Unlocking same-sign CPL: solvent effects on spectral form and racemisation kinetics in nine-coordinate chiral europium(III) complexes.

Understanding the factors that shape the circularly polarised luminescence (CPL) emission profiles of europium(III)-based CPL emitters to have specific sign properties, e. g. monosignate individual CPL transitions, is key to design novel complexes for applications ranging from advanced security inks to bio-probes for live cell imaging. In order to correlate structure and spectral characteristics, a photophysical and kinetic investigation has been conducted on a series of coordinatively saturated nine-coordinate europium(III) systems based on 1,4,7-triazacyclononane. We highlight that lanthanide emission is sensitive to changes in the ligand field by showing the linear dependence of total emission intensity ratios as a function of solvent polarity, for europium(III) complexes displaying an internal charge transfer (ICT) excited state. This sensitivity increases by a factor of 20 when studying changes in CPL spectra, rendering these complexes accurate probes of local polarity. Solvent polarity, solvent-specific effects, and the nature of the chromophores' coordinating donor atoms strongly influence the kinetic stability of europium(III) complexes with respect to enantiomer interconversion. Notably, we show that the choice of donor groups to coordinating to europium(III) and the nature and polarity of the solvent affects the rate of racemisation, leading to systems with very long half-lives at room temperature in non-polar media.

Two-Photon Circularly Polarized Luminescence of Chiral Eu Complexes.

We report the synthesis of chiral lanthanide complexes with extended π conjugation for efficient circularly polarized luminescence (CPL) via two-photon excitation (2PE). The pyridine bis-oxazoline (PyBox) core provides the chiral Ln3+ environment, while the extension of the conjugated backbone through the pyridine 4-position with a phenylacetylene unit increases the two-photon absorption cross section. This work presents an important step toward the development of chiral systems displaying enhanced nonlinear optical properties, with potential applications in imaging and sensing, as well as in photodynamic therapy due to the selective excitation of molecules within a specific focal volume.

Insights on the best release strategy from post-release movements and mortality patterns in an avian scavenger.

Conservation translocations involving vultures rely either on soft- or hard-release strategies. To investigate whether these strategies affect home range stability and survival, we compared the spatial behavior and mortality of 38 Griffon vultures (Gyps fulvus) released in Sardinia. Griffons were released after no acclimatization or after 3 (short) or 15 (long acclimatization) months in an aviary. In the two years that followed their release, griffons without acclimatization did not stabilize their home range size, while those subjected to long acclimatization stabilized it in the second year. Short-acclimatized griffons always had a large home range, soon after their release. The number of individuals that reached sexual maturity was higher (71.4%) in long-acclimatized griffons than in short-acclimatized ones (40%) or in griffons that were hard released (28.6%). Soft release with a long acclimatization period seems to be the most successful method to ensure stable home ranges and the survival of griffon vultures.

Rapid handheld time-resolved circularly polarised luminescence photography camera for life and material sciences.

Circularly polarised luminescence (CPL) is gaining a rapidly increasing following and finding new applications in both life and material sciences. Spurred by recent instrumental advancements, the development of CPL active chiral emitters is going through a renaissance, especially the design and synthesis of CPL active luminescent lanthanide complexes owing to their unique and robust photophysical properties. They possess superior circularly polarised brightness (CPB) and can encode vital chiral molecular fingerprints in their long-lived emission spectrum. However, their application as embedded CPL emitters in intelligent security inks has not yet been fully exploited. This major bottleneck is purely hardware related: there is currently no suitable compact CPL instrumentation available, and handheld CPL photography remains an uncharted territory. Here we present a solution: an all solid-state small footprint CPL camera with no moving parts to facilitate ad hoc time-resolved enantioselective differential chiral contrast (EDCC) based one-shot CPL photography (CPLP).

Enhancing monitoring and transboundary collaboration for conserving migratory species under global change: The priority case of the red kite.

Calls for urgent action to conserve biodiversity under global change are increasing, and conservation of migratory species in this context poses special challenges. In the last two decades the Convention on the Conservation of Migratory Species of Wild Animals (CMS) has provided a framework for several subsidiary instruments including action plans for migratory bird species, but the effectiveness and transferability of these plans remain unclear. Such laws and policies have been credited with positive outcomes for the conservation of migratory species, but the lack of international coordination and on-ground implementation pose major challenges. While research on migratory populations has received growing attention, considerably less emphasis has been given to integrating ecological information throughout the annual cycle for examining strategies to conserve migratory species at multiple scales in the face of global change. We fill this gap through a case study examining the ecological status and conservation of a migratory raptor and facultative scavenger, the red kite (Milvus milvus), whose current breeding range is limited to Europe and is associated with agricultural landscapes and restricted to the temperate zone. Based on our review, conservation actions have been successful at recovering red kite populations within certain regions. Populations however remain depleted along the southern-most edge of the geographic range where many migratory red kites from northern strongholds overwinter. This led us to a forward-looking and integrated strategy that emphasizes international coordination involving researchers and conservation practitioners to enhance the science-policy-action interface. We identify and explore key issues for conserving the red kite under global change, including enhancing conservation actions within and outside protected areas, recovering depleted populations, accounting for climate change, and transboundary coordination in adaptive conservation and management actions. The integrated conservation strategy is sufficiently general such that it can be adapted to inform conservation of other highly mobile species subject to global change.

Versatile Para-Substituted Pyridine Lanthanide Coordination Complexes Allow Late Stage Tailoring of Complex Function.

A series of cationic and neutral p-Br and p-NO2 pyridine substituted Eu(III) and Gd(III) coordination complexes serve as versatile synthetic intermediates. Nucleophilic aromatic substitution occurs readily at the para position under mild conditions, allowing C-N and C-C bond forming reactions to take place, permitting the introduction of azide, amino and alkynyl substituents. For Eu(III) complexes, this approach allows late stage tuning of absorption and emission spectral properties, exemplified by the lowering of the energy of an LMCT transition accompanied by a reduction in the Eu-Npy bond length. Additionally, these complexes provide direct access to the corresponding Eu(II) analogues. With the Gd(III) series, the nature of the p-substituent does not significantly change the EPR properties (linewidth, relaxation times), as required for their development as EPR spin probes that can be readily conjugated to biomolecules under mild conditions.

Analysis of 11 trace elements in flight feathers of Italian Sparrows in southern Italy: A study of bioaccumulation through age classes, variability in three years of sampling, and relations with body condition.

Trace elements have been acknowledged as one of the subtlest environmental hazards in all compartments of the total environment. Enhanced by activities in the anthroposphere, they accumulate in the atmosphere, lithosphere, and hydrosphere. Eventually, trace elements can bioaccumulate or biomagnifiy in the biosphere, with harmful effects on animals occupying higher trophic levels, including humans. Accordingly, there is great interest in assessing and monitoring trace element concentrations in the biosphere, and birds, especially passerines, have been commonly chosen as biomonitors. In this study, the concentration of 11 trace elements was measured (i.e. aluminum, chromium, manganese, iron, nickel, copper, zinc, arsenic, cadmium, barium, and lead) in flight feathers of Italian Sparrows, a common bird species hitherto not analysed in this respect. Samples were collected in an agricultural area in southern Italy, where a mosaic of natural environments, urbanized areas and industrial facilities can be found. Linear mixed modelling was applied to the analysis of flight feathers in juveniles, juvenile birds moulting to adulthood, and adults in three sampling years on 184 birds. Results are timely as they add new data to the scarce available information on Ba and As in bird feathers and showed clear bioaccumulation patterns from juveniles to adults for As, Cr, and Cd. Moreover, the modelling approach showed that the concentration of elements such as As, Cd and Cr can be variable across the years and that some elements, notably Cd and Ba, were inversely correlated with body mass and wing length, respectively, suggesting potential negative effects on bird health. Finally, when modelling bird body condition and trace elements, results showed that Cd and Ba negatively affect birds regardless of age or sampling year. Thus, the Italian Sparrow could be considered as a valuable biomonitor for trace elements in the total environment, especially for Cd and Ba.

Laparoscopic hepatectomy for HCC in elderly patients: risks and feasibility.

BACKGROUND: Laparoscopic liver resection (LLR) appears to be safe and effective as open liver resection (OLR) for hepatocellular carcinoma (HCC). However, studies comparing LLR with ORL in elderly patients are limited. The purpose of this study is to compare the clinical outcomes of LLR versus OLR for HCC in elderly patients. METHODS: A retrospective analysis was made comparing laparoscopic (n = 11) and open (n = 18) liver resections in elderly patients performed at the University of Naples "Federico II" between January 2010 and December 2014. Demographic data, operative and postoperative outcomes were analyzed. RESULTS: Demographic and tumor characteristics of laparoscopic and OLRs were similar. There were also no significant differences in operating room time. Patients undergoing OLR had increased rate of minor complications (33 vs. 0%), longer lengths of stay (6 vs. 3 days) and higher blood loss (310 ± 84 vs. 198 ± 34 ml). There were no significant differences in major complication rates or 90-day mortality. DISCUSSION: LLR is safe and feasible as OLR for treatment of HCC in selected elderly patients.

Laparoscopic distal pancreatectomy in elderly patients: is it safe?

BACKGROUND: Laparoscopic distal pancreatectomy (LDP) appears to be safe and effective as open distal pancreatectomy (ODP) for benign or borderline malignant lesion. However, studies comparing LDP with ODP in elderly patients are limited. The purpose of this study is to compare the clinical outcomes of these two several approaches in elderly patients. METHODS: A retrospective analysis was carried out by comparing laparoscopic (n = 7) and open (n = 15) distal pancreatectomy in elderly patients performed at the University of Naples "Federico II" and University of Perugia between January 2012 and December 2015. Demographic data, operative and postoperative outcomes were analyzed. RESULTS: Demographic and tumor characteristics of laparoscopic and ODP were similar. There were also no significant differences in operating room time. Patients undergoing LDP had lower blood loss, first flatus time, diet start time and postoperative hospital stay. There were no significant differences in complication rates or 90-day mortality. DISCUSSION: LDP is safe and feasible as ODP in selected elderly patients.

Fast track for elderly patients: is it feasible for colorectal surgery?

BACKGROUND: Fast-track program has been applied in several surgical fields. However, currently many surgical patients are elderly over 70 years of age, and discussion about the application of such protocols for elderly patients is inadequate. MATERIALS AND METHODS: The present study was designed to consider the safety and feasibility of application of a fast-track program after colorectal surgery in elderly patients. A total of 76 elderly patients with colorectal cancer who underwent laparoscopic colorectal resection were randomly assigned to receive either the fast-track care program (n = 40) or the conventional perioperative care protocol (control group, n = 36). The fast track protocol included no preoperative mechanical bowel irrigation, immediate oral alimentation and earlier postoperative ambulation exercise. The length of postoperative hospital stay, the length of time to regain bowel function and the rate of postoperative complications were compared between the two groups. RESULTS: The length of time to regain bowel function, including the passage of flatus [32 (24-40) h vs 42 (32-52) h], and to start a liquid diet (13 [10-16] h v/s 43 [36-50] h) were significantly shorter in patients receiving the fast track care protocol compared with those receiving the conventional care protocol. A shorter duration of postoperative hospital stay was recorded in patients receiving the fast-track program than in those receiving conventional care [6 (5-7) days v/s 9.5 (7-12) days]. A reduced percentage of patients who developed general complications was also observed in the fast-track group (5.0% v/s 18%). CONCLUSION: Fast-track after laparoscopic colorectal surgery can be safely applied in carefully selected elderly patients older than age 70 years. The fast-track recovery program resulted in a more rapid postoperative recovery, earlier discharge from hospital and fewer general complications compared with a conventional postoperative protocol.

Kidney transplantation and large anastomotic pseudoaneurysm. Transplant management considerations.

AIM: Pseudoaneurysm (PA) at the anastomosis site in kidney transplantation is a rare but serious complication that usually requires graft nephrectomy. Literature reports are sporadic and usually focused on limb rather than graft salvage. In this paper we focus on this last point. MATERIAL OF STUDY: 6 patients presenting large PA at the anastomosis between iliac and graft artery were identified in our series. The diagnosis was performed with US, AngioTC scan and angiography. Blood cultures and labeled leukocyte scintigraphy were also performed. All patients underwent open surgery. RESULTS: Transplant nephrectomy was needed in all cases except one, in which it was possible to perform a graft replanting on hypogastric artery. Our perioperative mortality and morbidity rate was recorded. DISCUSSION: Etiology of PA is multifactorial, however an association with chronic rejection or infection must be also considered. Our mortality and morbidity rates are in accordance to literature. In our experience we observed only large PA so to require an open surgery but this approach has allowed the rescue of graft functioning just in a single case. Endovascular procedures are linked to higher rate of graft salvage than surgery but they can be used just in selected cases. CONCLUSIONS: Our experience and literature review led us to believe that the rate of graft salvage in patients with large PA at anastomosis site could be improved only by a planned therapeutic program that includes surgical and endovascular approach, taking the advantages of both technique and overcoming their limits.