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Exfoliated black phosphorus (bP) embedded into a polymer is preserved from oxidation, is stable to air, light, and humidity, and can be further processed into devices without degrading its properties. Most of the examples of exfoliated bP/polymer composites involve a single polymer matrix. Herein, we report the preparation of biphasic polystyrene/poly(methyl methacrylate) (50/50 wt.%) composites containing few-layer black phosphorus (fl-bP) (0.6-1 wt.%) produced by sonicated-assisted liquid-phase exfoliation. Micro-Raman spectroscopy confirmed the integrity of fl-bP, while scanning electron microscopy evidenced the influence of fl-bP into the coalescence of polymeric phases. Furthermore, the topography of thin films analyzed by atomic force microscopy confirmed the effect of fl-bP into the PS dewetting, and the selective PS etching of thin films revealed the presence of fl-bP flakes. Finally, a block copolymer/fl-bP composite (1.2 wt.%) was prepared via in situ reversible addition-fragmentation chain transfer (RAFT) polymerization by sonication-assisted exfoliation of bP into styrene. For this sample, 31 P solid-state NMR and Raman spectroscopy confirmed an excellent preservation of bP structure.

The chemical functionalization of 2D exfoliated black phosphorus (2D BP) continues to attract great interest, although a satisfactory structural characterization of the functionalized material has seldom been achieved. Herein, we provide the first complete structural characterization of 2D BP functionalized with rare discrete Pd 2 units, obtained through a mild decomposition of the organometallic dimeric precursor [Pd(η 3 -C 3 H 5 )Cl] 2 . A multitechnique approach, including HAADF-STEM, solid-state NMR, XPS, and XAS, was used to study in detail the morphology of the palladated nanosheets (Pd 2 /BP) and to unravel the coordination of Pd 2 units to phosphorus atoms of 2D BP. In particular, XAS, backed up by DFT modeling, revealed the existence of unprecedented interlayer Pd-Pd units, sandwiched between stacked BP layers. The preliminary application of Pd 2 /BP as a catalyst for the hydrogen evolution reaction (HER) in acidic medium highlighted an activity increase due to the presence of Pd 2 units.

Legionnaires' disease (LD) is a severe pneumonia caused by bacteria belonging to the genus Legionella . This is a major public health concern and infections are steadily increasing worldwide. Several sources of infection have been identified, but they have not always been linked to human isolates by molecular match. The well-known Legionella contamination of private homes has rarely been associated with the acquisition of the disease, although some patients never left their homes during the incubation period. This study demonstrated by genomic matching between clinical and environmental Legionella isolates that the source of an LD cluster was a private building. Monoclonal antibodies and sequence-based typing were used to type the isolates, and the results clearly demonstrated the molecular relationship between the strains highlighting the risk of contracting LD at home. To contain this risk, the new European directive on the quality of water intended for human consumption has introduced for the first time Legionella as a microbiological parameter to be investigated in domestic water systems. This should lead to a greater attention to prevention and control measures for domestic Legionella contamination and, consequently, to a possible reduction in community acquired LD cases.

In September 2018 in Brescia province, northern Italy, an outbreak of Legionnaires' disease (LD) caused by Legionella pneumophila serogroup 2 ( Lp2 ) occurred. The 33 cases (two fatal) resided in seven municipalities along the Chiese river. All cases were negative by urinary antigen test (UAT) and most were diagnosed by real-time PCR and serology. In only three cases, respiratory sample cultures were positive, and Lp2 was identified and typed as sequence type (ST)1455. In another three cases, nested sequence-based typing was directly applied to respiratory samples, which provided allelic profiles highly similar to ST1455. An environmental investigation was undertaken immediately and water samples were collected from private homes, municipal water systems, cooling towers and the river. Overall, 533 environmental water samples were analysed and 34 were positive for Lp . Of these, only three samples, all collected from the Chiese river, were Lp2 ST1455. If and how the river water could have been aerosolised causing the LD cases remains unexplained. This outbreak, the first to our knowledge caused by Lp2 , highlights the limits of UAT for LD diagnosis, underlining the importance of adopting multiple tests to ensure that serogroups other than serogroup 1, as well as other Legionella species, are identified.

Bidimensional (2D) materials are nowadays being developed as outstanding candidates for electronic and optoelectronic components and devices. Targeted applications include sensing, energy conversion, and storage. Phosphorene is one of the most promising systems in this context, but its high reactivity under atmospheric conditions and its small-area/lab-scale deposition techniques have hampered the introduction of this material in real-world applications so far. However, phosphorene oxides in the form of low-dimensional structures (2D PO x ) should behave as an electroresponsive material according to recent theoretical studies. In the present work, we introduce electrospraying for the deposition of stoichiometric and large-area 2D PO x nanoflakes starting from a suspension of liquid-phase-exfoliated phosphorene. We obtained 2D PO x nanostructures with a mean surface area two orders of magnitude larger than phosphorene structures obtained with standard mechanical and liquid exfoliation techniques. X-ray spectroscopy and high-resolution electron microscopy confirmed the P 2 O 5 -like crystallographic structure of the electrosprayed flakes. Finally, we experimentally demonstrated for the first time the electromechanical responsivity of the 2D P 2 O 5 nanoflakes, through piezoresponse force microscopy (PFM). This work sheds light on the possible implementation of phosphorus oxide-based 2D nanomaterials in the value chain of fabrication and engineering of devices, which might be easily scaled up for energy-harvesting/conversion applications., Competing Interests: The authors declare no competing financial interest., (© 2021 American Chemical Society.)

Nowadays, prostate cancer is the most widespread tumour in worldwide male population. Actually, brachytherapy is the most advanced radiotherapy strategy for the local treatment of prostate cancer. It consists in the placing of radioactive sources closed to the tumour side thus killing cancer cells. However, brachytherapy causes the same adverse effects of external-beam radiotherapy. Therefore, alternative treatment approaches are required for enhancing radiotherapy effectiveness and reducing toxic symptoms. Nanostructured exfoliated black phosphorus (2D BP) may represent a strategic tool for local cancer therapy because of its capability to induce singlet oxygen production and act as photosensitizer. Hence, we investigated 2D BP in vitro effect on healthy and cancer prostate cell behavior. 2D BP was obtained through liquid exfoliation. 2D BP effect on healthy and cancer prostate cell behaviors was analyzed by investigating cell viability, oxidative stress and inflammatory marker expression. 2D BP inhibited prostate cancer cell survival, meanwhile promoted healthy prostate cell survival in vitro by modulating oxidative stress and immune response with and without near-infrared light (NIR)-irradiation. Nanostructured 2D BP is able to inhibit in vitro prostate cancer cells survival and preserve healthy prostate cell vitality through the control of oxidative stress and immune response, respectively.

Enhanced laboratory-based surveillance of invasive meningococcal disease (IMD) in Italy was only assessed indirectly by numerically comparing surveillance data cases with hospital discharge records (HDR). In this study, we evaluated the completeness, timeliness and sensitivity of the IMD surveillance in Italy from 2015 to 2018. Completeness and timeliness were described at the national and subnational level. A capture-recapture analysis was conducted to evaluate the sensitivity and positive predictive value (PPV) using HDR as the external source with a combination of deterministic and probabilistic approaches. The characteristics of the unmatched vs. matched cases were compared using multivariable Poisson modeling. Overall, the completeness of data improved, except for specific variables. Timeliness of notifications also improved to a median of 4 days from onset to reporting. For the years 2015-2017, the sensitivity of the surveillance was estimated at 71.4% and the PPV at 77.5%, changing to 80.6% and 66.9% respectively after removing cases with a secondary meningitis diagnosis. We noted substantial sub-national differences. In 2018 sensitivity was 66.5% (135/203) and the PPV was 79.4% (135/170). The adjusted relative risk of being unmatched in 2015-2017 was higher in cases that were ≥60 years, had missing information or symptom onset in December. The IMD surveillance system overall performs well with completeness and timeliness improving in time. Specific challenges identified for individual variables should guide further improvement. Notwithstanding limitations posed by the comparison database, sensitivity and PPV are promising. The study highlights that promoting etiological ascertainment in people ≥60 years and addressing sub-national challenges are the main current challenges to address., Competing Interests: No conflict of interest is declared.

In July 2018, a large outbreak of Legionnaires' disease (LD) caused by Legionella pneumophila serogroup 1 (Lp1) occurred in Bresso, Italy. Fifty-two cases were diagnosed, including five deaths. We performed an epidemiological investigation and prepared a map of the places cases visited during the incubation period. All sites identified as potential sources were investigated and sampled. Association between heavy rainfall and LD cases was evaluated in a case-crossover study. We also performed a case-control study and an aerosol dispersion investigation model. Lp1 was isolated from 22 of 598 analysed water samples; four clinical isolates were typed using monoclonal antibodies and sequence-based typing. Four Lp1 human strains were ST23, of which two were Philadelphia and two were France-Allentown subgroup. Lp1 ST23 France-Allentown was isolated only from a public fountain. In the case-crossover study, extreme precipitation 5-6 days before symptom onset was associated with increased LD risk. The aerosol dispersion model showed that the fountain matched the case distribution best. The case-control study demonstrated a significant eightfold increase in risk for cases residing near the public fountain. The three studies and the matching of clinical and environmental Lp1 strains identified the fountain as the source responsible for the epidemic.

Since its discovery, the environmental instability of exfoliated black phosphorus (2D bP) has emerged as a challenge that hampers its wide application in chemistry, physics, and materials science. Many studies have been carried out to overcome this drawback. Here we show a relevant enhancement of ambient stability in few-layer bP decorated with nickel nanoparticles as compared to pristine bP. In detail, the behavior of the Ni-functionalized material exposed to ambient conditions in the dark is accurately studied by Transmission Electron Microscopy (TEM), Raman Spectroscopy, and high resolution x-ray Photoemission and Absorption Spectroscopy. These techniques provide a morphological and quantitative insight of the oxidation process taking place at the surface of the bP flakes. In the presence of Ni nanoparticles (NPs), the decay time of 2D bP to phosphorus oxides is more than three time slower compared to pristine bP, demonstrating an improved structural stability within 20 months of observation.

In 2017, a chikungunya outbreak in central Italy later evolved into a secondary cluster in southern Italy, providing evidence of disease emergence in new areas. Officials have taken action to raise awareness among clinicians and the general population, increase timely case detection, reduce mosquito breeding sites, and promote mosquito bite prevention.

Mechanically exfoliated two-dimensional (2D) black phosphorus (bP) is epitaxially terminated by monolayers and multilayers of tetracosane, a linear alkane, to form a weakly interacting van der Waals heterostructure. Atomic force microscopy (AFM) and computational modelling show that epitaxial domains of alkane chains are ordered in parallel lamellae along the principal crystalline axis of bP, and this order is extended over a few layers above the interface. Epitaxial alkane multilayers delay the oxidation of 2D bP in air by 18 hours, in comparison to 1 hour for bare 2D bP, and act as an electrical insulator, as demonstrated using electrostatic force microscopy. The presented heterostructure is a technologically relevant insulator-semiconductor model system that can open the way to the use of 2D bP in micro- and nanoelectronic, optoelectronic and photonic applications.

This work aims at characterizing for the first time the 31 P spin interactions determining the nuclear magnetic resonance (NMR) properties of solid black phosphorus (bP) and of its few-layer exfoliated form (fl-bP). Indeed, the knowledge of these properties is still very poor, despite the great interest received by this layered phosphorus allotrope and its exfoliated 2D form, phosphorene. By combining density functional theory (DFT) calculations and solid-state NMR experiments on suspensions of fl-bP nanoflakes and on solid bP, it has been possible to characterize the 31 P homonuclear dipolar and chemical shift interactions, identifying the network of 31 P nuclei more strongly dipolarly coupled and highlighting two kinds of magnetically nonequivalent 31 P nuclei. These results add an important missing piece of information to the fundamental chemico-physical knowledge of bP and support future extensive applications of NMR spectroscopy to the characterization of phosphorene-based materials.

Over the last three years an unprecedented flow of migrants arrived in Europe. There is evidence that vaccine preventable diseases have caused outbreaks in migrant holding centres. These outbreaks can be favored by a combination of factors including low immunization coverage, bad conditions that migrants face during their exhausting journey and overcrowding within holding facilities. In 2017, we conducted an online survey in Croatia, Greece, Italy, Malta, Portugal and Slovenia to explore the national immunization strategies targeting irregular migrants, refugees and asylum seekers. All countries stated that a national regulation supporting vaccination offer to migrants is available. Croatia, Italy, Portugal and Slovenia offer to migrant children and adolescents all vaccinations included in the National Immunization Plan; Greece and Malta offer only certain vaccinations, including those against diphtheria-tetanus-pertussis, poliomyelitis and measles-mumps-rubella. Croatia, Italy, Malta and Portugal also extend the vaccination offer to adults. All countries deliver vaccinations in holding centres and/or community health services, no one delivers vaccinations at entry site. Operating procedures that guarantee the migrants' access to vaccination at the community level are available only in Portugal. Data on administered vaccines is available at the national level in four countries: individual data in Malta and Croatia, aggregated data in Greece and Portugal. Data on vaccination uptake among migrants is available at national level only in Malta. Concluding, although diversified, strategies for migrant vaccination are in place in all the surveyed countries and generally in line with WHO and ECDC indications. Development of procedures to keep track of migrants' immunization data across countries, development of strategies to facilitate and monitor migrants' access to vaccinations at the community level and collection of data on vaccination uptake among migrants should be promoted to meet existing gaps., (Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The burgeoning interest in two-dimensional (2D) black phosphorus (bP) contributes to the expansion of its applications in numerous fields. In the present study, 2D bP is used as a support for homogeneously dispersed palladium nanoparticles directly grown on it by a wet chemical process. Electron energy loss spectroscopy-scanning transmission electron microscopy analysis evidences a strong interaction between palladium and P atoms of the bP nanosheets. A quantitative evaluation of this interaction comes from the X-ray absorption spectroscopy measurements that show a very short Pd-P distance of 2.26 Å, proving for the first time the existence of an unprecedented Pd-P coordination bond of a covalent nature. Additionally, the average Pd-P coordination number of about 1.7 reveals that bP acts as a polydentate phosphine ligand toward the surface of the Pd atoms of the nanoparticles, thus preventing their agglomeration and inferring with structural stability. These unique properties result in a superior performance in the catalytic hydrogenation of chloronitroarenes to chloroanilines, where a higher chemoselectivity in comparison to other heterogeneous catalyst based on palladium has been observed., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

We studied the chemical-physical nature of interactions involved in the formation of adducts of two-dimensional black phosphorus (2D BP) with organoboron derivatives of a conjugated fluorescent molecule (pyrene). Time-resolved fluorescence spectroscopy showed a stabilization effect of 2D BP on all derivatives, in particular for the adducts endowed with the boronic functionalities. Also, a stronger modulation of the fluorescence decay with oxygen was registered for one of the adducts compared to the corresponding organoboron derivative alone. Nuclear magnetic resonance experiments in suspension and density functional theory simulations confirmed that only noncovalent interactions were involved in the formation of the adducts. The energetic gain in their formation arises from the interaction of P atoms with both C atoms of the pyrene core and the B atom of the boronic functionalities, with a stronger contribution from the ester with respect to the acid one. The interaction results in the lowering of the band gap of 2D BP by around 0.10 eV. Furthermore, we demonstrated through Raman spectroscopy an increased stability toward oxidation in air of 2D BP in the adducts in the solid state (more than 6 months). The modification of the electronic structure at the interface between 2D BP and a conjugated organic molecule through noncovalent stabilizing interactions mediated by the B atom is particularly appealing in view of creating heterojunctions for optoelectronic, photonic, and chemical sensing applications.

The reactivity of ruthenium and manganese complexes bearing intact white phosphorus in the coordination sphere was investigated towards the low-valent transition-metal species [Cp'''Co] (Cp'''=η 5 -C 5 H 2 -1,2,4-tBu 3 ) and [L 0 M] (L 0 =CH[CHN(2,6-Me 2 C 6 H 3 )] 2 ; M=Fe, Co). Remarkably, and irrespective of the metal species, the reaction proceeds by the selective cleavage of two P-P edges and the formation of a square-planar cyclo-P 4 ligand. The reaction products [{CpRu(PPh 3 ) 2 }{CoCp'''}(μ,η 1:4 -P 4 )][CF 3 SO 3 ] (5), [{Cp BIG Mn(CO) 2 } 2 {CoCp'''}(μ,η 1:1:4 -P 4 )] (6) and [{Cp BIG Mn(CO) 2 } 2 {ML 0 }(μ,η 1:1:4 -P 4 )] (Cp BIG =C 5 (C 6 H 4 nBu) 5 ; L 0 =CH[CHN(2,6-Me 2 C 6 H 3 )] 2 ; M=Fe (7 a), Co (7 b)), respectively, were fully characterized by single-crystal X-ray diffraction and spectroscopic methods. The electronic structure of the cyclo-P 4 ligand in the complexes 5-7 is best described as a π-delocalized P 4 2- system, which is further stabilized by two and three metal moieties, respectively. DFT calculations envisaged a potential intermediate in the reaction to form 5, in which a quasi-butterfly-shaped P 4 moiety bridges the two metals and behaves as an η 3 -coordinated ligand towards the cobalt center., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Phosphorene, the 2D material derived from black phosphorus, has recently attracted a lot of interest for its properties, suitable for applications in materials science. The physical features and the prominent chemical reactivity on its surface render this nanolayered substrate particularly promising for electrical and optoelectronic applications. In addition, being a new potential ligand for metals, it opens the way for a new role of the inorganic chemistry in the 2D world, with special reference to the field of catalysis. The aim of this review is to summarize the state of the art in this subject and to present our most recent results in the preparation, functionalization, and use of phosphorene and its decorated derivatives. We discuss several key points, which are currently under investigation: the synthesis, the characterization by theoretical calculations, the high pressure behavior of black phosphorus, as well as its decoration with nanoparticles and encapsulation in polymers. Finally, device fabrication and electrical transport measurements are overviewed on the basis of recent literature and the new results collected in our laboratories.

The transition metal mediated functionalization of P4 is an approach to develop a more sustainable production of organophosphorus compounds. In this paper a ruthenium complex is presented, in which the P4 unit can be selectively converted into new P4R2 molecules in a two-step synthesis. The unsaturated 16 electron species [RuX(Cp*)(PCy3)] (Cp* = C5Me5, X = Cl, Br) reacts with a half equivalent of P4 affording a bimetallic complex bearing a planar P4X2 moiety as a ligand. The latter eliminates chloride anions under reduction with magnesium. In this process the butadiene-like P4Cl2 ligand is converted into two weakly bound P2 units which bridge the ruthenium centers. In the presence of n-BuLi, the P4Cl2 unit can be selectively alkylated, yielding the planar organophosphorus ligand P4nBu2. A detailed analysis of the electronic properties and solid state structures of the compounds combined with DFT calculations and AIM analyses demonstrate that the P4 unit in all complexes acts as an electronically highly flexible, non-innocent ligand.

Nowadays chemotherapy is the main treatment for osteosarcoma disease, even if limited by the lack of selectivity between healthy and cancer cells during the inhibition of cell division. Herein, we propose the use of few-layer two-dimensional black phosphorous (2D bP) as an alternative tool for osteosarcoma treatment and report how 2D bP can stimulate newly forming bone tissue generation after osteosarcoma resection. In our study, we have developed an in vitro model to evaluate the efficacy of 2D bP material with and without near-infrared light irradiation treatment, and we have demonstrated that the presence of 2D bP without treatment inhibits the metabolic activity of osteosarcoma cells (SAOS-2) while inducing both the proliferation and the osteogenic differentiation of human preosteoblast cells (HOb) and mesenchymal stem cells. Furthermore, we also propose an in vitro coculture model (SAOS-2 and HOb cell lines) in order to study the effect of 2D bP on inflammatory response related to cancer. On this coculture model, 2D bP may increase anti-inflammatory cytokine generation (i.e., interleukin-10) and inhibit proinflammatory mediators synthesis (i.e., interleukin-6), thus suggesting the opportunity to prevent cancer-related inflammation. Finally, we have demonstrated that 2D bP represents a promising candidate for future regenerative medicine and anticancer applications.

Routine immunization of infants with conjugate vaccines against Haemophilus influenzae type b (Hib) has greatly reduced the incidence of invasive Hib disease; however changes in the epidemiology of H. influenzae disease have occurred. We describe the epidemiology of invasive H. influenzae disease and the characterization of isolates collected in Italy between 2012 and 2016. Trends in the overall incidence of invasive H. influenzae disease were calculated. Isolates were characterized by PCR capsular genotyping, antimicrobial susceptibility testing, ampicillin resistance-associated gene sequencing and MLST. Trends in incidence by serotype and serotype-specific distribution were estimated using multiple imputation of missing data. The overall incidence of invasive H. influenzae disease increased 22.5% yearly (from 0.11/100,000 in 2012 to 0.24/100,000 in 2016). Most cases (82.0%) were due to non-typeable H. influenzae (NTHi). An increasing trend in NTHi disease burden was estimated; the highest rise was among infants <12 months (40.8% annual increase). Invasive Hib disease showed a fluctuating trend with a clear increase in 2016, while we found an increasing trend for disease due to non-Hib capsulated serotypes in the elderly (32.9% annual increase). Ampicillin resistance mediated by either β-lactamase or altered penicillin-binding proteins 3 (PBP3) increased. In spite of genetic diversity of NTHi, sequence types (STs) associated with ampicillin resistance status were identified (ST103/ST106 linked to β-lactamase production and ST14 linked to a specific PBP3 substitution pattern). The increasing trend in invasive NTHi disease in infants is of concern underlying the need for the development of a future vaccine against NTHi., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Objective: To describe the trend of invasive pneumococcal disease in the years 2008-2014; to verify the impact of the conjugate vaccine and monitor the occurrence of serotype replacement., Design: Prospective observational study based on data from the national surveillance for invasive bacterial diseases coordinated by the Istituto superiore di sanità., Setting and Participants: Seven Italian regions (A.P. Bolzano, A.P. Trento, Emilia-Romagna, Friuli-Venezia Giulia, Lombardia, Piemonte, Veneto), accounting for 43% of the national population., Main Outcome Measures: Number of cases and incidence of invasive pneumococcal diseases: global, stratified by age groups and by serotypes included or not in the PCV13., Results: In 2008-2014, in the 0-4 age group IPD incidence for all serotypes decreased from 7.1 to 2.9/100,000; incidence for vaccine serotypes (VT) decreased from 5.5 to 1.1/100,000, while incidence for non-vaccine serotypes (NVT) increased from 1.6 to 2.0/100,000 (2.5 in 2013). In the >64 age group, IPD incidence increased from 5.3 to 7.5/100,000; VT incidence decreased from 3.9 to 3.2 (4.9 in 2010 and 4.3 in 2013), whereas NVT incidence increased from 1.4 to 4.4/100,000., Conclusion: Use of the conjugate vaccine has reduced the number of cases of IPD by VT in children; the increase in IPD by NVT, above all in older age groups, suggests a serotype replacement.

Molecular typing methods for discriminating different bacterial isolates are essential epidemiological tools in prevention and control of Legionella infections and outbreaks. A selection of 56 out of 184 Legionella pneumophila serogroup 1 (Lp1) clinical isolates, collected from different Italian regions between 1987 and 2012, and stored at the National Reference Laboratory for Legionella, were typed by monoclonal antibody (MAb) subgrouping, amplified fragment length polymorphism (AFLP) and sequence based typing (SBT). These strains were isolated from 39 community (69.6%), 14 nosocomial (25%) and 3 travel associated (5.4%) Legionnaires'disease cases. MAb typing results showed a prevalence of MAb 3/1 positive isolates (75%) with the Philadelphia subgroup representing 35.7%, followed by Knoxville (23.2%), Benidorm (12.5%), Allentown/France (1.8%), Allentown/France-Philadelphia (1.8%). The remaining 25% were MAb 3/1 negative, namely 11 Olda (19.6%), 2 Oxford (3.6%) and 1 Bellingham (1.8%) subgroups. AFLP analysis detected 20 different genomic profiles. SBT analysis revealed 32 different sequence types (STs) with high diversity of STs (IODSTs=0.952) 12 of which were never described before. ST1 and ST23 were most frequently isolated as observed worldwide. A helpful analysis of data from SBT, MAb subgrouping and AFLP is provided, as well as a comparison to the Lp1 types investigated from other countries. This study describes the first Italian Lp1 strains database, providing molecular epidemiology data useful for future epidemiological investigations, especially of travel associated Legionnaires' diseases (TALD) cases, Italy being the country associated with the highest number of clusters., (Copyright © 2014 Elsevier GmbH. All rights reserved.)

The terminal rhenium(I) phosphaethynolate complex [Re(PCO)(CO)(2)(triphos)] has been prepared in a salt metathesis reaction from Na(OCP) and [Re(OTf)(CO)(2)(triphos)]. The analogous isocyanato complex [Re(NCO)(CO)(2)(triphos)] has been likewise prepared for comparison. The structure of both complexes was elucidated by X-ray diffraction studies. While the isocyanato complex is linear, the phosphaethynolate complex is strongly bent around the pnictogen center. Computations including natural bond orbital (NBO) theory, natural resonance theory (NRT), and natural population analysis (NPA) indicate that the isocyanato complex can be viewed as a classic Werner-type complex, that is, with an electrostatic interaction between the Re(I) and the NCO group. The phosphaethynolate complex [Re(P=C=O)(CO)(2)(triphos)] is best described as a metallaphosphaketene with a Re(I)-phosphorus bond of highly covalent character., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The dynamic behavior in solution of eight mono-hapto tetraphosphorus transition metal-complexes, trans-[Ru(dppm)(2)(H)(η(1)-P(4))]BF(4) ([1]BF(4)), trans-[Ru(dppe)(2)(H)(η(1)-P(4))]BF(4) ([2]BF(4)), [CpRu(PPh(3))(2)(η(1)-P(4))]PF(6) ([3]PF(6)), [CpOs(PPh(3))(2)(η(1)-P(4))]PF(6) ([4]PF(6)), [Cp*Ru(PPh(3))(2)(η(1)-P(4))]PF(6) ([5]PF(6)), [Cp*Ru(dppe)(η(1)-P(4))]PF(6) ([6]PF(6)), [Cp*Fe(dppe)(η(1)-P(4))]PF(6) ([7]PF(6)), [(triphos)Re(CO)(2)(η(1)-P(4))]OTf ([8]OTf), and of three bimetallic Ru(μ,η(1:2)-P(4))Pt species [{Ru(dppm)(2)(H)}(μ,η(1:2)-P(4)){Pt(PPh(3))(2)}]BF(4) ([1-Pt]BF(4)), [{Ru(dppe)(2)(H)}(μ,η(1:2)-P(4)){Pt(PPh(3))(2)}]BF(4) ([2-Pt]BF(4)), [{CpRu(PPh(3))(2))}(μ,η(1:2)-P(4)){Pt(PPh(3))(2)}]BF(4) ([3-Pt]BF(4)), [dppm=bis(diphenylphosphanyl)methane; dppe=1,2-bis(diphenylphosphanyl)ethane; triphos=1,1,1-tris(diphenylphosphanylmethyl)ethane; Cp=η(5)-C(5)H(5); Cp*=η(5)-C(5)Me(5) ] was studied by variable-temperature (VT) NMR and (31)P{(1)H} exchange spectroscopy (EXSY). For most of the mononuclear species, NMR spectroscopy allowed to ascertain that the metal-coordinated P(4) molecule experiences a dynamic process consisting, apart from the free rotation about the M-P(4) axis, in a tumbling movement of the P(4) cage while remaining chemically coordinated to the central metal. EXSY and VT (31)P NMR experiments showed that also the binuclear complex cations [1-Pt](+)-[3-Pt](+) are subjected to molecular motions featured by the shift of each metal from one P to an adjacent one of the P(4) moiety. The relative mobility of the metal fragments (Ru vs. Pt) was found to depend on the co-ligands of the binuclear complexes. For complexes [2]BF(4) and [3]PF(6), MAS, (31)P NMR experiments revealed that the dynamic processes observed in solution (i.e., rotation and tumbling) may take place also in the solid state. The activation parameters for the dynamic processes of complexes 1(+), 2(+), 3(+), 4(+), 6(+), 8(+) in solution, as well as the X-ray structures of 2(+), 3(+), 5(+), 6(+) are also reported. The data collected suggest that metal-coordinated P(4) should not be considered as a static ligand in solution and in the solid state., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The introduction of Haemophilus influenzae type b (Hib) conjugate vaccines has greatly reduced the incidence of invasive Hib disease. However, concern exists about the possible emergence of "strain replacement". We report the epidemiology and characterization of isolates from invasive H. influenzae disease in Italy through 2007-2009, 10 years after Hib vaccination was introduced. Invasive H. influenzae disease cases were detected through the National Surveillance of Invasive Bacterial Disease. Seventy-eight H. influenzae strains were serotyped and tested for antimicrobial susceptibility. Genetic basis of resistance to β-lactams was investigated. The annual incidence of invasive H. influenzae infection was 0.06/100,000 in 2007, 0.08/100,000 in 2008 and 0.09/100,000 in 2009 in all age groups. A slight increase in disease incidence has been observed in adults ≥65 years since 2007. Nonencapsulated (ncHi) predominated among H. influenzae isolates from all age groups: 61.5%, 76.0%, and 75.0% for <5, 5-64 and ≥65 years, respectively. Although ncHi mainly caused bacteremia, meningitis due to ncHi increased in comparison with previous data (38.6% in 2007-2009 vs. 26.2% 1997-2002). Prevalence of encapsulated non-Hib strains grew significantly (4.1% in 1997-2002 vs.16.7% in 2007-2009; p<0.001), although they remained rare. Resistance to ampicillin mediated by β-lactamase declined, but that due to altered penicillin-binding protein 3 increased. In conclusion, routine use of Hib vaccines produced both a drastic decrease in the number of invasive H. influenzae cases and epidemiological changes in disease. Overall, pediatric H. influenzae disease has become less common whereas there has been a slight increase of disease in the elderly. A marked change in the predominant serotype from Hib to ncHi has occurred. Changes in the H. influenzae population moderately affected antibiotic resistance trends., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

To assess in Italy the pre-pandemic susceptibility of the general population to the 2009 A/H1N1v influenza virus, 587 serum samples collected in 2004 were analyzed using haemagglutination-inhibition (HI), single-radial-haemolysis (SRH) and microneutralisation (MN) assays. Serum samples were stratified by age group, gender, and geographic area. Overall, using HI assay, the proportion of subjects showing antibodies cross-reacting with 2009 A/H1N1v virus at seroprotection level (>or=1:40) was estimated to be 6.7%, 12.4%, and 22.4% in individuals born between 2004 and 1949, 1948 and 1939, 1938 and 1909, respectively. With a HI antibody titre of >or=1:10, in the same birth cohort, the seroprotection levels were 13.5%, 19.2%, and 58.2%, respectively. The results suggest that the Italian population was not fully naïf to the current pandemic virus and that the possible previous exposure and immune response increases with age., ((c) 2010 Elsevier Ltd. All rights reserved.)

The comparison of the very similar compounds (Ph(3)P)(2)Pt(mu-S)(2)Pt(PPh(3))(2) (1) and (Ph(2)PyP)(2)Pt(mu-S)(2)Pt(PPh(2)Py)(2) (2) raises intriguing questions about the reliability of the reported Pt(2)S(2) core in 1, where the Pt-S bonds are the shortest ever reported. Also, the trans-annular S...S separation of 2.69 A is surprisingly shorter in 1 than in 2 (3.01 A), but no incipient coupling between two S(2-) bridges seems reasonable in this case. Various considerations lead to reformulate 1 as [(Ph(3)P)(2)Pt(mu-OH)(2)Pt(PPh(3))(2)](BF(4))(2), 3. The sets of cell parameters for 1 and 3 are not equal but two axes match, and the volume of 1 is exactly double. Simple matrices may be constructed to interconvert the direct and reciprocal crystalline cells, thus corroborating their identity of the compounds. It is concluded that, in the structure solution of 1, some atoms were either neglected (BF(4)(-) counterions) or ill identified (sulfido in place of hydroxo bridges), while the structure of 3 was solved by collecting only one-half of the possible reflections (hence, also the different space groups). A new preparation, crystallization and X-ray structure of 3 confirms the above points and dismisses any other theoretical conjecture about two electronically different Pt(2)S(2) cores in 1 and 2.

A series of cationic palladium complexes of general formula [Pd(Me)(MeCN)(N-N)][PF(6)] (N-N = (phen) 1 a, 4,7-dichloro-1,10-phenanthroline (4,7-Cl(2)-phen) 2 a, 4,7-diphenyl-1,10-phenanthroline (4,7-Ph(2)-phen) 3 a, 4-methyl-1,10-phenanthroline (4-Me-phen) 4 a, 4,7-dimethyl-1,10-phenanthroline (4,7-Me(2)-phen) 5 a, 5,5,6,6-tetrafluoro-5,6-dihydro-1,10-phenanthroline (F(4)-phen) 6 a, containing different substituted phenanthroline ligands, have been prepared from the corresponding neutral chloro derivatives [Pd(Me)(Cl)(N-N)], (1 b-6 b). The X-ray crystal structure of [Pd(Cl)(2)(4,7-Cl(2)-phen)] (2 b') was determined. DFT calculations show that the electron density on the metal is tuned by the substituents on the ligands. The catalytic behavior of complexes 1 a-6 a in the CO/styrene and CO/p-Me-styrene copolymerizations was studied in detail, showing that the generated catalysts are active for at least 90 h, yielding copolymers of high molecular weight. A firm correlation between the electron density on palladium on the one hand and the catalytic activity of the complexes and the molecular weight and the stereochemistry of the polyketones synthesized on the other hand has been established: the catalyst containing the F(4)-phen is thus far the most active among those tested, yielding the syndiotactic CO/styrene copolymer with a stereoregularity of 96 % (uu triad) and with an M(w) value of 1 000 000.

In Italy, 35 clusters of travel associated Legionnaires' disease were identified from July 2002, when the European Guidelines for Control and Prevention of Travel Associated Legionnaires' Disease have been adopted by the EWGLINET network, to October 2003. Eight per cent (28.6%) would not have been identified without the network. The clusters detected were small, ranging from 2 cases to a maximum of 6. All clusters involved 5 camping sites and 30 hotels/residences, and an overall of 87 patients. The diagnosis was confirmed in 92.0% of the cases and mainly performed by urinary antigen detection (84.7%). A clinical isolate was available only in one case. Following environmental investigations, samples were collected for all the 35 clusters from the water system, and Legionella pneumophila was found in 23 occasions (65.7%). In 15 resorts out of 35, investigations were already in progress at the time of EWGLI cluster notification, since in Italy full environmental investigation is performed even after notification of a single case. Control measures were implemented in all accommodation sites at risk and one hotel only was closed. In all the 35 clusters, reports were completed and sent on time, highlighting that it is possible to comply with the procedures requested by the European Guidelines.

The availability of new polysaccharide-protein conjugate vaccines against Neisseria meningitidis serogroup C prompted European National Health authorities to carefully monitor isolate characteristics. In Italy, during 1999-2001, the average incidence was 0.4 cases per 100,000 inhabitants. Serogroup B was predominant and accounted for 75% of the isolates, followed by serogroup C with 24%. Serogroup C was isolated almost twice as frequently in cases of septicemia than in cases of meningitis, and the most common phenotypes were C:2a:P1.5 and C:2b:P1.5. Among serogroup B meningococci, the trend of predominant phenotypes has changed from year to year, with a recent increase in the frequency of B:15:P1.4. Only a few meningococci had decreased susceptibility to penicillin, and, in the penA gene, all of these strains had exogenous DNA blocks deriving from the DNA of commensal Neisseria flavescens, Neisseria cinerea, and Neisseria perflava/sicca. Fluorescent amplified fragment-length polymorphism analysis revealed the nonclonal nature of the strains with decreased susceptibility to penicillin.