Pyrene, a Test Case for Deep-Ultraviolet Molecular Photophysics

We determined the complete relaxation dynamics of pyrene in ethanol from the second bright state, employing experimental and theoretical broadband heterodyne detected transient grating and two-dimensional photon echo (2DPE) spectroscopy, using pulses with duration of 6 fs and covering a spectral range spanning from 250 to 300 nm. Multiple lifetimes are assigned to conical intersections through a cascade of electronic states, eventually leading to a rapid population of the lowest long-living excited state and subsequent slow vibrational cooling. The lineshapes in the 2DPE spectra indicate that the efficiency of the population transfer depends on the kinetic energy deposited into modes required to reach a sloped conical intersection, which mediates the decay to the lowest electronic state. The presented experimental–theoretical protocol paves the way for studies on deep-ultraviolet-absorbing biochromophores ubiquitous in genomic and proteic systems

Importance of electronic self-consistency in the TDDFT based treatment of nonadiabatic molecular dynamics

A mixed quantum-classical approach to simulate the coupled dynamics of electrons and nuclei in nanoscale molecular systems is presented. The method relies on a second order expansion of the Lagrangian in time-dependent density functional theory (TDDFT) around a suitable reference density. We show that the inclusion of the second order term renders the method a self-consistent scheme and improves the calculated optical spectra of molecules by a proper treatment of the coupled response. In the application to ion-fullerene collisions, the inclusion of self-consistency is found to be crucial for a correct description of the charge transfer between projectile and target. For a model of the photoreceptor in retinal proteins, nonadiabatic molecular dynamics simulations are performed and reveal problems of TDDFT in the prediction of intra-molecular charge transfer excitations.Comment: 9 pages, 8 figures. Minor changes in content wrt older versio

Renormalization--Group Solutions for Yukawa Potential

The self--similar renormalization group is used to obtain expressions for the spectrum of the Hamiltonian with the Yukawa potential. The critical screening parameter above which there are no bound states is also obtained by this method. The approach presented illustrates that one can achieve good accuracy without involving extensive numerical calculations, but invoking instead the renormalization--group techniques.Comment: 1 file, 12 pages, RevTe

Multiple sulfatase deficiency with neonatal manifestation.

Multiple Sulfatase Deficiency (MSD; OMIM 272200) is a rare autosomal recessive inborn error of metabolism caused by mutations in the sulfatase modifying factor 1 gene, encoding the formylglycine-generating enzyme (FGE), and resulting in tissue accumulation of sulfatides, sulphated glycosaminoglycans, sphingolipids and steroid sulfates. Less than 50 cases have been published so far. We report a new case of MSD presenting in the newborn period with hypotonia, apnoea, cyanosis and rolling eyes, hepato-splenomegaly and deafness. This patient was compound heterozygous for two so far undescribed SUMF1 mutations (c.191C > A; p.S64X and c.818A > G; p.D273G)

Clinical and molecular characterization of 40 patients with classic Ehlers--Danlos syndrome: identification of 18 COL5A1 and 2 COL5A2 novel mutations.

Classic Ehlers-Danlos syndrome (cEDS) is a rare autosomal dominant connective tissue disorder that is primarily characterized by skin hyperextensibility, abnormal wound healing/atrophic scars, and joint hypermobility. A recent study demonstrated that more than 90% of patients who satisfy all of these major criteria harbor a type V collagen (COLLV) defect. This cohort included 40 patients with cEDS who were clinically diagnosed according to the Villefranche nosology. The flowchart that was adopted for mutation detection consisted of sequencing the COL5A1 gene and, if no mutation was detected, COL5A2 analysis. In the negative patients the presence of large genomic rearrangements in COL5A1 was investigated using MLPA, and positive results were confirmed via SNP-array analysis. We report the clinical and molecular characterization of 40 patients from 28 families, consisting of 14 pediatric patients and 26 adults. A family history of cEDS was present in 9 patients. The majority of the patients fulfilled all the major diagnostic criteria for cEDS; atrophic scars were absent in 2 females, skin hyperextensibility was not detected in a male and joint hypermobility was negative in 8 patients (20% of the entire cohort). Wide inter- and intra-familial phenotypic heterogeneity was observed. We identified causal mutations with a detection rate of approximately 93%. In 25/28 probands, COL5A1 or COL5A2 mutations were detected. Twenty-one mutations were in the COL5A1 gene, 18 of which were novel (2 recurrent). Of these, 16 mutations led to nonsense-mediated mRNA decay (NMD) and to COLLV haploinsufficiency and 5 mutations were structural. Two novel COL5A2 splice mutations were detected in patients with the most severe phenotypes. The known p. (Arg312Cys) mutation in the COL1A1 gene was identified in one patient with vascular-like cEDS. Our findings highlight that the three major criteria for cEDS are useful and sufficient for cEDS clinical diagnosis in the large majority of the patients. The borderline patients for whom these criteria fail can be diagnosed when minor signs of connective tissue diseases and family history are present and when genetic testing reveals a defect in COLLV. Our data also confirm that COL5A1 and COL5A2 are the major, if not the only, genes involved in cEDS

Thermessaite-(NH4), (NH4)2AlF3(SO4), a new fumarole mineral from la Fossa crater at Vulcano, Aeolian Islands, Italy

Thermessaite-(NH4), ideally (NH4)2AlF3(SO4), is a new mineral found as a medium- to high-temperature (about 250-300°C) fumarole encrustation at the rim of La Fossa crater, Vulcano, Aeolian Islands, Italy. The mineral deposited as aggregates of micrometer-sized sharp prismatic crystals on the surface of a pyroclastic breccia in association with thermessaite, sulfur, arcanite, mascagnite, and intermediate members of the arcanite-mascagnite series. The new mineral is colorless to white, transparent, non-fluorescent, has a vitreous luster, and a white streak. The calculated density is 2.185 g/cm3. Thermessaite-(NH4) is orthorhombic, space group Pbcn, with a = 11.3005(3) Å, b = 8.6125(3) Å, c = 6.8501(2) Å, V = 666.69(4) Å3, Z = 4. The eight strongest reflections in the X-ray powder-diffraction data [d in Å (I) (hkl)] are: 5.65 (100) (200), 4.84 (89) (111), 6.85 (74) (110), 3.06 (56) (112), 3.06 (53) (221), 3.08 (47) (311), 2.68 (28) (022), 2.78 (26) (130). The average chemical composition, determined by quantitative SEM-EDS (N by difference), is (wt%): K2O 3.38, Al2O325.35, SO336.58, F 26.12, (NH4)2O 22.47, O = F -11.00, total 102.90. The empirical chemical formula, calculated on the basis of 7 anions pfu, is [(NH4)1.85K0.15]Σ2.00Al106F2.94-S0.98O3.06. The crystal structure, determined from single-crystal X-ray diffraction data [R(F) = 0.0367], is characterized by corner-sharing AlF4O2octahedra which form [001] octahedral chains by sharing two trans fluoride atoms [Al-F2 = 1.8394(6) Å]. Non-bridging Al-F1 distances are shorter [1.756(1) Å]. The two trans oxygen atoms [Al-O = 1.920(2) Å] are from SO4tetrahedra. NH4+ions occur in layers parallel to (100) which alternate regularly with (100) layers containing ribbons of corner-sharing AlF4O2octahedra and associated SO4 groups. The NH4+ions are surrounded by five oxygen atoms and by four fluorine atoms. The mineral is named as the (NH4)-analogue of thermessaite, K2AlF3(SO4), and corresponds to an anthropogenic phase found in the burning Anna I coal dump of the Anna mine, Aachen, Germany. Both mineral and mineral name have been approved by the IMA-CNMNC commission (IMA 2011-077)

The “sant’angelo in criptis” cave church in santeramo in colle (Apulia, south italy): A multidisciplinary study for the evaluation of conservation state and stability assessment

Sant’Angelo in Criptis (Santeramo in Puglia, South Italy) is a karst cave located in the Alta Murgia National Park (aspiring geopark), presently degraded, but with signs of intense past visiting activity for worship, as testified by the beautiful wall paintings and the large number of inscriptions and engravings on the cave walls. With the aim to permit the desirable restoration and the following fruition of this ancient geo-cultural heritage, a multidisciplinary investigation of the cave was carried out in this study. The 3D cave model permitted a detailed map of the area and highlighted that the cave vault, although very regular, somewhere presents chimneys that develop upwards, indicating areas where the rock thickness is now very small. The stability analysis indicates that presently, the cave does not show remarkable signs of instability, but block failures, toppling and roof collapse are possible. Archaeometry investigations confirmed the past importance of this holy site, as testified by the overlapping in the paintings of three different pictorial cycles and the use of precious pigments, thus confirming the necessity of preservation through a conservation management strategy for a full future fruition of the cave

The effect of spatial variables on the economic and environmental performance of bioenergy production chains

The aim of this paper is to understand the impacts of spatial variables on the performance of bioenergy production chains (BPCs). Even though the strong debates continue on the use of first generation biomass for bioenergy production, many countries continue to utilize it as an alternative energy source. Several studies have been carried out on biomass transformation efficiency, on environmental impacts of using crop in biofuel production, and on its negative effects on increasing food prices. However, less attention has been paid to the role played by the spatial variables on the performance measures of BPCs. In this paper, we analyse how three spatial variables, i.e. cultivation area size, land dispersion, and accessibility to cultivation areas, can affect the performance of energy-balanced BPC, which produces its own electric and thermal energy demand. The chain is represented as a network of processes, where all inputs and outputs are geographically referred and analysed in a theoretical case example. We propose an enterprise input–output (EIO) model, which can be used as an accounting tool to compute the main materials and energy flows-related costs and as a planning tool to evaluate the chain performance in different scenarios. Finally, the proposed model is applied to an actual case study, to investigate the opportunity to establish a sunflower-based BPC in Apulia region (Italy) and to assess its performance. Results show that higher land dispersion degree and less area accessibility levels reduce the economic and environmental performance of the BPCs. The construction of the energy-balanced chain reduces the negative environmental impacts caused by fossil energy use in the processes of the BPC. Managerial implications can also be obtained from actual case study about the biodiesel plant location decisions