Highly luminescent scintillating hetero-ligand MOF nanocrystals with engineered Stokes shift for photonic applications.

Large Stokes shift fast emitters show a negligible reabsorption of their luminescence, a feature highly desirable for several applications such as fluorescence imaging, solar-light managing, and fabricating sensitive scintillating detectors for medical imaging and high-rate high-energy physics experiments. Here we obtain high efficiency luminescence with significant Stokes shift by exploiting fluorescent conjugated acene building blocks arranged in nanocrystals. Two ligands of equal molecular length and connectivity, yet complementary electronic properties, are co-assembled by zirconium oxy-hydroxy clusters, generating crystalline hetero-ligand metal-organic framework (MOF) nanocrystals. The diffusion of singlet excitons within the MOF and the matching of ligands absorption and emission properties enables an ultrafast activation of the low energy emission in the 100 ps time scale. The hybrid nanocrystals show a fluorescence quantum efficiency of ~60% and a Stokes shift as large as 750 meV (~6000 cm-1), which suppresses the emission reabsorption also in bulk devices. The fabricated prototypal nanocomposite fast scintillator shows benchmark performances which compete with those of some inorganic and organic commercial systems.

Quasi-thresholdless Photon Upconversion in Metal-Organic Framework Nanocrystals.

Photon upconversion based on sensitized triplet-triplet annihilation ( sTTA) is considered as a promising strategy for the development of light-managing materials aimed to enhance the performance of solar devices by recovering unused low-energy photons. Here, we demonstrate that, thanks to the fast diffusion of excitons, the creation of triplet pairs in metal-organic framework nanocrystals ( nMOFs) with size smaller than the exciton diffusion length implies a 100% TTA yield regardless of the illumination condition. This makes each nMOF a thresholdless, single-unit annihilator. We develop a kinetic model for describing the upconversion dynamics in a nanocrystals ensemble, which allows us to define the threshold excitation intensity  Ithbox required to reach the maximum conversion yield. For materials based on thresholdless annihilators, Ithbox is determined by the statistical distribution of the excitation energy among nanocrystals. The model is validated by fabricating a nanocomposite material based on nMOFs, which shows efficient upconversion under a few percent of solar irradiance, matching the requirements of real life solar technologies. The statistical analysis reproduces the experimental findings, and represents a general tool for predicting the optimal compromise between dimensions and concentration of nMOFs with a given crystalline structure that minimizes the irradiance at which the system starts to fully operate.

Highly Fluorescent Metal-Organic-Framework Nanocomposites for Photonic Applications.

Metal-organic frameworks (MOFs) are porous hybrid materials built up from organic ligands coordinated to metal ions or clusters by means of self-assembly strategies. The peculiarity of these materials is the possibility, according to specific synthetic routes, to manipulate both the composition and ligands arrangement in order to control their optical and energy-transport properties. Therefore, optimized MOFs nanocrystals (nano-MOFs) can potentially represent the next generation of luminescent materials with features similar to those of their inorganic predecessors, that is, the colloidal semiconductor quantum dots. The luminescence of fluorescent nano-MOFs is generated through the radiative recombination of ligand molecular excitons. The uniqueness of these nanocrystals is the possibility to pack the ligand chromophores close enough to allow a fast exciton diffusion but sufficiently far from each other preventing the aggregation-induced effects of the organic crystals. In particular, the formation of strongly coupled dimers or excimers is avoided, thus preserving the optical features of the isolated molecule. However, nano-MOFs have a very small fluorescence quantum yield (QY). In order to overcome this limitation and achieve highly emitting systems, we analyzed the fluorescence process in blue emitting nano-MOFs and modeled the diffusion and quenching mechanism of photogenerated singlet excitons. Our results demonstrate that the excitons quenching in nano-MOFs is mainly due to the presence of surface-located, nonradiative recombination centers. In analogy with their inorganic counterparts, we found that the passivation of the nano-MOF surfaces is a straightforward method to enhance the emission efficiency. By embedding the nanocrystals in an inert polymeric host, we observed a +200% increment of the fluorescence QY, thus recovering the emission properties of the isolated ligand in solution.

Metal Nanoclusters with Synergistically Engineered Optical and Buffering Activity of Intracellular Reactive Oxygen Species by Compositional and Supramolecular Design.

Metal nanoclusters featuring tunable luminescence and high biocompatibility are receiving attention as fluorescent markers for cellular imaging. The recently discovered ability of gold clusters to scavenge cytotoxic reactive oxygen species (ROS) from the intracellular environment extends their applicability to biomedical theranostics and provides a novel platform for realizing multifunctional luminescent probes with engineered anti-cytotoxic activity for applications in bio-diagnostics and conceivably cellular therapy. This goal could be achieved by using clusters of strongly reactive metals such as silver, provided that strategies are found to enhance their luminescence while simultaneously enabling direct interaction between the metal atoms and the chemical surroundings. In this work, we demonstrate a synergic approach for realizing multifunctional metal clusters combining enhanced luminescence with strong and lasting ROS scavenging activity, based on the fabrication and in situ protection of Ag nanoclusters with a supramolecular mantle of thiolated-Au atoms (Ag/Au-t). Confocal imaging and viability measurements highlight the biocompatibility of Ag/Au-t and their suitability as fluorescent bio-markers. ROS concentration tests reveal the remarkable scavenging activity of Ag-based clusters. Proliferation tests of cells in artificially stressed culture conditions point out their prolonged anti-cytotoxic effect with respect to gold systems, ensuring positive cell proliferation rates even for long incubation time.

Achieving the photon up-conversion thermodynamic yield upper limit by sensitized triplet-triplet annihilation.

Triplet-triplet annihilation (TTA) based up-conversion is a promising strategy for light harvesting the low-energy tail of the solar spectrum with photovoltaic technologies. Here, we present a bi-component system for photon managing via TTA that allows bypassing the classical statistic limit of 2/5 in the singlet generation, achieving a near unitary conversion efficiency. This result is obtained because of the peculiar relative position of the triplet and singlet energy levels of perylene, used as up-converter and emitter. The system shows a record red-to-blue external up-conversion yield of ∼10% under an irradiance of 1 sun.

Broadband up-conversion at subsolar irradiance: triplet-triplet annihilation boosted by fluorescent semiconductor nanocrystals.

Conventional solar cells exhibit limited efficiencies in part due to their inability to absorb the entire solar spectrum. Sub-band-gap photons are typically lost but could be captured if a material that performs up-conversion, which shifts photon energies higher, is coupled to the device. Recently, molecular chromophores that undergo triplet-triplet annihilation (TTA) have shown promise for efficient up-conversion at low irradiance, suitable for some types of solar cells. However, the molecular systems that have shown the highest up-conversion efficiency to date are ill suited to broadband light harvesting, reducing their applicability. Here we overcome this limitation by combining an organic TTA system with highly fluorescent CdSe semiconductor nanocrystals. Because of their broadband absorption and spectrally narrow, size-tunable fluorescence, the nanocrystals absorb the radiation lost by the TTA chromophores, returning this energy to the up-converter. The resulting nanocrystal-boosted system shows a doubled light-harvesting ability, which allows a green-to-blue conversion efficiency of ∼12.5% under 0.5 suns of incoherent excitation. This record efficiency at subsolar irradiance demonstrates that boosting the TTA by light-emitting nanocrystals can potentially provide a general route for up-conversion for different photovoltaic and photocatalytic applications.

Effect of an external magnetic field on the up-conversion photoluminescence of organic films: the role of disorder in triplet-triplet annihilation.

We have investigated the influence of the magnetic field on the triplet-triplet annihilation process in organic films using a model multicomponent system for blue delayed up-conversion photoluminescence. In such a way, we have derived simple analytical expressions to estimate the overall annihilation probability, outlining the peculiar role played by the disorder and demonstrating that the triplet-triplet fusion in solid films is a diffusion limited process.

Growth of SnO(2) nanocrystals controlled by erbium doping in silica.

We investigate the effects of erbium doping on SnO(2) nanoclustering in Sn-doped silica. Vibrational spectroscopy data from Raman and infrared absorption measurements show nanostructuring effects on the SnO(2) nanophase. Ultraviolet absorption spectra evidence a gap shift ascribable to size-dependent quantum confinement, also suggesting a role of erbium doping in determining cluster sizes and the amount of localized states on the nanophase boundary. Transmission electron microscopy confirms and details the spectroscopic data. As a result of these measurements, we find that the nanocrystal size distribution becomes narrower, increasing the erbium concentration, while the density of localized states at the nanocrystal surface decreases. The distribution of erbium ions among the possible environments is then examined through simultaneous spectroscopy of luminescence excited by nanocrystal-to-erbium energy transfer and the absorption of nanocrystal luminescence by erbium ions. This analysis shows that erbium behaves as an extrinsic nucleation centre of the SnO(2) nanophase at low doping levels, whereas at high concentrations it modifies the matrix, hindering the growth of SnO(2) crystals and passivating the interface.

[Risks and benefits of influenza and pneumococcal immunization in HIV-1 infected individuals]. / Rischi e benefici delle vaccinazioni anti-influenzale ed anti-pneumococcica in individui HIV-1 positivi.

Influenza and Streptococcus pneumoniae diseases can cause severe complications in HIV-1 infected individuals leading to increases in hospital admission and even death. Both vaccinations are recommended for such individuals, but some studies reported that such immunizations may stimulate an increase of HIV-1 viral load and decrease of CD4+ cells count. A review of published studies, including our studies carried out in HIV-1 infected former drugs addicts, indicates that influenza and pneumococcal vaccinations are well tolerated in individuals with HIV-1, and do not induce deterioration of the course of HIV-1 infection, even though the immune response to vaccination is lower than that one observed in immunocompetent individuals. Therefore the lack of significant changes of virological and immunological parameters indicates that such immunizations can be safely administrated to HIV-1 infected individuals.

Self-starting mode locking of a cw Nd:YAG laser using cascaded second-order nonlinearities.

The nonlinear mode variations induced by the equivalent third-order susceptibility resulting from cascaded secondorder nonlinearities in an intracavity lithium triborate crystal are exploited for mode locking of a cw Nd:YAG laser. The loss modulations are provided by a slit, as in the Kerr-lens mode-locking scheme. The mode-locking process is self-starting and produces nearly transform-limited pulses of 14-ps duration with 0.5-W average power.

Placental teratoma with three-germ layer differentiation.

A rare case of placental teratoma is described. Major features were the presentation as a pedunculated mass from the fetal surface of the placenta, the mixture of different tissues derived from all three germ layers (skin with dermal appendages, ganglion-like cells, and nervous structures, gut structures, osteocartilagineous and smooth and striated muscle), and the absence of segmental organization.

[Clinical and statistical observations on closed chest injuries]. / Considerazioni clinco-statistiche sui traumi chiusi del torace.

The importance of AR for a prompt and upkeep therapy is underlined by the Authors on the base of a statistical and clinical study about 67 cases of thoracic trauma treated from January 1975 to November 1979. The different alteration of the chest wall and surrounding structures are taken into consideration. The possible association of thoracic trauma with head trauma, severe shock and bony traumatism are also considered from a statistical and from a clinical point of view. The various therapeutic measures in case of thoracic trauma are also mentioned.

[Complications of subarachnoid anesthesia]. / Complicazioni dell'anestesia subaracnoidea.

Complications and accidents in subarachnoid anaesthesia, their frequency, and methods for their prevention are described. Reference is also made to a personal series in which the low incidence of untoward consequence was probably attributable to the precautions described.

[The plaster cast syndrome 2 cases of intestinal gastric emphysema]. / Sindrome da corsetto gessato. Due casi di enfisema gastrico intestinale.

Two clinical cases of acute gastric dilatation (Cast syndrome) in wearers of surgical corsets for kyphoscoliosis are described. One patient died in spite of surgical treatment, whereas the other responded favourably to conservative management. Fifty cases from the literature are examined. The seriousness and rapid progression of the syndrome are clear from its persistently high mortality (22%). Treatment was conservative in 70% of cases: antishock therapy, nasogastric aspiration, removal of the cast, while duodenojejunostomy was performed in the other 30%. In the two cases described, the seriousness of gastric distress due to compression of the duodenum by the aorta and mesentery was furthered evident from the observation of interstitial gastric emphysema.