Synthesis,Structure, Chemical and Energetic Characterization of 1,3‐Dinitramino‐2‐nitroxy‐propane

The title compound, 1,3‐dinitramino‐2‐nitroxy‐propane ( 1 ) was prepared in high yield (85 %) and characterized by multinuclear NMR (¹H, ¹³C, ¹⁴N) and vibrational (IR, Raman) spectroscopy. The molecular structure in the solid state was elucidated by single crystal X‐ray diffraction. 1 crystallizes in the orthorhombic space group P_nma with a crystal density of ρ = 1.798 g cm^?3. Compound 1 melts at 166 °C and decomposes at 168 °C. The impact (7 J), friction (96 N) and electrostatic discharge sensitivities (0.6 J) were determined experimentally. The detonation parameters of 1 were calculated using a combined quantum chemical (CBS‐4M) calculation and a chemical equilibrium calculation based on the steady‐state model of detonation: Q = ?5998 kJ kg^?1, P = 339 kbar, D = 8895 m s^?1. The experimentally determined detonation velocity (fiber optic method) agrees well with the calculated values. In comparison with picric acid (PA) and nitropenta (PETN), compound 1 shows superior detonation characteristics when detonated in a confined space.     

The role of phosphorylated residues in peptide-peptide noncovalent complexes formation

Electrospray mass spectrometry (ESI-MS) has become the tool of choice for the study of noncovalent complexes. Our previous work has highlighted the role of phosphorylated amino acid residues in the formation of noncovalent complexes through electrostatic interaction with arginine residues’ guanidinium groups. In this study, we employ tandem mass spectrometry to investigate the gas-phase stability and dissociation pathways of these noncovalent complexes. The only difference in the three phosphopeptides tested is the nature of the phosphorylated amino acid residue. In addition the absence of acidic residues and an amidated carboxyl terminus insured that the only negative charge came from the phosphate, which allowed for the comparison of the noncovalent bond between arginine residues and each of the different phosphorylated residues. Dissociation curves were generated by plotting noncovalent complex ion intensities as a function of the nominal energy given to the noncovalent complex ion before entering the collision cell. These results showed that noncovalent complexes formed with phosphorylated tyrosine were the most stable, followed by serine and threonine, which had similar stability.     

Detection of ATP-binding to growth factors

It was shown in previous work that the interaction of growth factors (GFs) with adenosine triphosphate (ATP) is essential for their neuroprotective effect. Here we investigated the nature of the association of human basic fibroblast growth factor (bFGF), nerve growth factor (NGF), and brain-derived neurotrophic factor (BDNF) with ATP. It was demonstrated that this interaction involves the formation of non-covalent ATP-GF complexes that are labile at low pH and that could be selectively purified and subjected to electrospray and MALDI-TOF mass spectrometry. The results obtained with these techniques indicated that the stability of the complexes is high. Main features of the procedure used here are: (1) reversed-phase purification of nucleotide-protein non-covalent complexes, (2) their detection with MALDI-TOF-MS using acid-free matrix, and/or (3) their measurement with ESI-MS using soft desolvation conditions. The methodology was successful in providing proof for the presence of various nucleotide-GF complexes. It was extended to other nucleotide-binding proteins (ribonuclease A) as well as proteins that do not exhibit nucleotide binding (lysozyme) as positive and negative control, respectively. Thus, the method demonstrated its general use for the investigation of a wide range of proteins interacting with nucleotides as long as their complexes are sufficiently stable to accommodate the experimental conditions.     

Reactivity of phosphonodithioato-dppt Ni(II) mixed ligand complexes with halogens: first example of a metal-coordinating tribromide anion

The first example of a metal complex containing a tribromide anion is presented and characterised by X-ray diffraction. Hybrid DFT calculations were used to investigate the nature of the bond in coordinating trihalides and the differences with the corresponding mono-halide complexes.     

Tetrachlorinated tetraazaperopyrenes (TAPPs): highly fluorescent dyes and semiconductors for air-stable organic n-channel transistors and complementary circuits

A range of 2,9-perfluoroalkyl-substituted tetraazaperopyrene (TAPP) derivatives (1-5) was synthesised by reacting 4,9-diamino-3,10-perylenequinone diimine (DPDI) with the corresponding carboxylic acid chloride or anhydride in the presence of a base. The reaction of compounds 1-4 with dichloroisocyanuric acid (DIC) in concentrated sulphuric acid resulted in the fourfold substitution of the tetraazaperopyrene core, yielding the 2,9-bisperfluoroalkyl-4,7,11,14-tetrachloro-1,3,8,10-tetraazaperopyrenes 6-9, respectively. The optical and electrochemical data demonstrate the drastic influence of the core substitution on the properties. All compounds are highly luminescent (fluorescence quantum yields of up to Φ=0.8). The LUMO energies of the tetrachlorinated TAPP derivatives (determined by cyclic voltammetry and computed by DFT calulations) were found to be below -4?eV. In the course of this work the performance of TAPP derivatives in organic thin-film transistors (TFTs) was investigated, and their n-channel characteristics with field-effect mobilities of up to 0.14?cm(2) V(-1) s(-1) and an on/off current ratio of >10(6) were confirmed. Long-term stabilities of 3-4 months under ambient conditions of the devices were established. Complementary inverters and ring oscillators with n-channel TFTs based on compound 8 and p-channel TFTs based on dinaphtho-[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) were fabricated on a glass substrate.     

Identification of novel liver X receptor activators by structure-based modeling

Liver X receptors (LXRs) are members of the nuclear receptor family. Activators of LXRs are of high pharmacological interest as LXRs regulate cholesterol, fatty acid, and carbohydrate metabolism as well as inflammatory processes. On the basis of different X-ray crystal structures, we established a virtual screening workflow for the identification of novel LXR modulators. A two-step screening concept to identify active compounds included 3D-pharmacophore filters and rescoring by shape alignment. Eighteen virtual hits were tested in vitro applying a reporter gene assay, where concentration-dependent activity was proven for four novel lead structures. The most active compound 10, a 1,4-naphthochinone, has an estimated EC?? of around 5 μM.     

Exploring ultrafast H-atom elimination versus photofragmentation pathways in pyrazole following 200 nm excitation

The role of ultraviolet photoresistance in many biomolecules (e.g., DNA bases and amino acids) has been extensively researched in recent years. This behavior has largely been attributed to the participation of dissociative (1)πσ* states localized along X-H (X ═ N, O) bonds, which facilitate an efficient means for rapid nonradiative relaxation back to the electronic ground state via conical intersections or ultrafast H-atom elimination. One such species known to exhibit this characteristic photochemistry is the UV chromophore imidazole, a subunit in the biomolecules adenine and histidine. However, the (1)πσ* driven photochemistry of its structural isomer pyrazole has received much less attention, both experimentally and theoretically. Here, we probe the ultrafast excited state dynamics occurring in pyrazole following photoexcitation at 200 nm (6.2 eV) using two experimental methodologies. The first uses time-resolved velocity map ion imaging to investigate the ultrafast H-atom elimination dynamics following direct excitation to the lowest energy (1)πσ* state (1(1)A" ← X(1)A'). These results yield a bimodal distribution of eliminated H-atoms, situated at low and high kinetic energies, the latter of which we attribute to (1)πσ* mediated N-H fission. The time constants extracted for the low and high energy features are ~120 and <50 fs, respectively. We also investigate the role of ring deformation relaxation pathways from the first optically bright (1)ππ* state (2(1)A' ← X(1)A'), by performing time-resolved ion yield measurements. These results are modeled using a (1)ππ* → ring deformation → photofragmentation mechanism (a model based on comparison with theoretical calculations on the structural isomer imidazole) and all photofragments possess appearance time constants of <160 fs. A comparison between time-resolved velocity map ion imaging and time-resolved ion yield measurements suggest that (1)πσ* driven N-H fission gives rise to the dominant kinetic photoproducts, re-enforcing the important role (1)πσ* states have in the excited state dynamics of biological chromophores and related aromatic heterocycles.     

1,3,6,8-Tetraazapyrenes: synthesis, solid-state structures, and properties as redox-active materials

A series of new tetraazapyrene (TAPy) derivatives has been synthesized by reducing 1,4,5,8-tetranitronaphthalene to its corresponding tin salt (I) and reacting it with perfluorinated alkyl or aryl anhydrides. The resulting 2,7-disubstituted TAPy molecules and the known parent compound 1,3,6,8-tetraazapyrene (II) have been further derivatized by core chlorination and bromination. The brominated compounds served as starting materials for Suzuki cross-coupling reactions with electron-poor arylboronic acids. Single-crystal X-ray analyses established polymorphism for some TAPy compounds. The ground-state geometries of all new TAPy derivatives were modeled with DFT methods [B3PW91/6-31 g(d,p) and B3PW91/6-311+g(d,p)], especially focusing on the energies of the lowest unoccupied molecular orbital (LUMO) and the electron affinities (EA) of the molecules. The results of the calculations were confirmed experimentally by cyclic voltammetry to evaluate the substitution effects at the 2 and 7 position and the core positions, respectively, and gave LUMO energy levels that range from -3.57 to -4.14 eV. Fabrication of organic field-effect transistors (OFETs) with several of these tetraazapyrenes established their potential as organic n-type semiconductors.     

Second campaign of microclimate monitoring in the carcer tullianum: temporal and spatial correlation and gradients evidenced by multivariate analysis

Background

This paper discusses results obtained in the second monitoring campaign of the Carcer Tullianum, a particular hypogeum environment located in the historical centre of Rome (Italy). In the first paper we stressed the need to apply chemometric tools to this kind of studies in order to obtain full and significant information; really information on sampling design, sensors (type, number, position) and instrument validation seems to be not easy to find in literature for researches dealing with monitoring of indoor environments. Also in this case three main parameters (temperature, humidity, illuminance) were monitored in the complex construction by an inexpensive self-assembled system along some horizontal and vertical vectors together with some measurements of oxygen, carbon dioxide and barometric pressure. With respect to the first campaign, we used a higher number of sensors to cover a new excavated zone; for the same reason, as well as to take into account the presence of visitors, a different experimental design was adopted.

Results

Different data treatments were applied to data coming from all the used sensors. A good view of the microclimate was obtained that also resulted coherent with the different position of the three rooms constituting the monitored site (Carcer, Tullianum, Convent). Classical time plots resulted useful to evidence the correlation of the main monitored parameters (T, RH% and illuminance) with macroclimate, as well as their delay in following macroclimate. Box-Whisker and Gain-Loss graphs evidenced at the best the microclimate differences between the three rooms; an almost hypogean microclimate was evidenced for the lower room (Tullianum) where humidity values range between 90 and 100% while lower values, but anyway higher than the external, and spread more widely were measured passing to Convent and Carcer with minimum values around 50% for the last. A scarce or very scarce correlation with macroclimate was evidenced for all the three main measured parameters. Lighting results mainly dependent on artificial light and only in few cases, but unfortunately in the most precious zone, illuminance exceeds values suggested by Normative.

Conclusions

Box-Whisker and Gain-Loss graphs allowed us to have the best view of the microclimate for all the monitored rooms. The influence of lighting by lamps on the other monitored parameters resulted overlapped and clearly topped the solar one. The worst situation was found in the Carcer, where the presence of the main chandelier worsens the state of the frescoed walls, already subjected to wide changes in temperature and humidity. Also the lighthouse located above the Convent provokes lighting exceeding values suggested by Normative while, as expected, LEDs resulted as suitable source of light from a conservation point of view. Susanne Heidi Plattner, Patrizia Fortini and Maria Pia Sammartino contributed equally to this work