradiation and dosage conditions

GEOMAGIA50.v3: 1. general structure and modifications to the archeological and volcanic database

Background: GEOMAGIA50.v3 is a comprehensive online database providing access to published paleomagnetic, rock magnetic, and chronological data from a variety of materials that record Earth’s magnetic field over the past 50 ka.Findings: Since its original release in 2006, the structure and function of the database have been updated and a significant number of data have been added. Notable modifications are the following: (1) the inclusion of additional intensity, directional and metadata from archeological and volcanic materials and an improved documentation of radiocarbon dates; (2) a new data model to accommodate paleomagnetic, rock magnetic, and chronological data from lake and marine sediments; (3) a refinement of the geographic constraints in the archeomagnetic/volcanic query allowing selection of particular locations; (4) more flexible methodological and statistical constraints in the archeomagnetic/volcanic query; (5) the calculation of predictions of the Holocene geomagnetic field from a series of time varying global field models; (6) searchable reference lists; and (7) an updated web interface. This paper describes general modifications to the database and specific aspects of the archeomagnetic and volcanic database. The reader is referred to a companion publication for a description of the sediment database.Conclusions: The archeomagnetic and volcanic part of GEOMAGIA50.v3 currently contains 14,645 data (declination, inclination, and paleointensity) from 461 studies published between 1959 and 2014. We review the paleomagnetic methods used to obtain these data and discuss applications of the data within the database. The database continues to expand as legacy data are added and new studies published. The web-based interface can be found at http://geomagia.gfz-potsdam.de webcite

GEOMAGIA50.v3: 2. A new paleomagnetic database for lake and marine sediments

Background: GEOMAGIA50.v3 for sediments is a comprehensive online database providing access to published paleomagnetic, rock magnetic, and chronological data obtained from lake and marine sediments deposited over the past 50 ka. Its objective is to catalogue data that will improve our understanding of changes in the geomagnetic field, physical environments, and climate.Findings: GEOMAGIA50.v3 for sediments builds upon the structure of the pre-existing GEOMAGIA50 database for magnetic data from archeological and volcanic materials. A strong emphasis has been placed on the storage of geochronological data, and it is the first magnetic archive that includes comprehensive radiocarbon age data from sediments. The database will be updated as new sediment data become available.Conclusions: The web-based interface for the sediment database is located at http://geomagia.gfz-potsdam.de/geomagiav3/SDquery.php webcite. This paper is a companion to Brown et al. (Earth Planets Space doi:10.1186/s40623-015-0232-0, 2015) and describes the data types, structure, and functionality of the sediment database

Air-stable Solid-state Photoluminescence Standards for Quantitative Measurements Based on 4'-phenyl-2,2':6',2''-Terpyridine Complexes with Trivalent Lanthanides

Correct photoluminescence quantum yield (PLQY) determination in the solid state is vital for numerous application fields, such as photovoltaics, solid lighting or the development of phosphors. In order to increase the limited number of suitable standards for such determinations, two new Ln 3+ -based complexes with 4′-phenyl-2,2′ : 6′,2"-terpyridine γ-[Ln 4 (OAc) 12 (ptpy) 2 ] ( 1-Eu with europium and 1-Tb with terbium) are presented. The corresponding complexes show solid-state QYs of 58(4) % and 46(3) %, respectively, exhibiting broadband absorption in the UV range from 380-200 nm. As Ln 3+ ions in general exhibit narrow f - f transitions, spectral regions with a broadness of 20-35 nm can be checked. Both complexes have suitable thermal stability, up to 270 °C, and are stable with respect to air and humidity, for 1-Eu up to 75 % and for 1-Tb up to 53 % relative humidity. These complexes are altogether suitable as standards to increase the reliability of PLQY determination and proposed to be used for a relative PLQY determination in the solid stat

Insights from geodynamo simulations into long-term geomagnetic field behaviour

Detailed knowledge of the long-term spatial configuration and temporal variability of the geomagnetic field is lacking because of insufficient data for times prior to 10 ka. We use realisations from suitable numerical simulations to investigate three important questions about stability of the geodynamo process: is the present field representative of the past field; does a time-averaged field actually exist; and, supposing it exists, how long is needed to define such a field. Numerical geodynamo simulations are initially selected to meet existing criteria for morphological similarity to the observed magnetic field. A further criterion is introduced to evaluate similarity of long-term temporal variations. Allowing for reasonable uncertainties in the observations, observed and synthetic axial dipole moment frequency spectra for time series of order a million years in length should be fit by the same power law model. This leads us to identify diffusion time as the appropriate time scaling for such comparisons. In almost all simulations, intervals considered to have good morphological agreement between synthetic and observed field are shorter than those of poor agreement. The time needed to obtain a converged estimate of the time-averaged field was found to be comparable to the length of the simulation, even in non-reversing models, suggesting that periods of stable polarity spanning many magnetic diffusion times are needed to obtain robust estimates of the mean dipole field. Long term field variations are almost entirely attributable to the axial dipole; nonzonal components converge to long-term average values on relatively short timescales (15-20 kyr). In all simulations, the time-averaged spatial power spectrum is characterised by a zigzag pattern as a function of spherical harmonic degree, with relatively higher power in odd degrees than in even degrees. We suggest that long-term spatial characteristics of the observed field may emerge on averaging times that are within reach for the next generation of global time-varying paleomagnetic field models.

Recent investigations of the 0-5 geomagnetic field recorded by lava flows

Sherpa Romeo green journal (pre or post print only)We present a synthesis of paleomagnetic directional data collected from 873 lava flows at 17 different locations under the collaborative Time Averaged geomagnetic Field Initiative (TAFI). The data range from 05 Ma in age, and provide new high quality data with improved spatial coverage. Data quality at each site is measured using k, the best estimate of the Fisherian precision parameter, and its influence on inclination anomaly and VGP dispersion is evaluated by systematically excluding data with successively higher values of k. When combined with regional compilations from NW USA, SW USA, Japan, New Zealand, Hawaii, Mexico, S. Pacific and the Indian Ocean, a data set of 2283 pairs of declination and inclination data, with k>100, and VGP latitudes greater than 45 is obtained. This is a more than 7fold increase over similar quality data in the existing Global Paleomagnetic Database (GPMDB). The new data set spans 78 S to 53 N, and has sufficient temporal and spatial sampling to allow characterization of latitudinal variations in the timeaveraged field (TAF) and paleosecular variation (PSV) for the Brunhes and Matuyama epochs, and for the 0–5 Myr interval combined. PSV, as measured by dispersion of virtual geomagnetic poles, shows less latitudinal variation than predicted by current statistical PSV models. Variation of inclination anomaly with latitude is assessed using 2parameter zonal TAF models – these have axial quadrupole contributions of 2% – 4% of the axial dipole term, and axial octupole contributions of 3% – 5%. Approximately 2% of the octupole signature is likely the result of bias incurred by averaging unit vectors. The new data set provides significant improvement over previous compilations, and can contribute to a new generation of global paleomagnetic field models.Ye