Ultrasound-assisted addition of alcohols to N-acyliminium ions mediated by In(OTf)3 and synthesis of 1,2,3-triazoles

An easy and mild approach using ultrasound-assisted reaction addition of alcohols to N-acyliminium ion mediated by Lewis acid, In(OTf)₃, allowed the synthesis of ether pyrrolidinones; next, the products were converted to 1,2,3-triazoles using click chemistry reaction conditions. The products in both reactions were afforded in moderate to good yields.     

Spirostaphylotrichin W,a spirocyclic γ-lactam isolated from liquid culture of Pyrenophora semeniperda, a potential mycoherbicide for cheatgrass (Bromus tectorum) biocontrol

A novel spirocyclic γ-lactam, named spirostaphylotrichin W (1), was isolated together with the well known and closely related spirostaphylotrichins A, C, D, R and V, as well as triticone E, from the liquid cultures of Pyrenophora semeniperda (anamorph: Drechslera), a seed pathogen proposed for cheatgrass (Bromus tectorum) biocontrol. Spirostaphylotrichin W was characterized as (3S*,4S*,5S*,6S*,9Z,10Z)-4,6-dihydroxy-2,3-dimethoxy-3-methyl-10-propyliden-2-azaspiro [4.5]dec-8-ene-1,7-dione, by spectroscopic and chemical methods. The relative stereochemistry of spirostaphylotrichin W was assigned using NOESY experiments and in comparison to those of spirostaphylotrichin V (2) and triticone E (6). In fact, the relative stereochemistry at C-3 was the same of that of 2, while that at C-4 and C-6 was inverted in respect to that reported, respectively, for 2 and 6. In a B. tectorum coleoptile bioassay at concentration of 10⁻³, spirostaphylotrichin A proved to be the most active compound, followed by spirostaphylotrichins C and D. Spirostaphylotrichin W and V showed mild toxicity while spirostaphylotrichin R and triticone E were not active. When tested on host and non-host plants by leaf puncture bioassay, spirostaphylotrichins A, C and D caused the appearance of necrotic spots while the other compounds were inactive.     

Synthesis of functionalized N-triazolyl maleimides

An easy and mild two-step one-pot reaction allowed the synthesis of functionalized N-triazolyl maleimide. Next, the addition of propargyl alcohol and propargyl amine to the N-acyliminium ion mediated by Lewis acid, In(OTf)₃, allowed the introduction of a second 1,2,3-triazol ring at position 5 of the amide. The products in both reactions were achieved in moderate to good yields.     

G-Quadruplex Recognition by DARPIns through Epitope/Paratope Analogy**

We investigated the mechanisms leading to the specific recognition of Guanine Guadruplex (G4) by DARPins peptides, which can lead to the design of G4 s specific sensors. To this end we carried out all-atom molecular dynamic simulations to unravel the interactions between specific nucleic acids, including human-telomeric (h-telo), Bcl-2, and c-Myc, with different peptides, forming a DARPin/G4 complex. By comparing the sequences of DARPin with that of a peptide known for its high affinity for c-Myc, we show that the recognition cannot be ascribed to sequence similarity but, instead, depends on the complementarity between the three-dimensional arrangement of the molecular fragments involved: the α-helix/loops domain of DARPin and the G4 backbone. Our results reveal that DARPins tertiary structure presents a charged hollow region in which G4 can be hosted, thus the more complementary the structural shapes, the more stable the interaction.     

Driving Organic Nanocrystals Dissolution Through Electrochemistry

We have recently discussed how organic nanocrystal dissolution appears in different morphologies and the role of the solution pH in the crystal detriment process. We also highlighted the role of the local molecular chemistry in porphyrin nanocrystals having comparable structures: in water-based acid solutions, protonation of free-base porphyrin molecules is the driving force for crystal dissolution, whereas metal (Zn^II) porphyrin nanocrystals remain unperturbed. However, all porphyrin types, having an electron rich π-structure, can be electrochemically oxidized. In this scenario, a key question is: does electrochemistry represent a viable strategy to drive the dissolution of both free-base and metal porphyrin nanocrystals? In this work, by exploiting electrochemical atomic force microscopy (EC-AFM), we monitor in situ and in real time the dissolution of both free-base and metal porphyrin nanocrystals, as soon as molecules reach the oxidation potential, showing different regimes according to the applied EC potential.     

Combined Experimental and Multivariate Model Approaches for Glycoalkaloid Quantification in Tomatoes

The intake of tomato glycoalkaloids can exert beneficial effects on human health. For this reason, methods for a rapid quantification of these compounds are required. Most of the methods for α-tomatine and dehydrotomatine quantification are based on chromatographic techniques. However, these techniques require complex and time-consuming sample pre-treatments. In this work, HPLC-ESI-QqQ-MS/MS was used as reference method. Subsequently, multiple linear regression (MLR) and partial least squares regression (PLSR) were employed to create two calibration models for the prediction of the tomatine content from thermogravimetric (TGA) and attenuated total reflectance (ATR) infrared spectroscopy (IR) analyses. These two fast techniques were proven to be suitable and effective in alkaloid quantification (R² = 0.998 and 0.840, respectively), achieving low errors (0.11 and 0.27%, respectively) with the reference technique.     

Threshold photoemission spectroscopy in solids

Threshold photoemission spectroscopy (TPES) is used to measure the Fe 2p spectrum of a stainless steel sample. The obtained spectrum is compared with analogous spectra measured by X-ray photoemission and absorption spectroscopies. The results of this comparison suggest that resonant two-electron autoionization processes, rather than direct photoemission from the core level, are the main mechanisms contributing to the signal. Limits and applicability of this experimental approach to investigate bulk electronic properties in solids are discussed.     

Work function and negative electron affinity of ultrathin barium fluoride films

Thin films of barium fluorides with different thicknesses were deposited on GaAs substrate by electron beam evaporation. The aim of the work was to identify the best growth conditions for the production of coatings with a low work function suitable for the anode of hybrid thermionic-photovoltaic (TIPV) devices. The chemical composition and work function φ of the films with different thicknesses were investigated by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). The lowest value of φ = 2.1 eV was obtained for the film with a thickness of ~2 nm. In the valence band spectra of the films at low kinetic energy, near the cutoff, a characteristic peak of negative electron affinity was present. This effect contributed to a further reduction of the film's work function.     

XPS study of Cr segregation in a martensitic stainless steel

Cr martensitic steels are promising materials for structural applications in future nuclear fusion reactors. Because the embrittlement after tempering treatments can be a serious problem, the fracture mode of a steel with 10.5 wt% of Cr treated at 700°C for 18 h has been investigated through Charpy tests in the temperature range from −100°C to +150°C. X-ray photoelectron spectroscopy (XPS) analyses carried out on the fracture surfaces evidenced the segregation of Cr in both ductile and brittle (quasicleavage) fields. The unexpected result indicates that Cr segregation weakens the atomic bonds; thus, the fracture path in both the cases corresponds to the zones with higher Cr content.