Background Understanding the regional vascular delivery of particles to tumour sites is a prerequisite for developing new diagnostic and therapeutic composites for treatment of oncology patients. We describe a novel imageable 67 Ga-radiolabelled polymer composite that is biocompatible in an animal tumour model and can be used for preclinical imaging investigations of the transit of different sized particles through arterial networks of normal and tumour-bearing organs. Results Radiolabelling of polymer microspheres with 67 Ga was achieved using a simple mix and wash method, with tannic acid as an immobilising agent. Final in vitro binding yields after autoclaving averaged 94.7%. In vivo stability of the composite was demonstrated in New Zealand white rabbits by intravenous administration, and intrahepatic artery instillations were made in normal and VX2 tumour implanted rabbit livers. Stability of radiolabel was sufficient for rabbit lung and liver imaging over at least 3 hours and 1 hour respectively, with lung retention of radiolabel over 91%, and retention in both normal and VX2 implanted livers of over 95%. SPECT-CT imaging of anaesthetised animals and planar imaging of excised livers showed visible accumulation of radiolabel in tumours. Importantly, microsphere administration and complete liver dispersal was more easily achieved with 8 μm diameter MS than with 30 μm MS, and the smaller microspheres provided more distinct and localised tumour imaging. Conclusion This method of producing 67 Ga-radiolabelled polymer microspheres is suitable for SPECT-CT imaging of the regional vascular delivery of microspheres to tumour sites in animal models. Sharper distinction of model tumours from normal liver was obtained with smaller MS, and tumour resolution may be further improved by the use of 68 Ga instead of 67 Ga, to enable PET imaging.

Garnet scintillators often suffer from undesired afterglow, the origin of which is not always well-understood. A possible origin is contamination with transition metal (TM) ions. These impurities can act as traps giving rise to afterglow. Alternatively, they may show long-lived (microsecond) d-d emission. Here we present a systematic study on the role of 3d TM impurities in (Lu,Gd)(3)(Ga,Al)(5)O-12 garnet scintillators. Scintillator disks intentionally doped with ppm levels of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, or Zn were studied to identify TM-related traps in thermoluminescence (TSL) glow curves and their role in afterglow. For Ti, V, and Cr additional TSL peaks were observed that gave rise to RT afterglow in the 10(-2)-10(3) s time range, depending on garnet composition. On the millisecond time scale long-lived red/near-infrared emission was observed from Mn and Fe impurities, explained by spin-forbidden d-d emission. We show that afterglow can be reduced by the use of ultrapure raw materials. Other solutions include bandgap engineering for the garnet host to modify trap depths and applying optical filters to block the spin-forbidden d-d emission. The present study provides an insightful overview of the role of 3d TM impurities on afterglow in Ce-doped scintillators and procedures to predict and reduce afterglow. These insights will aid the development of Ce-doped garnets with superior afterglow behavior.

PURPOSE:Selective internal radiation therapy (SIRT) is an effective treatment option for liver tumors, using Y-90-loaded polymer microspheres that are delivered via catheterization of the hepatic artery. Since Y-90 is a beta emitter and not conveniently imaged by standard clinical instrumentation, dosimetry is currently evaluated in each patient using a surrogate particle, 99mTechnetium-labeled macroaggregated albumin (99mTc-MAA). We report a new composite consisting of 99mTc-labeled nanoparticles attached to the same polymer microspheres as used for SIRT, which can be imaged with standard SPECT.METHODS:Carbon nanoparticles with an encapsulated core of 99mTc were coated with the polycation protamine sulfate to provide electrostatic attachment to anionic polystyrene sulfonate microspheres of different sizes (30, 12, and 8 µm). The in vivo stability of these composites was determined via intravenous injection and entrapment in the capillary network of normal rabbit lungs for up to 3 hours. Furthermore, we evaluated their biodistribution in normal rabbit livers, and livers implanted with VX2 tumors, following intrahepatic artery instillation.RESULTS:We report distribution tests for three different sizes of radiolabeled microspheres and compare the results with those obtained using 99mTc-MAA. Lung retention of the radiolabeled microspheres ranged from 72.8% to 92.9%, with the smaller diameter microspheres showing the lowest retention. Liver retention of the microspheres was higher, with retention in normal livers ranging from 99.2% to 99.8%, and in livers with VX2 tumors from 98.2% to 99.2%. The radiolabeled microspheres clearly demonstrated preferential uptake at tumor sites due to the increased arterial perfusion produced by angiogenesis.CONCLUSION:We describe a novel use of radiolabeled carbon nanoparticles to generate an imageable microsphere that is stable in vivo under the shear stress conditions of arterial networks. Following intra-arterial instillation in the normal rabbit liver, they distribute in a distinct segmented pattern, with the smaller microspheres extending throughout the organ in finer detail, while still being well retained within the liver. Furthermore, in livers hosting an implanted VX2 tumor, they reveal the increased arterial perfusion of tumor tissue resulting from angiogenesis. These novel composites may have potential as a more representative mimic of the vascular distribution of therapeutic microspheres in patients undergoing SIRT.

Red-emitting Mn 4+ -doped fluorides are a promising class of materials to improve the color rendering and luminous efficacy of white light-emitting diodes (w-LEDs). For w-LEDs, the luminescence quenching temperature is very important, but surprisingly no systematic research has been conducted to understand the mechanism for thermal quenching in Mn 4+ -doped fluorides. Furthermore, concentration quenching of the Mn 4+ luminescence can be an issue but detailed investigations are lacking. In this work, we study thermal quenching and concentration quenching in Mn 4+ -doped fluorides by measuring luminescence spectra and decay curves of K 2 TiF 6 :Mn 4+ between 4 and 600 K and for Mn 4+ concentrations from 0.01% to 15.7%. Temperature-dependent measurements on K 2 TiF 6 :Mn 4+ and other Mn 4+ -doped phosphors show that quenching occurs through thermally activated crossover between the 4 T 2 excited state and 4 A 2 ground state. The quenching temperature can be optimized by designing host lattices in which Mn 4+ has a high 4 T 2 state energy. Concentration-dependent studies reveal that concentration quenching effects are limited in K 2 TiF 6 :Mn 4+ up to 5% Mn 4+ . This is important, as high Mn 4+ concentrations are required for sufficient absorption of blue LED light in the parity-forbidden Mn 4+ d – d transitions. At even higher Mn 4+ concentrations (>10%), the quantum efficiency decreases, mostly due to direct energy transfer to quenching sites (defects and impurity ions). Optimization of the synthesis to reduce quenchers is crucial for developing more efficient highly absorbing Mn 4+ phosphors. The present systematic study provides detailed insights into temperature and concentration quenching of Mn 4+ emission and can be used to realize superior narrow-band red Mn 4+ phosphors for w-LEDs.

Mn4+-doped fluorides show narrow red line emission under blue light excitation and are therefore promising materials to improve the color rendering and luminous efficacy of white light emitting diodes (wLEDs). The synthesis of Mn4+-doped fluorides is however challenging and so far only a few efficient Mn4+-doped fluoride phosphors have been reported. In this work we present the synthesis and optical properties of a novel Cs2HfF6:Mn4+ phosphor. The Cs2HfF6:Mn4+ phosphor is prepared via a two-step co-precipitation method and shows bright red Mn4+ luminescence around 620nm under blue light excitation. Detailed insight in the luminescence properties is obtained by studying the Mn4+ emission and luminescence decay down to cryogenic temperatures. The Cs2HfF6:Mn4+ phosphor has a photoluminescence quantum efficiency higher than 80%, which makes it an interesting red-emitting material for wLEDs and other lighting applications. As the Mn4+ emission from Cs2HfF6:Mn4+ shows quenching above 100°C (T½ = 403K), the use of this phosphor will be limited to low-power LED lighting.

White light emitting diodes (LEDs) are nowadays widely applied in general lighting and consumer electronics. Due to their superior energy efficiency and long operation lifetime, white LEDs are considered to be the light sources of the future, and it is anticipated that white LEDs will largely replace incandescent and fluorescent lamps in the coming ten years. Commercial white LEDs are composed of blue-emitting (In,Ga)N LEDs and luminescent materials (‘phosphors’) that convert part of the blue LED emission to yellow and red light. Both yellow and red conversion phosphors are necessary to generate warm white light with a good color quality. The red phosphors that are currently used in white LEDs are Eu2+-doped nitrides. These phosphors have a high efficiency and stability, but a major drawback is that their Eu2+ emission band extends into the deep-red spectral region where the eye sensitivity is low. This causes the efficiency of the white LED to decrease significantly. A worldwide search is therefore aimed at finding efficient narrow band red-emitting materials that can be excited by blue light. The results presented in this thesis provide new insights in the synthesis and luminescence of two types of narrow band red-emitting phosphors: Mn4+-doped phosphors and Eu2+-activated phosphates. We describe the synthesis and optical properties of new Mn4+-doped phosphors and investigate how the Mn4+ emission and energy levels are influenced by the host lattice the Mn4+ ions are situated in. Furthermore, we show which processes are responsible for thermal quenching and concentration quenching of the Mn4+ luminescence in Mn4+-doped phosphors. Both these effects are crucial for the performance of white LEDs containing Mn4+ phosphors. Finally, we study the unusual narrow yellow/red Eu2+ luminescence of Eu2+-activated phosphates through extensive low-temperature spectroscopic measurements. The results show that the unusual narrow yellow/red Eu2+ luminescence can be caused by deformations in the excited state of Eu2+.

Mn4+-activated hexafluoroaluminates are promising red-emitting phosphors for white light emitting diodes (w-LEDs). Here, we report the synthesis of Na3AlF6:Mn4+, K3AlF6:Mn4+ and K2NaAlF6:Mn4+ phosphors through a simple two-step co-precipitation method. Highly monodisperse large (~20 μm) smoothed-octahedron shaped crystallites are obtained for K2NaAlF6:Mn4+. The large size, regular shape and small size distribution are favorable for application in w-LEDs. All Mn4+-doped hexafluoroaluminates show bright red Mn4+ luminescence under blue light excitation. We compare the optical properties of Na3AlF6:Mn4+, K3AlF6:Mn4+ and K2NaAlF6:Mn4+ at room temperature and 4 K. The luminescence measurements reveal that multiple Mn4+ sites exist in M3AlF6:Mn4+ (M = Na, K), which is explained by the charge compensation that is required for Mn4+ on Al3+ sites. Thermal cycling experiments show that the site distribution changes after annealing. Finally, we investigate thermal quenching and show that the luminescence quenching temperature is high, around 460–490 K, which makes these Mn4+-doped hexafluoroaluminates interesting red phosphors for w-LEDs. The new insights reported on the synthesis and optical properties of Mn4+ in the chemically and thermally stable hexafluoroaluminates can contribute to the optimization of red-emitting Mn4+ phosphors for w-LEDs.

Assessing the mechanisms of micro-structural change and their effect on transport properties using digital core analysis requires balancing field of view and resolution. This typically leads to the compromise of working with relatively small samples, where boundary effects can be substantial. A direct comparison with experiment, as e.g. desirable to eliminate unknown parameters and integrate numerical and physical experiments, needs to consider these boundary effects. Here we develop a workflow to define measuring windows within a sample where these boundary effects are minimised allowing the integration of physical and numerical experiment. We consider in particular sleeve leakage and use a radial partitioning of the solutions to various transport equations to derive relevant regional measures, which may be used for the development of cross-correlations between physical properties.Samples of Bentheimer and Castlegate sandstone as well as Mt. Gambier limestone and a sucrosic dolomite are considered. The sample plugs are encased in rubber sleeves and micro-CT images acquired at ambient conditions. Using these high-resolution images we calculate transport properties, namely permeability and electrical conductivity, and analyse the resulting field solutions with regard to flux across different regions of interest. The latter are selected on the basis of distance to the sample sleeve inner surface. Clear bypassing at the sleeve-sample interface in terms of elevated fluxes is observed for all samples, although to different extent. We consider different sleeve boundary conditions to define a measuring window minimising these effects, use the procedure to compare flux averages defined over these measuring windows with conventional choices of simulation domains, and compare resulting physical cross-correlations. (C) 2016 Elsevier Ltd. All rights reserved.

In this article, a detailed analysis of the structure–property correlation of the decay times of the spin-forbidden and spin-enabled transitions of Yb2+ in the halidoperovskites CsCaX3 and CsSrX3 (X = Cl, Br, I) is presented.

The radiative transition probability is a fundamental property for optical transitions. Extensive research, theoretical and experimental, has been conducted to establish the relation between the photonic environment and electric dipole (ED) transition probabilities. Recent work shows that the nanocrystal (NC)-cavity model accurately describes the influence of the refractive index n on ED transition rates for emitters in NCs. For magnetic dipole (MD) transitions, theory predicts a simple n3 dependence. However, experimental evidence is sparse and difficult to obtain. Here we report Eu3+-(with distinct ED+MD transitions) and Gd3+-(MD transitions) doped β-NaYF4 NC model systems to probe the influence of n on ED and MD transition probabilities through luminescence lifetime and ED/MD intensity ratio measurements. The results provide strong experimental evidence for an n3 dependence of MD transition probabilities. This insight is important for understanding and controlling the variation of spectral distribution in emission spectra by photonic effects.

Palaeospondylus gunni Traquair, 1890 is an enigmatic Devonian vertebrate whose taxonomic affinities have been debated since it was first described. Most recently, Palaeospondylus has been identified as a stem-group hagfish (Myxinoidea). However, one character questioning this assignment is the presence of three semicircular canals in the otic region of the cartilaginous skull, a feature of jawed vertebrates. Additionally, new tomographic data reveal that the following characters of crown-group gnathostomes (chondrichthyans + osteichthyans) are present in Palaeospondylus: a longer telencephalic region of the braincase, separation of otic and occipital regions by the otico-occipital fissure, and vertebral centra. As well, a precerebral fontanelle and postorbital articulation of the palatoquadrate are characteristic of certain chondrichthyans. Similarities in the structure of the postorbital process to taxa such as Pucapampella, and possible presence of the ventral cranial fissure, both support a resolution of Pa. gunni as a stem chondrichthyan. The internally mineralized cartilaginous skeleton in Palaeospondylus may represent a stage in the loss of bone characteristic of the Chondrichthyes.

Rice (Oryza sativa) was domesticated in the Yangtze Valley region at least 6000-8000 years ago, yet the timing of dispersal of domesticated rice to Southeast Asia is contentious. Often rice is not well-preserved in archaeobotanical assemblages at early Neolithic sites in the wet tropics of Southeast Asia and consequently rice impressions in pottery have been used as a proxy for rice cultivation despite their uncertain taxonomic and domestication status. In this research, we use microCT technology to determine the 3D microscale morphology of rice husk and spikelet base inclusions within pottery sherds from early Neolithic sites in Vietnam. In contrast to surface impressions, microCT provides images of the entire husk and spikelet base preserved within the pottery, including the abscission scar characteristic of domesticated rice. This research demonstrates the potential of microCT to be a new, non-destructive method for the identification of domesticated plant remains within pottery sherds, especially in contexts where archaeobotanical preservation is poor and chaff-tempered sherds are rare and unavailable for destructive analysis. The method has the potential to greatly advance the understanding of crop domestication and agricultural dispersal for ceramic cultures in different parts of the world.

Multi-scalar geoarchaeological investigations were conducted on several samples of sediment (dolomite cave sediments, ferricrete ridge, speleothem, tufa and tufa cave sediments) from four early hominin fossil-bearing sites (Taung Type Site, Haasgat, Drimolen Main Quarry, Elandsfontein) in different South African karst environments. The study was designed to test the value of geoarchaeological techniques for identifying and characterising environments of deposition and diagenetic processes involved in site formation within different mediums and different karst environments. The traditional petrographic method is weighed against two relatively new methodological contributions to site formation and diagenesis: Computed Tomography (CT) and automated Quantitative Evaluation of Minerals using Energy Dispersive Spectroscopy (QEM-EDS), employing QEMSCAN® technology. An integrated micro-sampling approach is outlined for successful cross-correlation between techniques. The study demonstrates that different analyses vary in their ability to visualise different types of process – primary and secondary. Thin section petrography remains the ‘gold standard’ for analyses conducted at the micro-scale, while QEM-EDS and CT offer exciting potential to perform meso-scale analyses and are best utilised as complementary rather than alternative techniques to petrography.

Red emitting Mn4+-doped crystalline materials have potential for application in light emitting devices and therefore it is important to understand how the optical properties of Mn4+ are influenced by the host lattice the Mn4+ ions are situated in. In this work we investigate the effect of the host cations in the second coordination sphere on the Mn4+ emission by studying the luminescence of Mn4+ ions doped into three isostructural rare earth (RE) stannate RE2Sn2O7 pyrochlores (RE3+ = Y3+, Lu3+ or Gd3+). It is found that the energies of the Mn4+ T-4(1) and T-4(2) states significantly increase with decreasing Mn4+-O2- distance, whereas the energy of the E-2 level shows a small shift to higher energies from RE3+ = Gd3+ to Lu3+ to Y3+. The observed trend for the E-2 level energy is not related to the size of the RE3+ ion and is not in line with theoretical calculations reported previously. Low temperature emission spectra of the RE2Sn2O7:Mn4+ phosphors reveal that only asymmetrical vibronic modes couple to the E-2 -> (4)A(2) transition and furthermore show there is significant and unexpected local disorder for Mn4+ in Gd2Sn2O7 that is not observed for Mn4+ in the other hosts. Photoluminescence decay measurements demonstrate that the luminescence of RE2Sn2O7:Mn4+ is strongly quenched below room temperature which is assigned to non-radiative relaxation via a low-lying O2- -> Mn4+ charge-transfer state. (C) 2016 Elsevier B.V. All rights reserved.

The mandible and dentition of the Early Cretaceous monotreme Teinolophos trusleri. Alcheringa 40, xx-xx. ISSN 0311-5518.The monotreme Teinolophos trusleri Rich, Vickers-Rich, Constantine, Flannery, Kool & van Klaveren, 1999 from the Early Cretaceous of Australia is redescribed and reinterpreted here in light of additional specimens of that species and compared with the exquisitely preserved Early Cretaceous mammals from Liaoning Province, China. Together, this material indicates that although T. trusleri lacked a rod of postdentary bones contacting the dentary, as occurs in non-mammalian cynodonts and basal mammaliaforms, it did not share the condition present in all living mammals, including monotremes, of having the three auditory ossicles, which directly connect the tympanic membrane to the fenestra ovalis, being freely suspended within the middle ear cavity. Rather, T. trusleri appears to have had an intermediate condition, present in some Early Cretaceous mammals from Liaoning, in which the postdentary bones cum ear ossicles retained a connection to a persisting Meckel's cartilage although not to the dentary. Teinolophos thus indicates that the condition of freely suspended auditory ossicles was acquired independently in monotremes and therian mammals. Much of the anterior region of the lower jaw of Teinolophos is now known, along with an isolated upper ultimate premolar. The previously unknown anterior region of the jaw is elongated and delicate as in extant monotremes, but differs in having at least seven antemolar teeth, which are separated by distinctdiastemata. The dental formula of the lower jaw of Teinolophos trusleri as now known is i2 c1 p4 m5. Both the deep lower jaw and the long-rooted upper premolar indicate that Teinolophos, unlike undoubted ornithorhynchids (including the extinct Obdurodon), lacked a bill.

The efficient narrow band emission of Eu2+ in Cs2MP2O7 (M = Ca2+, Sr2+) is characterized by a large Stokes shift and a high quenching temperature which makes the material promising for application in warm white LEDs. The unusual Eu2+ luminescence properties were reported recently but an explanation for the peculiar behavior is lacking. In this paper we aim at providing new insights in the luminescence of the Eu2+ emission in Cs2MP2O7 through measurements at cryogenic temperatures (down to 4K) and by comparison with the d–f luminescence of Ce3+ and Yb2+ in the same host. The results reveal a sharp onset of the Eu2+ emission and excitation bands at 4K. Usually the sharp onset for narrow excitation and emission bands coincide at an energy corresponding to the zero-phonon (purely electronic) transition, but for Eu2+ in Cs2MP2O7 there is a large shift of 3500cm−1 between the onsets, consistent with the large Stokes shift observed. The onset shift can be explained by emission from a lower energy distorted excited 4f65d1 state. For Ce3+, the f–d absorption bands are at energies expected based on the relation between the absorption energies for Eu2+ and Ce3+ reported by Dorenbos. Contrary to Eu2+, the emission for Ce3+ shows a normal Stokes shift and therefore the emission bands are at much higher energies than predicted from the energy of the Eu2+ emission and the Dorenbos relations. Based on the present results the unusually large Stokes shift for the Eu2+ emission in Cs2MP2O7 is assigned to a Jahn–Teller like deformation in the excited 4f65d1 state of Eu2+ that is not present in the 5d state of Ce3+.

BACKGROUND:Living gnathostomes (jawed vertebrates) comprise two divisions, Chondrichthyes (cartilaginous fishes, including euchondrichthyans with prismatic calcified cartilage, and extinct stem chondrichthyans) and Osteichthyes (bony fishes including tetrapods). Most of the early chondrichthyan ('shark') record is based upon isolated teeth, spines, and scales, with the oldest articulated sharks that exhibit major diagnostic characters of the group--prismatic calcified cartilage and pelvic claspers in males--being from the latest Devonian, c. 360 Mya. This paucity of information about early chondrichthyan anatomy is mainly due to their lack of endoskeletal bone and consequent low preservation potential.METHODOLOGY/PRINCIPAL FINDINGS:Here we present new data from the first well-preserved chondrichthyan fossil from the early Late Devonian (ca. 380-384 Mya) Gogo Formation Lägerstatte of Western Australia. The specimen is the first Devonian shark body fossil to be acid-prepared, revealing the endoskeletal elements as three-dimensional undistorted units: Meckel's cartilages, nasal, ceratohyal, basibranchial and possible epibranchial cartilages, plus left and right scapulocoracoids, as well as teeth and scales. This unique specimen is assigned to Gogoselachus lynnbeazleyae n. gen. n. sp.CONCLUSIONS/SIGNIFICANCE:The Meckel's cartilages show a jaw articulation surface dominated by an expansive cotylus, and a small mandibular knob, an unusual condition for chondrichthyans. The scapulocoracoid of the new specimen shows evidence of two pectoral fin basal articulation facets, differing from the standard condition for early gnathostomes which have either one or three articulations. The tooth structure is intermediate between the 'primitive' ctenacanthiform and symmoriiform condition, and more derived forms with a euselachian-type base. Of special interest is the highly distinctive type of calcified cartilage forming the endoskeleton, comprising multiple layers of nonprismatic subpolygonal tesserae separated by a cellular matrix, interpreted as a transitional step toward the tessellated prismatic calcified cartilage that is recognized as the main diagnostic character of the chondrichthyans.

Nanocrystals (NCs) doped with luminescent ions form an emerging class of materials. In contrast to excitonic transitions in semiconductor NCs, the optical transitions are localized and not affected by quantum confinement. The radiative decay rates of the dopant emission in NCs are nevertheless different from their bulk analogues due to photonic effects, and also the luminescence quantum yield (QY, important for applications) is affected. In the past, different theoretical models have been proposed to describe the photonic effects for dopant emission in NCs, with little experimental validation. In this work we investigate the photonic effects on the radiative decay rate of luminescent doped NCs using 4 nm LaPO4 NCs doped with Ce(3+) or Tb(3+) ions in different refractive index solvents and bulk crystals. We demonstrate that the measured influence of the refractive index on the radiative decay rate of the Ce(3+) emission, having near unity QY, is in excellent agreement with the theoretical nanocrystal-cavity model. Furthermore, we show how the nanocrystal-cavity model can be used to quantify the nonunity QY of Tb(3+)-doped LaPO4 NCs and demonstrate that, as a general rule, the QY is higher in media with higher refractive index.

Oriented strand board (OSB) is an important wood composite used in situations where fungal decay and termite attack can occur. To counter these threats, powdered zinc borate biocide is commonly added to OSB. The effectiveness of biocides depends on their even distribution within composites and resistance to leaching, but little is known about the distribution of zinc borate in OSB. Zinc is denser than wood and it should be possible to map its distribution in OSB using X-ray micro-CT. We test this hypothesis and chemically register zinc in OSB using SEM-EDX. Zinc borate particles aggregated at the wood-adhesive interface in OSB, creating interrupted lines of zinc oriented in the x-y plane. Zinc borate particles were also found in the lumens of wood cells. Zinc was distributed throughout OSB, although slightly less was present in the core of the composite than in surface layers. A network of zinc remained in OSB after leaching in water. The resistance of zinc to leaching may be due to its incorporation in glue-lines within OSB, in addition to its low water-solubility. We conclude that X-ray micro-CT is a powerful tool for studying the distribution of zinc in OSB and other wood composites containing zinc borate.