Spin-Vibronic Intersystem Crossing and Molecular Packing Effects in Heavy Atom Free Organic Phosphor.

We present a detailed investigation into the excited state properties of a planar symmetric azatriangulenetrione, HTANGO, which has received significant interest due to its high solid-state phosphorescence quantum yield and therefore potential as an organic room temperature phosphorescent (ORTP) dye. Using a model linear vibronic coupling Hamiltonian in combination with quantum dynamics simulations, we observe that intersystem crossing (ISC) in HTANGO occurs with a rate of ∼10 s , comparable to benzophenone, an archetypal molecule for fast ISC in heavy metal free molecules. Our simulations demonstrate that the mechanism for fast ISC is associated with the high density of excited triplet states which lie in close proximity to the lowest singlet states, offering multiple channels into the triplet manifold facilitating rapid population transfer. Finally, to rationalize the solid-state emission properties, we use quantum chemistry to investigate the excited state surfaces of the HTANGO dimer, highlighting the influence and importance of the rotational alignment between the two HTANGO molecules in the solid state and how this contributes to high phosphorescence quantum yield

Synthesis and characterisation of phosphorescent rhenium(I) complexes of hydroxy- and methoxy-substituted imidazo[4,5- f ]-1,10-phenanthroline ligands

Eight new fluorescent ligands (L1-L8) derived from the fused imidazo[4,5-f]-1,10-phenanthroline core, have been synthesised utilising a one-pot methodology. The ligands include two points of structural variety, allowing multiply-substituted aryl groups (including hydroxy and methoxy moieties) to be attached to the ligand core. The ligands L1-L8 are fluorescent (λem = 399–426 nm) and react with pentacarbonylbromorhenium to give coordination complexes of the form fac-[ReBr(CO)3(NˆN)] (where NˆN = L1-L8). The complexes were characterised using a variety of spectroscopic and analytical techniques, including single crystal X-ray diffraction studies on two examples. The rhenium complexes were all found to be luminescent, revealing classical 3MLCT emission at 579–587 nm in aerated solution with corresponding lifetimes in the range 149–166 ns

The Nature of Boulder-Rich Deposits in the Upper Big Flat Brook Drainage, Sussex County, New Jersey

The upper reaches of the Big Flat Brook drainage, northwest of Kittatinny Mountain, contain a variety of glacial, pro-glacial, and periglacial deposits from the Late Quaternary. The area is dominated by recessional moraines and ubiquitous ground moraine, along with meltwater deposits, drumlins, and possible postglacial periglacial features. We have identified a curious boulder-rich deposit in the vicinity of Lake Ocquittunk and Lake Wapalanne on upper Big Flat Brook. The area where these boulder deposits occur is mapped (1:24,000 surficial geology) as till. As mapped and observed, larger cobbles and boulders within the till are quartz-pebble conglomerate, quartzite, sandstone, and shale. The boulder-rich deposits differ from the typical till, however. Unlike the local till, which is more mixed in lithology, the boulder deposits are nearly exclusively Shawangunk conglomerate. The deposits are discontinuous, but appear to occur at a topographic level above the meltwater stream terraces. The boulders in the deposits lie partially embedded in soil, but are very closely spaced. The boulders range in size from ~20cm to over 100cm, and present a subrounded to subangular shape. There appears to be a fabric orientation of the boulders, NE-SW, with subsidiary orientations. As the boulder deposits differ from other mapped features in the area, we attempt to ascertain the origin for the deposits. Unique moraine dynamics, meltwater flood, periglacial slope movement, and slope-snow bank processes are possible explanations. Detailed examination of these boulder deposits will provide a finer explanation of the glacial and post-glacial geomorphic history of the area

1064 nm Dispersive Raman Microspectroscopy and Optical Trapping of Pharmaceutical Aerosols.

Raman spectroscopy is a powerful tool for investigating chemical composition. Coupling Raman spectroscopy with optical microscopy (Raman microspectroscopy) and optical trapping (Raman tweezers) allows microscopic length scales and, hence, femtolitre volumes to be probed. Raman microspectroscopy typically uses UV/visible excitation lasers, but many samples, including organic molecules and complex tissue samples, fluoresce strongly at these wavelengths. Here we report the development and application of dispersive Raman microspectroscopy designed around a near-infrared continuous wave 1064 nm excitation light source. We analyze microparticles (1-5 μm diameter) composed of polystyrene latex and from three real-world pressurized metered dose inhalers (pMDIs) used in the treatment of asthma: salmeterol xinafoate (Serevent), salbutamol sulfate (Salamol), and ciclesonide (Alvesco). For the first time, single particles are captured, optically levitated, and analyzed using the same 1064 nm laser, which permits a convenient nondestructive chemical analysis of the true aerosol phase. We show that particles exhibiting overwhelming fluorescence using a visible laser (514.5 nm) can be successfully analyzed with 1064 nm excitation, irrespective of sample composition and irradiation time. Spectra are acquired rapidly (1-5 min) with a wavelength resolution of 2 nm over a wide wavenumber range (500-3100 cm-1). This is despite the microscopic sample size and low Raman scattering efficiency at 1064 nm. Spectra of individual pMDI particles compare well to bulk samples, and the Serevent pMDI delivers the thermodynamically preferred crystal form of salmeterol xinafoate. 1064 nm dispersive Raman microspectroscopy is a promising technique that could see diverse applications for samples where fluorescence-free characterization is required with high spatial resolution

Perthes' disease of the hip: socioeconomic inequalities and the urban environment.

INTRODUCTION: Perthes' disease is a puzzling childhood hip disorder for which the aetiology is unknown. It is known to be associated with socioeconomic deprivation. Urban environments have also been implicated as a risk factor, however socioeconomic deprivation often occurs within urban environments and it is unclear if this association is the result of confounding. The objective of the current work was to gain a greater understanding of the influence of the urban/rural environment in Perthes' disease. METHODS: This was a descriptive observational study using the Scottish Morbidity Record, based in Scotland, UK using data from 2000-2010. A total of 443 patients with a discharge diagnosis of Perthes' disease were included. Socioeconomic deprivation was determined using the Scottish Index of Multiple Deprivation, and exposure to the 'urban environment' was recorded based on the Scottish Urban-Rural Classification. RESULTS: There was a strong association with socioeconomic deprivation, with rates among the most deprived quintile more than twice those of the most affluent (RR 2.1 (95% CI 1.5 to 2.9)). Urban areas had a greater rate of Perthes' disease discharges (RR 1.8 (95% CI 1.1 to 3.2)), though this was a reflection of greater deprivation in urban areas. Stratification for socioeconomic deprivation revealed similar discharge rates in urban and rural environments, suggesting that the aetiological determinants were not independently associated with urban environments. CONCLUSIONS: The occurrence of Perthes' disease within urban environments is high, yet this appears to be a reflection of higher socioeconomic deprivation exposure. Disease rates appear equivalent in similarly deprived urban and non-urban areas, suggesting that the determinant is not a consequence of the urban environment

Enhanced Cellular Immunity in Shrimp (Litopenaeus vannamei) after ‘Vaccination’

It has long been viewed that invertebrates rely exclusively upon a wide variety of innate mechanisms for protection from disease and parasite invasion and lack any specific acquired immune mechanisms comparable to those of vertebrates. Recent findings, however, suggest certain invertebrates may be able to mount some form of specific immunity, termed ‘specific immune priming’, although the mechanism of this is not fully understood (see Textbox S1). In our initial experiments, either formalin-inactivated Vibrio harveyi or sterile saline were injected into the main body cavity (haemocoel) of juvenile shrimp (Litopenaeus vannamei). Haemocytes (blood cells) from V. harveyi-injected shrimp were collected 7 days later and incubated with a 1∶1 mix of V. harveyi and an unrelated Gram positive bacterium, Bacillus subtilis. Haemocytes from ‘vaccinated’ shrimp showed elevated levels of phagocytosis of V. harveyi, but not B. subtilis, compared with those from saline-injected (non-immunised) animals. The increased phagocytic activity was characterised by a significant increase in the percentage of phagocytic cells. When shrimp were injected with B. subtilis rather than vibrio, there was no significant increase in the phagocytic activity of haemocytes from these animals in comparison to the non-immunised (saline injected) controls. Whole haemolymph (blood) from either ‘immunised’ or non-immunised’ shrimp was shown to display innate humoral antibacterial activity against V. harveyi that was absent against B. subtilis. However, there was no difference in the potency of antibacterial activity between V. harveyi-injected shrimp and control (saline injected) animals showing that ‘vaccination’ has no effect on this component of the shrimp's immune system. These results imply that the cellular immune system of shrimp, particularly phagocytosis, is capable of a degree of specificity and shows the phenomenon of ‘immune priming’ reported by other workers. However, in agreement with other studies, this phenomenon is not universal to all potential pathogens

Glial cells are functionally impaired in juvenile neuronal ceroid lipofuscinosis and detrimental to neurons.

The neuronal ceroid lipofuscinoses (NCLs or Batten disease) are a group of inherited, fatal neurodegenerative disorders of childhood. In these disorders, glial (microglial and astrocyte) activation typically occurs early in disease progression and predicts where neuron loss subsequently occurs. We have found that in the most common juvenile form of NCL (CLN3 disease or JNCL) this glial response is less pronounced in both mouse models and human autopsy material, with the morphological transformation of both astrocytes and microglia severely attenuated or delayed. To investigate their properties, we isolated glia and neurons from Cln3-deficient mice and studied their basic biology in culture. Upon stimulation, both Cln3-deficient astrocytes and microglia also showed an attenuated ability to transform morphologically, and an altered protein secretion profile. These defects were more pronounced in astrocytes, including the reduced secretion of a range of neuroprotective factors, mitogens, chemokines and cytokines, in addition to impaired calcium signalling and glutamate clearance. Cln3-deficient neurons also displayed an abnormal organization of their neurites. Most importantly, using a co-culture system, Cln3-deficient astrocytes and microglia had a negative impact on the survival and morphology of both Cln3-deficient and wildtype neurons, but these effects were largely reversed by growing mutant neurons with healthy glia. These data provide evidence that CLN3 disease astrocytes are functionally compromised. Together with microglia, they may play an active role in neuron loss in this disorder and can be considered as potential targets for therapeutic interventions

Stereoselective assembly of gigantic chiral molybdenum blue wheels using lanthanide ions and amino acids

The synthesis of chiral polyoxometalates (POMs) is a challenge because of the difficulty to induce the formation of intrinsically chiral metal-oxo frameworks. Herein we report the stereoselective synthesis of a series of gigantic chiral Mo Blue (MB) POM clusters 1–5 that are formed by exploiting the synergy between coordinating lanthanides ions as symmetry breakers to produce MBs with chiral frameworks decorated with amino acids ligands; these promote the selective formation of enantiopure MBs. All the compounds share the same framework archetype, based on {Mo124Ce4}, which forms an intrinsically chiral Δ or Λ configurations, controlled by the configurations of functionalized chiral amino acids. The chirality and stability of 1–5 in solution are confirmed by circular dichroism, 1H NMR, and electrospray ion mobility–mass spectrometry studies. In addition, the framework of the {Mo124Ce4} MB not only behaves as a host able to trap a chiral {Mo8} cluster that is not accessible by traditional synthesis but also promotes the transformation of tryptophan to kynurenine in situ. This work demonstrates the potential and applicability of our synthetic strategy to produce gigantic chiral POM clusters capable of host–guest chemistry and selective synthetic transformations