Global spatial risk assessment of sharks under the footprint of fisheries.

Effective ocean management and the conservation of highly migratory species depend on resolving the overlap between animal movements and distributions, and fishing effort. However, this information is lacking at a global scale. Here we show, using a big-data approach that combines satellite-tracked movements of pelagic sharks and global fishing fleets, that 24% of the mean monthly space used by sharks falls under the footprint of pelagic longline fisheries. Space-use hotspots of commercially valuable sharks and of internationally protected species had the highest overlap with longlines (up to 76% and 64%, respectively), and were also associated with significant increases in fishing effort. We conclude that pelagic sharks have limited spatial refuge from current levels of fishing effort in marine areas beyond national jurisdictions (the high seas). Our results demonstrate an urgent need for conservation and management measures at high-seas hotspots of shark space use, and highlight the potential of simultaneous satellite surveillance of megafauna and fishers as a tool for near-real-time, dynamic management.

GluN2B on adult-born granule cells modulates (R,S)-ketamine's rapid-acting effects in mice.

BACKGROUND: Standard antidepressant treatments often take weeks to reach efficacy and are ineffective for many patients. (R,S)-ketamine, an N-methyl-D-aspartate (NMDA) antagonist, has been shown to be a rapid-acting antidepressant and to decrease depressive symptoms within hours of administration. While previous studies have shown the importance of the GluN2B subunit of the NMDA receptor (NMDAR) on interneurons in the medial prefrontal cortex (mPFC), no study has investigated the influence of GluN2B-expressing adult-born granule cells (abGCs). METHODS: Here, we examined whether (R,S)-ketamine's efficacy depends upon these adult-born hippocampal neurons using a genetic strategy to selectively ablate the GluN2B subunit of the NMDAR from Nestin+ cells in male and female mice, tested across an array of standard behavioral assays. RESULTS: We report that in male mice, GluN2B expression on 6-week-old adult-born neurons is necessary for (R,S)-ketamine's effects on behavioral despair in the forced swim test (FST) and on hyponeophagia in the novelty suppressed feeding (NSF) paradigm, as well on fear behavior following contextual fear conditioning (CFC). In female mice, GluN2B expression is necessary for effects on hyponeophagia in the NSF. These effects were not replicated when ablating GluN2B from 2-week-old adult-born neurons. We also find that ablating neurogenesis increases fear expression in CFC, which is buffered by (R,S)-ketamine administration. CONCLUSIONS: In line with previous studies, these results suggest that 6-week-old adult-born hippocampal neurons expressing GluN2B partially modulate (R,S)-ketamine's rapid-acting effects. Future work targeting these 6-week-old adult-born neurons may prove beneficial for increasing the efficacy of (R,S)-ketamine.

Make It or Break It? Injury Impacts More Than Half of Deselected Athletes Who Dropped Out of the High-Performance Pathway System. A 4-Year Retrospective Cohort Study.

To investigate: (1) the injury epidemiology in an Australian academy; (2) how athletes transition through the high-performance sport (HPS) pathway; and (3) why athletes leave this HPS program. This retrospective cohort study was conducted at an Australian HPS academy over a 4-year period. Medical attention injuries were prospectively recorded. Injury incidence rates (IIR) and burden were calculated per 365 athlete-days, according to sport, sex, and pathway level. Athlete pathway levels were mapped to the Foundations, Talent, Elite, and Mastery (FTEM) framework. Reasons for athletes transitioning out were reported. Four hundred and eighty-one injuries were reported across 124 athletes at an IIR of 2.09 injuries per 365 athlete-days (95% CI = 1.91-2.29). Most athletes (103, 83.1%) were injured at least once over the 4-year period. IIRs increased (IRR = 1.17, 95% CI = 1.06-1.29, p = 0.001) as athletes progressed through the pathway. The most common reason for athlete attrition was deselection due to performance (n = 18), with 55.6% of these athletes sustaining an injury in the season prior to deselection. Injury burden was highest at E2 (119.5 days absence per 365 athlete-days (95% CI = 62.18-229.67)) and lowest at T4 (30.47 days absence per 365 athlete-days (95% CI = 21.98-42.24)). Injury occurrence is common across HPS, with IIRs increasing as athletes progressed to higher talent levels. Deselection due to poor performance was the main attrition factor, with more than half the deselected athletes impacted by injury prior to deselection. This study highlights an increased risk of deselection, following injury, and indicates the need for further development of prevention strategies targeting pathway athletes.

Injury incidence and prevalence in elite short-course triathletes: a 4-year prospective study.

OBJECTIVE: To characterise the prevalence, incidence rate (IR) and burden of injuries in elite short-course triathletes over a 4-year training and competition period. METHODS: Fifty elite Australian triathletes were prospectively monitored for injury during four consecutive seasons (2018-2021). Injuries requiring medical attention were prospectively recorded and further subcategorised according to time loss. The IR and burden (injury IR×mean injury severity) were calculated per 365 athlete days, with sex differences in IR compared using IR ratios (IRR) from negative binomial regression models. RESULTS: Two hundred and sixty-six injuries were reported in 46 (92.0%) athletes, of which 67.3% resulted in time loss. The injury IR was 1.87 injuries per 365 athlete days (95% CI 1.70 to 2.80), and comparable between sexes (IRR 0.82, 95% CI 0.64 to 1.04, p=0.109). Most injuries (70.7%) were training related. The most frequently injured body sites were the ankle (15.8%), foot (12.4%) and lower leg (12.0%). Bone stress injuries (BSIs) were the most burdensome injury type with 31.38 days of time loss per 365 days (95% CI 24.42 to 38.34). Twenty athletes (40.0%) reported at least one bone stress injury (BSI) (range 0-3). The rate of BSIs in female athletes was three times greater compared with male athletes (IRR 2.99, 95% CI 1.26 to 7.07, p=0.013). CONCLUSION: Two-thirds of injuries reported in elite short-course triathletes resulted in time loss, with the majority occurring during training activities. Foot, ankle and other lower leg injuries had the highest incidence, with BSIs carrying the highest injury burden. The considerably higher rate of BSI observed in female athletes warrants consideration for future prevention strategies in female triathletes.

Scaling of Activity Space in Marine Organisms across Latitudinal Gradients.

AbstractUnifying models have shown that the amount of space used by animals (e.g., activity space, home range) scales allometrically with body mass for terrestrial taxa; however, such relationships are far less clear for marine species. We compiled movement data from 1,596 individuals across 79 taxa collected using a continental passive acoustic telemetry network of acoustic receivers to assess allometric scaling of activity space. We found that ectothermic marine taxa do exhibit allometric scaling for activity space, with an overall scaling exponent of 0.64. However, body mass alone explained only 35% of the variation, with the remaining variation best explained by trophic position for teleosts and latitude for sharks, rays, and marine reptiles. Taxon-specific allometric relationships highlighted weaker scaling exponents among teleost fish species (0.07) than sharks (0.96), rays (0.55), and marine reptiles (0.57). The allometric scaling relationship and scaling exponents for the marine taxonomic groups examined were lower than those reported from studies that had collated both marine and terrestrial species data derived using various tracking methods. We propose that these disparities arise because previous work integrated summarized data across many studies that used differing methods for collecting and quantifying activity space, introducing considerable uncertainty into slope estimates. Our findings highlight the benefit of using large-scale, coordinated animal biotelemetry networks to address cross-taxa evolutionary and ecological questions.

Ventral hippocampal projections to infralimbic cortex and basolateral amygdala are differentially activated by contextual fear and extinction recall.

Fear and extinction learning are thought to generate distinct and competing memory representations in the hippocampus. How these memory representations modulate the expression of appropriate behavioral responses remains unclear. To investigate this question, we used cholera toxin B subunit to retrolabel ventral hippocampal (vHPC) neurons projecting to the infralimbic cortex (IL) and basolateral amygdala (BLA) and then quantified c-Fos immediate early gene activity within these populations following expression of either contextual fear recall or contextual fear extinction recall. Fear recall was associated with increased c-Fos expression in vHPC projections to the BLA, whereas extinction recall was associated with increased activity in vHPC projections to IL. A control experiment was performed to confirm that the apparent shift in projection neuron activity was associated with extinction learning rather than mere context exposure. Overall, results indicate that hippocampal contextual fear and extinction memory representations differentially activate vHPC projections to IL and BLA. These findings suggest that hippocampal memory representations orchestrate appropriate behavioral responses through selective activation of projection pathways.

Epidemiology of time-loss injuries within an Australian male professional football club: A 5-year prospective observational study of 21,343 player hours.

This study aimed to establish injury incidence rates (IIRs) and burden within an Australian male professional football club (n = 73) and to investigate longitudinal trends across five consecutive seasons (2016/17-2020/21). There was an overall IIR of 9.18 injuries per 1000 hours (h) (95% CI [7.89, 10.47]). The IIR was approximately seven times greater (rate ratio (RR): 6.85; 95% CI [5.13, 9.19]; p < 0.01) in matches (31.29 injuries per 1000 h; 95% CI [25.25, 37.33]) compared to training (4.49 injuries per 1000 h; 95% CI [3.51, 5.47]). The overall injury burden was 254.1 days lost per 1000 h (95% CI [220.9, 292.3]). Compared with the reference 2016/17 season, there were significant increases in minimal (RR: 6.94; 95% CI [1.27, 128.73]) and mild injuries (RR: 3.76; 95% CI [1.21, 16.39]) in season 2017/18 and decreases in moderate (RR: 0.40; 95% CI [0.19, 0.80]) and contact injuries (RR: 0.35; 95% CI [0.12, 0.90]) in season 2019/2020. Time-loss injury is common and represents a major burden in Australian male professional football, with injuries more frequently sustained during matches. Injury prevention practices should specifically be directed towards muscle/tendon and ligament injuries of the lower limb, particularly anterior cruciate ligament, ankle sprain and hamstring strain injuries.

Strategic Substitution of -OH/-NR2 (R=Et, Me) Imparts Colorimetric Switching between F- and Hg2+ by Salicyaldehyde/Benzaldehyde-Quinoxaline Conjugates.

We herein report two salicyaldehyde-quinoxaline (HQS and HQSN) conjugates and a benzaldehyde-quinoxaline (QBN) conjugate to fabricate selective chemosensors for F- and Hg2+ in the micromolar range. This work demonstrates how sensing outcomes are affected by modulating proton acidity by introducing an electron donating group, -NEt2 , in the probe backbone. Interestingly, the un-substituted probe HQS can selectively detect F- , whereas HQSN and QBN are selective for Hg2+ . In order to gain insights into the mechanism of sensing, geometry optimizations have been carried out on QS(-1) , QS(-1) ⋅⋅⋅HF, QSN(-1) and QSN(-1) ⋅⋅⋅HF and the experimental data are validated in terms of free energy and pKa values. Detailed DFT and TD-DFT analyses provide ample support towards the mechanism of sensing of the analytes.

A family of amphiphilic dioxidovanadium(V) hydrazone complexes as potent carbonic anhydrase inhibitors along with anti-diabetic and cytotoxic activities.

A family of dioxidovanadium(V) complexes (1-4) of the type [Na(H2O)x]+[VVO2(HL1-4)]- (x = 4, 4.5 and 7) where HL2- represents the dianionic form of 2-hydroxybenzoylhydrazone of 2-hydroxyacetophenone (H2L1, complex 1), 2-hydroxy-5-methylacetophenone (H2L2, complex 2), 2-hydroxy-5-methoxyacetophenone (H2L3, complex 3) and 2-hydroxy-5-chloroacetophenone (H2L4, complex 4), have been synthesized and characterized by analytical and spectral methods. These complexes exhibited the potential abilities to suppress the erythrocytes carbonic anhydrase enzymatic activity in type 1 and type 2 diabetic patients (in vitro), promising antidiabetic activity against T2 diabetic mice (in vivo). They also exhibited significant cytotoxic activity against cervical cancer (SiHa) cells (in vitro) as the IC50 value of complexes 1, 2 and 4 is substantially lower than the value found for cisplatin while that of 3 is comparable and follow the order: 4 < 1 < 2 < 3 and can kill the cells by apoptosis via the generation of reactive oxygen species (ROS). The complexes are soluble both in water and octanol media and also non-toxic at working concentrations. The antidiabetic activity of these four complexes follows the order: 4 > 2 > 1 > 3 while both the carbonic anhydrase and cytotoxic activity follow the order: 4 > 1 > 2 > 3 suggesting that complex 4, containing electron withdrawing Cl atom is the most reactive while 3 with electron donating OCH3 group is the least reactive species. The molecular docking study on hCA-I and hCA-II demonstrates that complexes interact via hydrogen bonding as well as different types of π-stacking.

A Quinoxaline-Naphthaldehyde Conjugate for Colorimetric Determination of Copper Ion.

This work facilitates detection of bivalent copper ion by a simple Schiff base probe QNH based on a quinoxaline-naphthaldehyde framework. The detailed study in absorption spectroscopy and theoretical aspects and crystal study of the probe and probe-copper complex has been discussed. The detection limit of the probe in the presence of Cu2+ is 0.45 µM in HEPES-buffer/acetonitrile (3/7, v/v) medium for absorption study. The reversibility of the probe-copper complex has been investigated by EDTA. The selective visual detection of copper has been established also in gel form.

A Window of Vascular Plasticity Coupled to Behavioral Recovery after Stroke.

Stroke causes remodeling of vasculature surrounding the infarct, but whether and how vascular remodeling contributes to recovery are unclear. We established an approach to monitor and compare changes in vascular structure and blood flow with high spatiotemporal precision after photothrombotic infarcts in motor cortex using longitudinal 2-photon and multiexposure speckle imaging in mice of both sexes. A spatially graded pattern of vascular structural remodeling in peri-infarct cortex unfolded over the first 2 weeks after stroke, characterized by vessel loss and formation, and selective stabilization of a subset of new vessels. This vascular structural plasticity was coincident with transient activation of transcriptional programs relevant for vascular remodeling, reestablishment of peri-infarct blood flow, and large improvements in motor performance. Local vascular plasticity was strongly predictive of restoration of blood flow, which was in turn predictive of behavioral recovery. These findings reveal the spatiotemporal evolution of vascular remodeling after stroke and demonstrate that a window of heightened vascular plasticity is coupled to the reestablishment of blood flow and behavioral recovery. Our findings support that neovascularization contributes to behavioral recovery after stroke by restoring blood flow to peri-infarct regions. These findings may inform strategies for enhancing recovery from stroke and other types of brain injury.SIGNIFICANCE STATEMENT An improved understanding of neural repair could inform strategies for enhancing recovery from stroke and other types of brain injury. Stroke causes remodeling of vasculature surrounding the lesion, but whether and how the process of vascular remodeling contributes to recovery of behavioral function have been unclear. Here we used longitudinal in vivo imaging to track vascular structure and blood flow in residual peri-infarct cortex after ischemic stroke in mice. We found that stroke created a restricted period of heightened vascular plasticity that was associated with restoration of blood flow, which was in turn predictive of recovery of motor function. Therefore, our findings support that vascular remodeling facilitates behavioral recovery after stroke by restoring blood flow to peri-infarct cortex.

Ferrocene-Functionalized Dithiocarbamate Zinc(II) Complexes as Efficient Bifunctional Catalysts for the One-Pot Synthesis of Chromene and Imidazopyrimidine Derivatives via Knoevenagel Condensation Reaction.

Four new mononuclear/coordination polymeric (CP) zinc(II) complexes (1-4) of ferrocenyl/pyridyl-functionalized dithiocarbamate ligands, N-ferrocenylmethyl-N-butyl dithiocarbamate (L1), N-ferrocenylmethyl-N-ethylmorpholine dithiocarbamate (L2), N-ferrocenylmethyl-N-2-(diethylamino)ethylamine dithiocarbamate (L3), and N-4-methoxybenzyl-N-3-methylpyridyl dithiocarbamate (L4), have been synthesized and characterized by elemental analyses, IR, UV-vis, and 1H and 13C{1H} NMR spectroscopic techniques. The solid-state structures of complexes 1, 3, and 4 have been determined by single-crystal X-ray crystallography as well as powder X-ray diffraction. Single-crystal X-ray crystallography revealed a monomeric structure for complex 1 but 1D polymeric structures for complexes 3 and 4. In all complexes, dithiocarbamate ligands are bonded to the Zn(II) metal ion in a S^S chelating mode, and in the CPs, N atoms on the 2-(diethylamino)ethylamine and 3-pyridyl functionalities in the ligands on the neighboring molecules are also bonded to metal centers, leading to the formation of either a discrete tetrahedral molecule in 1 or 1D CP structures in 3 and 4. The Zn(II) metal centers in the polymeric structures exhibited either square-pyramidal or octahedral geometries. The supramolecular structures in these complexes are sustained via C-H···π (ZnCS2, chelate; 3 and 4), C-H···π, and H···H interactions. The catalytic performances of complexes have also been assessed in the Knoevenagel condensation and one-pot multicomponent reactions. Catalysis results showed that the CP 3 acts as a heterogeneous bifunctional catalyst with excellent transformation efficiency at low catalyst loading.

Impaired recovery is associated with increased injury and illness: A retrospective study of 536 female netball athletes.

Sport science and medicine practitioners are interested in the relationships between training load, injury, and illness. The extent to which training preparedness is associated with workload-related injury and illness risk is debated. Therefore, this study applied multi-level mixed effect logistic regression to investigate time-dependent (±7- and ±28-day) relationships between training preparedness (fatigue, mood, motivation, soreness, stress, sleep duration, and quality), training load, injury, and illness in 536 elite and pre-elite female netball athletes. Absolute risk (AR ± 95% CI) of sustaining an injury (0.98 ± 0.06%, n = 1122 injuries, N = 254 athletes) or illness (1.09 ± 0.10%, n = 2881, N = 432 athletes) was calculated. All training preparedness variables combined resulted in an absolute risk of 0.88%-5.88% and 0.87%-20% for injury and illness, respectively. Injury and illness had significant (P < .05) bidirectional (ie, both increased and decreased) associations with physical (soreness) and physiological (sleep duration and quality), while illness also had negative (mood, motivation) and positive (stress) associations with psychological training preparedness variables. Low sleep duration in the 48-h period prior was associated (P = .005) with increased injury risk (OR = 0.91 ± 0.03; AR = 4.00%), while "very poor" sleep quality (OR = 0.59 ± 0.02; AR = 7.83%) or extremes of too little (<5 hours, OR = 1.01 ± 0.03; AR = 3.13%-14.29%) and too much (>10 hours, OR = 1.01 ± 0.03; AR = 2.61%-10.98%) sleep had bidirectional associations (P < .001) with an increased illness risk. Changes in training preparedness variables demonstrated bidirectional associations with injury and illness. These outcomes suggest that sport science and medicine practitioners should monitor sleep, physical, and psychological recovery status, to aid early detection and intervention regarding injury and illness symptomology.

Prevalence of impaired physiological function consistent with Relative Energy Deficiency in Sport (RED-S): an Australian elite and pre-elite cohort.

OBJECTIVES: Athlete health, training continuity and performance can be impeded as a result of Relative Energy Deficiency in Sport (RED-S). Here we report the point prevalence of symptoms described by the RED-S model in a mixed-sport cohort of Australian female athletes. METHODS: Elite and pre-elite female athletes (n=112) from eight sports completed validated questionnaires and underwent clinical assessment to assess the point prevalence of RED-S symptoms. Questionnaires included the Depression, Anxiety and Stress Questionnaire (DASS-21), Generalized Anxiety Disorder (GAD-7), Center for Epidemiological Studies Depression Scale (CES-D), SCOFF questionnaire for disordered eating, Low Energy Availability in Females Questionnaire (LEAF-Q), and a custom questionnaire on injury and illness. Clinical assessment comprised resting metabolic rate (RMR) assessment, dual-energy X-ray absorptiometry-derived body composition and bone mineral density, venous and capillary blood samples, and the Mini International Neuropsychiatric Interview (MINI 7.0.2). Descriptive prevalence statistics are presented. RESULTS: Almost all (80%) participants (age 19 (range 15-32) years; mass 69.5±10.3 kg; body fat 23.1%±5.0%) demonstrated at least one symptom consistent with RED-S, with 37% exhibiting between two and three symptoms. One participant demonstrated five symptoms. Impaired function of the immunological (28%, n=27), haematological (31%, n=33) and gastrointestinal (47%, n=51) systems were most prevalent. A moderate to high (11%-55%) prevalence of risk of low energy availability was identified via RMR and LEAF-Q, and identified mental illnesses were prevalent in one-third of the assessed cohort. CONCLUSION: Symptoms described by the RED-S model were prevalent in this cohort, supporting the need for improved awareness, monitoring and management of these symptoms in this population.

The Utility of the Low Energy Availability in Females Questionnaire to Detect Markers Consistent With Low Energy Availability-Related Conditions in a Mixed-Sport Cohort.

The Low Energy Availability in Females Questionnaire (LEAF-Q) was validated to identify risk of the female athlete triad (triad) in female endurance athletes. This study explored the ability of the LEAF-Q to detect conditions related to low energy availability (LEA) in a mixed sport cohort of female athletes. Data included the LEAF-Q, SCOFF Questionnaire for disordered eating, dual-energy X-ray absorptiometry-derived body composition and bone mineral density, Mini International Neuropsychiatric Interview, blood pressure, and blood metabolic and reproductive hormones. Participants were grouped according to LEAF-Q score (≥8 or <8), and a comparison of means was undertaken. Sensitivity, specificity, and predictive values of the overall score and subscale scores were calculated in relation to the triad and biomarkers relevant to LEA. Fisher's exact test explored differences in prevalence of these conditions between groups. Seventy-five athletes (18-32 years) participated. Mean LEAF-Q score was 8.0 ± 4.2 (55% scored ≥8). Injury and menstrual function subscale scores identified low bone mineral density (100% sensitivity, 95% confidence interval [15.8%, 100%]) and menstrual dysfunction (80.0% sensitivity, 95% confidence interval [28.4%, 99.5%]), respectively. The gastrointestinal subscale did not detect surrogate markers of LEA. LEAF-Q score cannot be used to classify athletes as "high risk" of conditions related to LEA, nor can it be used as a surrogate diagnostic tool for LEA given the low specificity identified. Our study supports its use as a screening tool to rule out risk of LEA-related conditions or to create selective low-risk groups that do not need management as there were generally high negative predictive values (range 76.5-100%) for conditions related to LEA.

The Effect of Guest Metal Ions on the Reduction Potentials of Uranium(VI) Complexes: Experimental and Theoretical Investigations.

Two mononuclear uranyl complexes, [UO2 L1 ] (1) and [UO2 L2 ]⋅0.5 CH3 CN⋅0.25 CH3 OH (2), have been synthesized from two multidentate N3 O4 donor ligands, N,N'-bis(5-methoxysalicylidene)diethylenetriamine (H2 L1 ) and N,N'-bis(3-methoxysalicylidene)diethylenetriamine (H2 L2 ), respectively, and have been structurally characterized. Both complexes 1 and 2 showed a reversible UVI /UV couple at -1.571 and -1.519 V, respectively, in cyclic voltammetry. The reduction potential of the UVI /UV couple shifted towards more positive potential on addition of Li+ , Na+ , K+ , and Ag+ metal ions to acetonitrile solutions of complex 2, and the resulting potential was correlated with the Lewis acidity of the metal ions and was also justified by theoretical DFT calculations. No such shift in reduction potential was observed for complex 1. All four bimetallic products, [UO2 L2 Li0.5 ](ClO4 )0.5 (3), [UO2 L2 Na(ClO4 )]2 (4), [UO2 L2 Ag(NO3 )(H2 O)] (5), and [(UO2 L2 )2 K(H2 O)2 ]PF6 (6), formed on addition of the Li+ , Na+ , Ag+ , and K+ metal ions, respectively, to acetonitrile solutions of complex 2, were isolated in the solid state and structurally characterized by single-crystal X-ray diffraction. In all the species, the inner N3 O2 donor set of the ligand encompasses the equatorial plane of the uranyl ion and the outer open compartment with O2 O'2 donor sites hosts the second metal ion.

Key viral immune genes and pathways identify elite athletes with URS.

PURPOSE: Habitual intense exercise may increase the incidence of upper respiratory symptoms (URS) in elite athletes. This study investigated whether immune gene expression could identify gene markers that discriminate athletes with a higher prevalence of URS. METHODS: This cross-sectional analysis of elite Australian athletes from various sports investigated whether athletes retrospectively reporting URS for two days or more in a month (n=38), had an altered immune gene expression profile compared with asymptomatic athletes (n=33). Peripheral blood samples were collected during Olympic selection events with corresponding URS data collected for the one-month period before sampling. Digital immune gene expression analysis was undertaken using the NanoString PanCancer Immune Profiling panel. RESULTS: Fifty immune genes were differentially expressed between the groups (p<0.05) and approximately 78% of these genes were more highly expressed in athletes reporting URS. Many of these genes were interferon-stimulated genes or genes involved in the Jak/Stat signalling pathway. Only interferon alpha inducible protein 27 (IFI27), an interferon stimulated gene involved in viral response, remained significantly higher in athletes reporting URS (log2 fold-difference=2.49, odds ratio 1.02 per unit increase; p<0.01) post-adjustment and discriminated athletes reporting URS from asymptomatic athletes with 78% accuracy. CONCLUSIONS: Expression of IFI27 could differentiate athletes reporting URS from asymptomatic athletes, a gene that is upregulated in the immune response to viral infection. Upregulation of viral signalling pathways provides novel information on the potential aetiology of URS in elite Olympic athletes.

Versatile {Cp2Ti} Grafted Hetero-Polyoxotungstate Clusters: Synthesis, Crystal Structure, and Photocurrent Properties.

Polyoxotungstate supported titanocene {Cp2Ti}2+ clusters H6{K8(Cp2Ti)2P4W24O88(PO4)2}·14H2O (1), H6[Na2P4W14O58(Cp2Ti)2]·12H2O (2), and H2[K6{Cp2Ti}{PW9O33(WO2)}2{NC5H3(COOK)2}(NC5H3(CH3)COOK)·22H2O] (3) have been synthesized, and their single crystal X-ray structures have revealed unprecedented and intriguing structural features. The synthesized compounds have been characterized by various spectroscopic techniques including UV-vis, cyclic voltammogram, NMR, ESI-MS, and inductive coupled plasma spectroscopy (ICP) in solution and also by IR, TGA, and diffuse reflectance in the solid state. Clusters 1 and 2 are rare examples of lacunary POM supported titanocene clusters obtained by incorporating various phosphorus heteroatoms to form elusive phosphotungstate assemblies, whereas 3 is an unprecedented organometallic as well as heteroleptic pyridyl functionalized POM. Clusters 1-3 show transient photocurrent ON/OFF behavior upon UV-light irradiation and also exhibit characteristic TiIV/III intravalence electron transfer. This behavior is also established by their cyclic voltammograms in mixed phosphate buffers (Na2HPO4/NaH2PO4) which show the evidence of POM supported {Cp2Ti}2+/+ species in their redox solution. Furthermore, ESR line broadening is also observed in these clusters at room temperature, a fact which also confirms the formation of partially reduced/oxidized {Cp2Ti}2+/+ species leading to TiIV/III intravalence electron transfers within all three clusters. The {Cp2Ti}2+ decorated polyoxometalate cluster 3 shows improved transient photocurrent behavior which may be due to the presence of pyridyl carboxyl ions which provide better surface contact for the cluster molecule through the carboxylate moiety to the ITO electrode.