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Modulation of optical properties of lead-free defective perovskites can contribute to design optimized materials for several applications ranging from photodetection to photocatalysis. Here, we explored two novel alloying strategies on Cs3Sb2Br9, by preparing by mechanochemical synthesis Sb/Bi and Br/I mixed systems. An unexpected band gap bowing has been observed in alloyed Sb/Bi compositions, showing lower absorption edges with respect to pure compounds. Such behavior has been computationally modelled suggesting the presence of local aggregates as the source of such reduction of the band gap. Further modulation of the optical properties has been achieved by halide alloying showing a progressive red-shift by increasing the iodide content. In both cases a full solubility at the solid state has been determined by means of diffraction and Raman spectroscopy. Overall, this study proposes and rationalizes doping strategies in the Cs3Sb2Br9 defective perovskite achieved through the use of a sustainable synthetic procedure such as mechanochemistry.

Solvent-assisted ligand exchange in the zirconium metal-organic framework (MOF) UiO-67 [Zr6O4(OH)4(PhPh)6; H2PhPh = biphenyl-4,4?-dicarboxylic acid] with the heterocyclic linkers H2TpTp (2,2?-bithiophene-5,5?-dicarboxylic acid) and H2TzTz (2,2?-bithiazole-5,5?-dicarboxylic acid) in an equimolar [Zr6] : linker ratio led to the corresponding MIXMOFs UiO-67-TpTp [Zr6O4(OH)4(PhPh)5(TpTp)] and UiO-67-TzTz [Zr6O4(OH)4(PhPh)5(TzTz)]. Both MOFs have been thoroughly characterized in the solid state. They show the same structural topology and crystal structure of UiO-67, as confirmed by powder X-ray diffraction. Their BET specific surface area is lower than that of their parent material (1700 and 1310 m2 g-1 for UiO-67-TpTp and UiO-67-TzTz, respectively, vs. 1877 m2 g-1 for UiO-67), while the thermal stability of UiO-67 (Tdec = 819 K) is maintained. The "diluted"inclusion, in the UiO-67 3D framework, of luminescent heterocyclic linkers emitting in the blue-green visible region induces luminescence in the final MOFs (emission ?max = 442 and 420 nm for UiO-67-TpTp and UiO-67-TzTz, respectively), preventing self-quenching effects caused by the proximity of the emitters in the crystal structure. Both MOFs have been tested as sensors for contaminants of emerging concern (CECs) in water: an emission intensity increase has been observed when suspended in contact with diclofenac sodium, fluoxetine, ibuprofen and sulfamethoxazole. In particular, UiO-67-TzTz has shown a linearly increasing trend for a specific concentration range (up to 30-40 ?M for diclofenac, fluoxetine and ibuprofen; up to 100 ?M for sulfamethoxazole). UiO-67-TzTz also behaves as an adsorbent vs. diclofenac, with a maximum adsorption capacity (Xm) of 62.5 mg g-1. These findings pave the way to the practical utilization of UiO-67-TzTz as a multifunctional material (i.e. CECs luminescent sensor and adsorbent at one time) for environmental remediation. This journal is

Mercury is one of the most toxic heavy metals. By virtue of its triple bond, the novel ligand 1,2-bis(1H-pyrazol-4- yl)ethyne (H2BPE) was expressly designed and synthesized to devise metal−organic frameworks (MOFs) exhibiting high chemical affinity for mercury. Two MOFs, Zn(BPE) and Zn(BPE)·nDMF [interpenetrated i-Zn and noninterpenetrated ni-Zn·S, respectively; DMF = dimethylformamide], were isolated as microcrystalline powders. While i-Zn is stable in water for at least 15 days, its suspension in HgCl2 aqueous solutions prompts its conversion into HgCl2@ni-Zn. A multitechnique approach allowed us to shed light onto the observed HgCl2-triggered i-Zn-to- HgCl2@ni-Zn transformation at the molecular level. Density functional theory calculations on model systems suggested that HgCl2 interacts via the mercury atom with the carbon−carbon triple bond exclusively in ni-Zn. Powder X-ray diffraction enabled us to quantify the extent of the i-Zn-to-HgCl2@ni-Zn transition in 100−5000 ppm HgCl2 (aq) solutions, while X-ray fluorescence and inductively coupled plasma-mass spectrometry allowed us to demonstrate that HgCl2 is quantitatively sequestered from the aqueous phase. Irradiating at 365 nm, an intense fluorescence is observed at 470 nm for ni-Zn·S, which is partially quenched for i-Zn. This spectral benchmark was exploited to monitor in real time the i-Zn-to-HgCl2@ni-Zn conversion kinetics at different HgCl2 (aq) concentrations. A sizeable fluorescence increase was observed, within a 1 h time lapse, even at a concentration of 5 ppb. Overall, this comprehensive investigation unraveled an intriguing molecular mechanism, featuring the disaggregation of a water-stable MOF in the presence of HgCl2 and the self-assembly of a different crystalline phase around the pollutant, which is sequestered and simultaneously quantified by means of a luminescence change. Such a case study might open the way to new-conception strategies to achieve real-time sensing of mercury-containing pollutants in wastewaters and, eventually, pursue their straightforward and costeffective purification., University of Insubria for partial funding, Programa Juan de la Cierva Formación (FJC2020-045043-I), MCIN/AEI/10.13039/501100011033, European Union NextGenerationEU/PRTR (Grants PID2020- 113608RB-I00 and TED2021-129886B-C41)

This work focuses on the impact of covalent organic frameworks' (COFs) pore flexibility in the adsorption and separation of benzene and cyclohexane. With this aim, we have selected the imine-linked 3D COFs COF-300 and LZU-111 as examples of flexible and rigid frameworks, respectively. Optimized syntheses at room temperature or in solvothermal conditions enabled us to selectively isolate the narrow-pore form of COF-300 (COF-300-rt) or a mixture of the narrow-pore and a larger-pore form (COF-300-st), respectively, with different textural properties (BET specific surface area = 39 or 1270 m

Aiming at extending the tagged zinc bipyrazolate metal-organic frameworks (MOFs) family, the ligand 3,3'-diamino-4,4'-bipyrazole (3,3'-H2 L) has been synthesized in good yield. The reaction with zinc(II) acetate hydrate led to the related MOF Zn(3,3'-L). The compound is isostructural with its mono(amino) analogue Zn(BPZNH2 ) and with Zn(3,5-L), its isomeric parent built with 3,5-diamino-4,4'-bipyrazole. The textural analysis has unveiled its micro-/mesoporous nature, with a BET area of 463 m2 g-1 . Its CO2 adsorption capacity (17.4 wt. % CO2 at pCO2 = 1 bar and T = 298 K) and isosteric heat of adsorption (Qst = 24.8 kJ mol-1 ) are comparable to that of Zn(3,5-L). Both Zn(3,3'-L) and Zn(3,5-L) have been tested as heterogeneous catalysts in the reaction of CO2 with the epoxides epichlorohydrin and epibromohydrin to give the corresponding cyclic carbonates at T = 393 K and pCO2 = 5 bar under solvent- and co-catalyst-free conditions. In general, the conversions recorded are higher than those found for Zn(BPZNH2 ), proving that the insertion of an extra amino tag in the pores is beneficial for the epoxidation catalysis. The best catalytic match has been observed for the Zn(3,5-L)/epichlorohydrin couple, with 64 % conversion and a TOF of 5.3 mmol(carbonate) (mmolZn )-1 h-1 . To gain better insights on the MOF-epoxide interaction, the crystal structure of the [epibromohydrin@Zn(3,3'-L)] adduct has been solved, confirming the existence of Br⋅⋅⋅(H)-N non-bonding interactions. To our knowledge, this study represents the first structural determination of a [epibromohydrin@MOF] adduct.

Supraventricular tachyarrhythmia (SVT) is the most common type of arrhythmia in childhood. Management can be challenging with an associated risk of mortality. A female neonate was diagnosed with episodes of SVT, controlled antenatally with digoxin. Flecainide was commenced prophylactically at birth. Despite treatment, the infant developed a narrow complex tachycardia at 5 days of age. The electrocardiogram features were suggestive of either re-entry tachycardia or of automatic atrial tachycardia (AAT). Following several unsuccessful treatments, a wide complex tachycardia developed. A transesophageal electrophysiological study led to a diagnosis of AAT. Stable sinus rhythm was finally achieved through increasing daily administrations of flecainide up to six times a day, in association with nadolol. The shortening of intervals to this extent has never been reported before and supports the evidence of a personal, age-specific variability in pharmacokinetics of flecainide. Larger studies are needed to better define the appropriate dose and timing of administration.

The new ditopic ligand [2,2'-(1,4-phenylene)bithiazole]-5,5'-dicarboxylic acid (H2TzPhTz) was synthesized in ~70% yield through a classical Hantzsch synthesis. Isolation of the dimethyl ester intermediate Me2TzPhTz as the trifluoroacetic acid adduct Me2TzPhTz·2CF3CO2H allowed its crystal structure determination, revealing that the constituting molecules are interconnected through an extended hydrogen-bond network. Reaction of H2TzPhTz with suitable ZnII and UVI salts yielded the 1-D coordination polymers [Zn(TzPhTz)(H2O)2] (Zn_TzPhTz) and [UO2(TzPhTz)(DMF)]·DMF (U_TzPhTz). The former is characterized by zig-zag chains with cis-{Zn(OCOO)4(OH2O)2} nodes and ?-?2:?2-TzPhTz2- spacers, while in the latter TzPhTz-bridged {UO2(TzPhTz)(DMF)}2 dimeric units form polymeric strands. In the solid state, both H2TzPhTz and Zn_TzPhTz emit in the blue-green visible region (?em = 474 and 477 nm, respectively). The two coordination polymers witness the versatility of H2TzPhTz as a linker toward d and f metal ions, and they should be considered as the preliminary step toward the preparation of TzPhTz-based metal-organic frameworks for practical applications in the field of luminescence sensing.

Metal-Organic Frameworks (MOFs) are a class of nanoporous materials that in recent years have gained great attention for their widespread application in several fields of materials science (catalysis, luminescence, gas storage and separation). MOFs have an extraordinary versatility in their design achieved through a tailored combination of organic linkers and inorganic nodes. This characteristic gives to MOFs unique advantages, including control of their pore size, high specific surface areas and the possibility to include suitable functional groups on their linkers' skeleton. In this work, we describe the synthesis and full characterization of the bicyclic ditopic linker 2,2'-biselenophene-5,5'-dicarboxylic acid (H2SpSp) specifically designed for MOFs construction. Afterwards, the corresponding zirconium MOF [Zr6O4(OH)4(SpSp)3.8Cl4.4] (1) has been prepared and the crystallographic analysis has revealed that it is isostructural with its bitiophene and bithiazole analogues. Therefore, three new mixed-linker MOFs containing biselenophene (H2SpSp), bithiophene (H2ThTh) and bithiazole (H2TzTz) linkers have been synthesized, in detail the two double-mixed [Zr6O4(OH)4(SpSp)2.6(ThTh)1.3Cl4.2] (2) and [Zr6O4(OH)4(SpSp)2(TzTz)1.8Cl4.4] (3), as well as the triple-mixed [Zr6O4(OH)4(SpSp)1.6(ThTh)1.2(TzTz)1.4Cl3.6] (4). Compounds 1-4 have been tested for luminescent applications, emitting at wavelengths falling in the blue-green visible region under UV irradiation.

[EN] Three metal-organic frameworks with the general formula Co(BPZX) (BPZX(2-) = 3-X-4,4'-bipyrazolate, X = H, NH2, NO2) constructed with ligands having different functional groups on the same skeleton have been employed as heterogeneous catalysts for aerobic liquid-phase oxidation of cumene with O-2 as oxidant. O-2 adsorption isotherms collected at p(O2) = 1 atm and T = 195 and 273 K have cast light on the relative affinity of these catalysts for dioxygen. The highest gas uptake at 195 K is found for Co(BPZ) (3.2 mmol/g (10.1 wt % O-2)), in line with its highest BET specific surface area (926 m(2)/g) in comparison with those of Co(BPZNH(2)) (317 m(2)/g) and Co(BPZNO(2)) (645 m(2)/g). The O-2 isosteric heat of adsorption (Q(2)) trend follows the order Co(BPZ) > Co(BPZNH(2)) > Co(BPZNO(2)). Interestingly, the selectivity in the cumene oxidation products was found to be dependent on the tag present in the catalyst linker: while cumene hydroperoxide (CHP) is the main product obtained with Co(BPZ) (84% selectivity to CHP after 7 h, p(O2) = 4 bar, and T = 363 K), further oxidation to 2-phenyl-2-propanol (PP) is observed in the presence of Co(BPZNH(2)) as the catalyst (69% selectivity to PP under the same experimental conditions)., S.G., R.V., and M.M. acknowledge Universita dell'Insubria for partial funding. G.G. thanks the Italian MIUR through the PRIN 2017 Project Multi-e: Multielectron Transfer for the Conversion of Small Molecules: an Enabling Technology for the Chemical Use of Renewable Energy (20179337R7) for financial support. G.G. thanks the TRAINER project (Catalysts for Transition to Renewable Energy Future) ref. ANR-17-MPGA-0017 for support. C.P. thanks the University of Camerino and the Italian MIUR throughout the PRIN 2015 Project Towards a Sustainable Chemistry (20154 x 9ATP_002). This project has also received funding from the European Union's Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No. 641887 (project acronym: DEFNET) and the Spanish Government through projects MAT2017-82288-C2-1-P and Severo Ochoa (SEV-2016-0683). Professor Norberto Masciocchi (University of Insubria, Como, Italy) is acknowledged for fruitful discussions. The authors are also grateful to Dr. Giulia Tuci (CNR-ICCOM Florence, Italy) for help with the XPS curve fitting. The Microscopy Service of the Universitat Politècnica de València is gratefully acknowledged for the electron microscopy measurements.

A series of copper(II) pyrazolates were synthesized employing different synthetic approaches. By refluxing either [Cu3(μ3-OH)(μ-pz)3(CH3COO)2(pzH)] (pzH = pyrazole) or [Cu(μ-pz)2·H2O]n in water, [Cu(μ-pz)(μ-OH)]n (1) was unexpectedly obtained, whereas the reactions of copper(II) acetate hydrate with pzH or 4-XpzH (4-XpzH = 4-Xpyrazole, X = Cl, Br, I) in dimethylformamide (DMF) by microwave-assisted solvothermal syntheses yielded the compounds [Cu(μ-pz)2(μ-DMF)]n (2DMF) or [Cu(μ-4-Xpz)2(μ-DMF)]n (3DMF–5DMF). As unveiled by powder X-ray diffraction, all these compounds are 1-D coordination polymers showing square planar trans-CuN2O2 (1) or octahedral trans-CuN4O2 (2DMF–5DMF) metal centers, reasonably involved in through-bond antiferromagnetic interactions (magnetic susceptibility in the range 0.91–1.56 B.M.). Theoretical calculations carried out on these compounds at the B3LYP-D* level confirmed the structural aspects and IR spectroscopy features unveiled experimentally. Upon heating, 2DMF–5DMF reversibly lose DMF to give the corresponding low-crystallinity coordination polymers [Cu(μ-pz)2]n (2) and [Cu(μ-4-Xpz)2]n (3–5), of which only 3 was characterized in the past. In order to shed light on the local-level structural features of 2, 4 and 5, UV-Vis-NIR absorption and fluorescence emission spectroscopy measurements were performed, the results suggesting a tetrahedral stereochemistry for the metal centres.

The bicyclic ditopic linker 2,2'-biselenophene-5,5'-dicarboxylic acid (H2SpSp), specifically designed for metal-organic framework (MOF) construction, has been synthesized in good yield and fully characterized. The corresponding zirconium MOF (Zr-MOF) [Zr6O4(OH)4(SpSp)3.8Cl4.4] (1; where missing linkers are replaced by chloride anions as shown by X-ray fluorescence and elemental analysis) is isostructural with its bithiophene and bithiazole analogues. Starting from 1, an extension of the biselenophene-based Zr-MOF family has been successfully achieved, exploiting the structural analogy of the five-membered heterocycles selenophene, thiophene, and thiazole. Thus, three mixed-linker MOFs containing variable amounts of different bis(heterocyclic) dicarboxylic acids have been prepared and fully characterized: the two double-mixed [Zr6O4(OH)4(SpSp)2.6(TpTp)1.3Cl4.2] (2; H2TpTp = 2,2'-bithiophene-5,5'-dicarboxylic acid) and [Zr6O4(OH)4(SpSp)2(TzTz)1.8Cl4.4] (3; H2TzTz = 2,2'-bithiazole-5,5'-dicarboxylic acid) materials, as well as the triple-mixed [Zr6O4(OH)4(SpSp)1.6(TpTp)1.2(TzTz)1.4Cl3.6] (4) compound. The four MOFs are luminescent under UV irradiation, exhibiting emission wavelengths falling in the blue-green visible region, as observed for their constitutive linkers. These materials open new horizons in the preparation of porous luminescent sensors or multicolor emitters for light-emitting diodes.

As natural allies against Venetian supremacy in the Adriatic, Dubrovnik and Ancona had developed trade relations from medieval times. They reached their heyday in the sixteenth century, after the weakening of Venice under papal pressure and defeat in the battle of Agnadello, but also the Ottoman expansion in the Balkans and Hungarian downfall. By taking control of the Balkan trade, under special tributary terms with the Ottomans, Ragusans enjoyed most favourable privileges. The merchants of Ancona, whose port welcomed Ragusan ships laden with goods from the Balkans and the Levant, were attracted by the trade prospects across the Adriatic. Migration routes between the two Adriatic shores intensifi ed. Archival sources from as early as the fi fteenth century provide data on merchants from the Marche region with residence in Dubrovnik, from which they found it easier to manage their affairs in the Levant. At the same time, the Ragusans opened a consulate in Pesaro, a city from which, together with Ancona and Fermo, came the majority of Marche merchants. Besides trade, archive series Debiti di Notaria and Noli e Sicurtà of the State Archives in Dubrovnik testify to other business dealings undertaken by foreigners from the region of Marche in Dubrovnik, such as credit and insurance activities. Thus it comes as no surprise that these circumstances proved fertile ground for personal relations: Cvijeta Zuzorić, famous Ragusan poetess, spent many years in Ancona with her family, while the writer Michele Gabrieli alias Monaldi, originally from Prato, was highly esteemed by the Ragusan philosopher Nikola Vitov Gozze, who chose him as collocutor in his Discorsi sopra le Metheore d’Aristotile, published in Venice in 1584. Among many distinguished persons who arrived in Dubrovnik from the region of Marche in this period was Girolamo Matteucci, Archbishop of Dubrovnik from 1579 to 1583, and his cousin, Saporoso Matteucci, who acted as the “general of the armsˮ of the Dubrovnik Republic from 1570 to 1577. A name also worthy of mention is Ciriaco Gualterucci, who, upon the prompting of Ragusan merchants in Belgrade, supplied the Serbian market with liturgical books. Although the business relations between Dubrovnik and the cities of the region of Marche developed to mutual satisfaction, the Ragusans managed to protect their monopoly by keeping the ambitious outsiders from the other shore of the Adriatic as partners in smaller merchant ventures, and thus represented no threat to the Ragusan leading business position.

ObjectivesTo compare necrotising enterocolitis (NEC) prevention practices and NEC associated factors between units from eight countries of the International Network for Evaluation of Outcomes of Neonates, and to assess their association with surgical NEC rates.DesignProspective unit-level survey combined with retrospective cohort study.SettingNeonatal intensive care units in Australia/New Zealand, Canada, Finland, Israel, Spain, Sweden, Switzerland and Tuscany (Italy).PatientsExtremely preterm infants born between 240to 286weeks’ gestation, with birth weightsExposuresNEC prevention practices (probiotics, feeding, donor milk) using responses of an on-line pre-piloted questionnaire containing 10 questions and factors associated with NEC in literature (antenatal steroids, c-section, indomethacin treated patent ductus arteriosus and sepsis) using cohort data.Outcome measuresSurgical NEC rates and death following NEC using cohort data.ResultsThe survey response rate was 91% (153 units). Both probiotic provision and donor milk availability varied between 0%–100% among networks whereas feeding initiation and advancement rates were similar in most networks. The 9792 infants included in the cohort study to link survey results and cohort outcomes, revealed similar baseline characteristics but considerable differences in factors associated with NEC between networks. 397 (4.1%) neonates underwent NEC surgery, ranging from 2.4%–8.4% between networks. Standardised ratios for surgical NEC were lower for Australia/New Zealand, higher for Spain, and comparable for the remaining six networks.ConclusionsThe variation in implementation of NEC prevention practices and in factors associated with NEC in literature could not be associated with the variation in surgical NEC incidence. This corroborates the current lack of consensus surrounding the use of preventive strategies for NEC and emphasises the need for research.

This is the first case of NBAS disease detected by NBS for primary immunodeficiency. NBS with KRECs is revealing unknown potentialities detecting conditions that benefit from early recognition like NBAS deficiency. Immune phenotyping should be mandatory in patients with NBAS deficiency since they can exhibit severe immunodeficiency with hypogammaglobulinemia as the most frequent finding. Fever during infections is a known trigger of acute liver failure in this syndrome, so immune dysfunction, should never go unnoticed in NBAS deficiency in order to start adequate therapy and prophylaxis.

The new coordination polymers (CPs) [Zn(tr2ad)Cl2]n, {[Cu(tr2ad)Cl]Cl∙4H2O}n, [Cd2(tr2ad)Cl4]n, {[Cu(tr2ad)(NO3)](NO3)}n and {[Cd(tr2ad)(NO3)](NO3)∙H2O}n were obtained in the form of air- and moisture-stable microcrystalline powders by the solvothermal reactions of zinc(II), copper(II) and cadmium(II) chlorides or nitrates with the ligand 1,3-bis(1,2,4-triazol-4-yl)adamantane (tr2ad). Investigation of the thermal behaviour assessed the thermal stability of these CPs, with [Cd2(tr2ad)Cl4]n starting to decompose only around 365 &deg, C. As retrieved by powder X-ray diffraction, while [Zn(tr2ad)Cl2]n features 1-D chains along which the metal centre shows a tetrahedral geometry and the spacer is exo-bidentate, the other CPs contain 2-D double-layers in which the metal ions possess an octahedral stereochemistry and the linker is exo-tetradentate. A comparative structural analysis involving known coordination compounds containing the tr2ad ligand enabled us to disclose (i) the versatility of the ligand, as far as the coordination modes are concerned, (ii) the variability in crystal structure dimensionality, ranging from 1-D to 3-D, (iii) the fact that, to the best of our knowledge, [Zn(tr2ad)Cl2]n is the first ZnII-based CP containing the tr2ad spacer.

Na temelju izvora u Državnom arhivu u Dubrovniku i Archivio di Stato i Archivio Communale u Anconi rekonstruira se gusta mreža trgovačkih veza između poslovnih ljudi iz pokrajine Marche i Dubrovnika tijekom 16. stoljeća. Prilagodivši se izmijenjenim političkim odnosima na Balkanskom poluotoku nakon osmanskih osvajanja i ugarskog sloma 1526. u Mohačkoj bitci, brojni trgovci iz Ancone, Pesara i Ferma prepoznali su važnost dubrovačkih poslovnih veza u istočnojadranskom zaleđu i na starim pravcima prema Carigradu. Zato su osobno angažirani u Dubrovniku, baveći se trgovinom, ali i kreditnim poslovima, zajmovima i osiguranjem. Dubrovčani su ipak zaštitili svoj monopol, a iskoristili su interese susjeda s druge obale Jadrana da otvore konzulat u Pesaru. Dobre poslovne veze urodile su i nizom privatnih, kad su nekadašnji došljaci iz pokrajine Marche odlučili trajno se nastaniti u Dubrovniku., As natural allies against Venetian supremacy in the Adriatic, Dubrovnik and Ancona had developed trade relations from medieval times. They reached their heyday in the sixteenth century, after the weakening of Venice under papal pressure and defeat in the battle of Agnadello, but also the Ottoman expansion in the Balkans and Hungarian downfall. By taking control of the Balkan trade, under special tributary terms with the Ottomans, Ragusans enjoyed most favourable privileges. The merchants of Ancona, whose port welcomed Ragusan ships laden with goods from the Balkans and the Levant, were attracted by the trade prospects across the Adriatic. Migration routes between the two Adriatic shores intensifi ed. Archival sources from as early as the fi fteenth century provide data on merchants from the Marche region with residence in Dubrovnik, from which they found it easier to manage their affairs in the Levant. At the same time, the Ragusans opened a consulate in Pesaro, a city from which, together with Ancona and Fermo, came the majority of Marche merchants. Besides trade, archive series Debiti di Notaria and Noli e Sicurtà of the State Archives in Dubrovnik testify to other business dealings undertaken by foreigners from the region of Marche in Dubrovnik, such as credit and insurance activities. Thus it comes as no surprise that these circumstances proved fertile ground for personal relations: Cvijeta Zuzorić, famous Ragusan poetess, spent many years in Ancona with her family, while the writer Michele Gabrieli alias Monaldi, originally from Prato, was highly esteemed by the Ragusan philosopher Nikola Vitov Gozze, who chose him as collocutor in his Discorsi sopra le Metheore d’Aristotile, published in Venice in 1584. Among many distinguished persons who arrived in Dubrovnik from the region of Marche in this period was Girolamo Matteucci, Archbishop of Dubrovnik from 1579 to 1583, and his cousin, Saporoso Matteucci, who acted as the “general of the armsˮ of the Dubrovnik Republic from 1570 to 1577. A name also worthy of mention is Ciriaco Gualterucci, who, upon the prompting of Ragusan merchants in Belgrade, supplied the Serbian market with liturgical books. Although the business relations between Dubrovnik and the cities of the region of Marche developed to mutual satisfaction, the Ragusans managed to protect their monopoly by keeping the ambitious outsiders from the other shore of the Adriatic as partners in smaller merchant ventures, and thus represented no threat to the Ragusan leading business position.

Il saggio intende affrontare gli aspetti economici del pellegrinaggio. Il caso analizzato e quello della Santa Casa di Loreto che, dopo il Concilio di Trento, si impone come il maggiore santuario mariano dell’Europa cattolica. Dopo aver richiamato i momenti fondamentali che favoriscono l’emergere del culto lauretano, dalle origini trecentesche alla definitiva affermazione nei due decenni successivi alla meta del Quattrocento, segnati dal forte bisogno di trasferire la sacralita della Terrasanta in Occidente in seguito alla caduta di Costantinopoli (1453), viene analizzato l’andamento del fenomeno peregrinatorio. Quando il flusso assume dimensioni di massa, per rispondere ai bisogni espressi dai pellegrini occorre provvedere non solo ai servizi religiosi, ma anche ai servizi di accoglienza. Il saggio si concentra infine sul tema delle elemosine. Nel caso di Loreto e possibile quantificare con precisione (e per quasi quattro secoli: dagli inizi del Cinquecento agli inizi del Novecento) il flusso delle offerte lasciate dai pellegrini nelle casse del santuario della Santa Casa; si tratta di dati molto dettagliati ed estremamente significativi non solo per comprendere i meccanismi di finanziamento interno di un grande santuario, ma anche ai fini di una storia del comportamento religioso nell’Europa di eta moderna. Sono dati da non sopravvalutare, viste le difficolta interpretative che sollevano, ma di indiscutibile valore. Nell’ultimo cinquantennio gli storici delle mentalita sono andati alla ricerca di indicatori quantitativi che permettessero uno studio seriale degli atteggiamenti e delle pratiche religiose: la documentazione lauretana permette ora di offrire un ulteriore contributo in questa direzione.

Wound healing is a specific host immune response for restoration of tissue integrity. Experimental studies demonstrated an alteration of growth factors activity due to their reduced synthesis, increased degradation and inactivation. In wound healing platelets play an essential role since they are rich of a-granules growth factors (platelet derived growth factor––PDGF; transforming growth factor-b––TGF-b; vascular endothelial growth factor––VEGF). Topical use of platelet gel (PG), hemocomponent obtained from mix of activated platelets and cryoprecipitate, gives the exogenous and in situ adding of growth factors (GF). The hemocomponents are of autologous or homologous origin. We performed a technique based on: multicomponent apheretic procedure to obtain plasma rich platelet and cryoprecipitate; manual processing in an open system, in sterile environment, for gel activation. Every step of the gel synthesis was checked by a quality control programme. The therapeutic protocol consists of the once-weekly application of PG. Progressive reduction of the wound size, granulation tissue forming, wound bed detersion, regression and absence of infective processes were considered for evaluating clinical response to hemotherapy. 24 patients were enrolled. They had single or multiple cutaneous ulcers with different ethiopathogenesis. Only 3 patients could perform autologous withdrawal; in the others homologous hemocomponent were used, always considering suitability and traceability criteria for transfusional use of blood. Complete response was observed in 9 patients, 2 were subjected to cutaneous graft, 4 stopped treatment, 9 had partial response and are still receiving the treatment. In each case granulation tissue forming increased following to the first PG applications, while complete re-epithelization was obtained later. Pain was reduced in every treated patient. Topical haemotherapy with PG may be considered as an adjuvant treatment of a multidisciplinary process, useful to enhance therapy of cutaneous ulcers. � 2004 Elsevier Ltd. All rights reserved.

Introduction Understanding the mechanisms by which some individuals are able to naturally control HIV-1 infection is an important goal of AIDS research. We here describe the case of an HIV-1+ woman, CASE1, who has spontaneously controlled her viremia for the last 14 of her 20 years of infection. Methods CASE1 has been clinically monitored since 1993. Detailed immunological, virological and histological analyses were performed on samples obtained between 2009 and 2011. Results As for other Elite Controllers, CASE1 is characterized by low to undetectable levels of plasma HIV-1 RNA, peripheral blood mononuclear cell (PBMC) associated HIV-1 DNA and reduced in vitro susceptibility of target cells to HIV-1 infection. Furthermore, a slow rate of virus evolution was demonstrated in spite the lack of assumption of any antiretroviral agent. CASE1 failed to transmit HIV-1 to either her sexual male partner or to her child born by vaginal delivery. Normal values and ratios of T and B cells were observed, along with normal histology of the intestinal mucosa. Attempts to isolate HIV-1 from her PBMC and gut-derived cells were unsuccessful, despite expression of normal cell surface levels of CD4, CCRC5 and CXCR4. CASE1 did not produce detectable anti-HIV neutralizing antibodies in her serum or genital mucosal fluid although she displayed potent T cell responses against HIV-1 Gag and Nef. CASE1 also possessed multiple genetic polymorphisms, including HLA alleles (B*14, B*57, C*06 and C*08.02) and HLA-C single nucleotide polymorphisms (SNPs, rs9264942 C/C and rs67384697 del/del), that have been previously individually associated with spontaneous control of plasma viremia, maintenance of high CD4+ T cell counts and delayed disease progression. Conclusions CASE1 has controlled her HIV-1 viremia below the limit of detection in the absence of antiretroviral therapy for more than 14 years and has not shown any sign of immunologic deterioration or disease progression. Co-expression of multiple protective HLA alleles, HLA-C SNPs and strong T cell responses against HIV-1 proteins are the most likely explanation of this very benign case of spontaneous control of HIV-1 disease progression. Electronic supplementary material The online version of this article (doi:10.1186/s12967-014-0335-6) contains supplementary material, which is available to authorized users.

Mycobacterium genavense is a frequently missed agent of disseminated disease in AIDS patients. The increasing frequency with which such organism is being isolated in Italy suggested a comparison of local survey with data reported in literature. Isolates presumed to belong to the species M. genavense were centralized and identified by means of genomic sequencing and/or HPLC analysis of cell wall mycolic acids; clinical data were obtained from relevant patients' record and collected using a proper questionnaire. In 24 cases in which this organism has been isolated in Italy M. genavense was grown, prevalently from blood, in liquid medium after an average of six weeks of incubation. In overwhelming majority, patients were males, presented other opportunistic diseases and were characterized by very low CD4+ counts (average 23/μl); most frequent symptoms were fever, anemia and weight loss. All but two patients, who died before the mycobacterial infection was diagnosed, were treated with at least three drugs; the mean survival was close to one year. A review of literature reports revealed a wide overlapping of clinical and microbiological features.

Sorafenib (SO) was the first targeted agent to produce significant improvements in overall survival in patients with advanced hepatocellular carcinoma (HCC). We report the case of a cirrhotic patient with chronic hepatitis C virus infection; locally advanced, unresectable, multinodular HCC, and portal vein tumor thrombosis, who achieved complete tumor regression following SO treatment. The patient was treated with SO 400 mg twice daily, which was subsequently reduced to 200 mg twice daily due to the occurrence of hand–foot skin reaction. The patient also received the following concomitant medications: Synchro-Levels® (Alphrema, Varese, Italy), silymarin and vitamin E. Long-term treatment with reduced SO dosage and Synchro-Levels resulted in a sustained radiological and clinical response with normalization of α-fetoprotein levels. Observed side effects were mostly low grade and manageable following dose adjustments. After 44 months of treatment the patient was in good physical condition, which suggests that a complete response with long-term SO is achievable in patients with locally advanced HCC.