Picosecond Structural Relaxation of Abietic Acid Based Amine End Capped Para‐Phenylenevinylene Trimers in Solution

The synthesis and photophysical properties of six new abietic acid based amine end‐capped p‐phenylenevinylene trimers (AECPV3) in their lowest excited singlet states are presented. The AECPV3 compounds show a large red‐shift of both the absorption (25–30 nm) and emission (37–42 nm) maxima with respect to those of the corresponding trimers. Picosecond time‐resolved fluorescence data reveal the presence of a fast conformational relaxation process (40–62 ps) of the initially excited compounds, leading to more planar conformers. The conformational relaxation time is proportional to the volume of both the side chain and the amine groups.     

Methodology to Quantify and Screen the Demineralization of Teeth by Immersing Them in Acidic Drinks (Orange Juice,Coca-Cola™, and Grape Juice): Evaluation by ICP OES

Oral health problems may occur as a result of the ingestion of acid drinks. The objective of this in vitro study was to quantify and screen the concentration of potassium (K), phosphorus (P), calcium (Ca), magnesium (Mg), manganese (Mn), zinc (Zn), iron (Fe), copper (Cu), barium (Ba), lead (Pb), arsenic (As), cadmium (Cd), aluminum (Al), cobalt (Co), chromium (Cr), molybdenum (Mo), sodium (Na), nickel (Ni), selenium (Se), and vanadium (V) released from bovine incisors during an erosive challenge at different times of exposure when immersed in Coca-Cola™, orange juice, and grape juice. A total of 240 samples of bovine incisor teeth were used for the erosive challenge and allocated in groups. Digestion of drinks was performed using microwave-assisted digestion. The content in acidic drinks was monitored before and after the erosive challenge at exposure times of 1, 5, and 60 min using inductively coupled plasma optical emission spectrometry (ICP OES). The drinks’ pH varied slightly during the erosive challenge but remained below the critical value of pH 5 to cause tooth demineralization. The concentrations of elements released from the bovine incisors during the in vitro erosive challenge depend on exposure times when immersed in acidic beverages. For some elements such as Ca, Mn, Zn, Fe, Cu, Ba, Pb, As, and Cd, quantified in acidic drinks, grape juice had greater erosive potential than Coca-Cola™ and orange juice. Quantification and monitoring of chemical elements in bovine teeth can be performed considering a longer erosive time and other types of acidic drinks. Further analysis using human teeth is still not available and must be conducted. The demineralization of teeth not only occurs in acidic beverages; physical and chemical factors play other roles and should be investigated.     

Identification of New Potential Inhibitors of Quorum Sensing through a Specialized Multi-Level Computational Approach

Biofilms are aggregates of microorganisms anchored to a surface and embedded in a self-produced matrix of extracellular polymeric substances and have been associated with 80% of all bacterial infections in humans. Because bacteria in biofilms are less amenable to antibiotic treatment, biofilms have been associated with developing antibiotic resistance, a problem that urges developing new therapeutic options and approaches. Interfering with quorum-sensing (QS), an important process of cell-to-cell communication by bacteria in biofilms is a promising strategy to inhibit biofilm formation and development. Here we describe and apply an in silico computational protocol for identifying novel potential inhibitors of quorum-sensing, using CviR—the quorum-sensing receptor from Chromobacterium violaceum—as a model target. This in silico approach combines protein-ligand docking (with 7 different docking programs/scoring functions), receptor-based virtual screening, molecular dynamic simulations, and free energy calculations. Particular emphasis was dedicated to optimizing the discrimination ability between active/inactive molecules in virtual screening tests using a target-specific training set. Overall, the optimized protocol was used to evaluate 66,461 molecules, including those on the ZINC/FDA-Approved database and to the Mu.Ta.Lig Virtual Chemotheca. Multiple promising compounds were identified, yielding good prospects for future experimental validation and for drug repurposing towards QS inhibition.     

Differential Tunneling-Driven and Vibrationally-Induced Reactivity in Isomeric Benzazirines

Quantum mechanical tunneling of heavy-atoms and vibrational excitation chemistry are unconventional and scarcely explored types of reactivity. Once fully understood, they might bring new avenues to conduct chemical transformations, providing access to a new world of molecules or ways of exquisite reaction control. In this context, we present here the discovery of two isomeric benzazirines exhibiting differential tunneling-driven and vibrationally-induced reactivity, which constitute exceptional results for probing into the nature of these phenomena. The isomeric 6-fluoro- and 2-fluoro-4-hydroxy-2H-benzazirines ( 3-a and 3′-s ) were generated in cryogenic krypton matrices by visible-light irradiation of the corresponding triplet nitrene ³ 2-a , which was produced by UV-light irradiation of its azide precursor. The 3′-s was found to be stable under matrix dark conditions, whereas 3-a spontaneously rearranges (τ_1/2 ∼64 h at 10 and 20 K) by heavy-atom tunneling to ³ 2-a . Near-IR-light irradiation at the first OH stretching overtone frequencies (remote vibrational antenna) of the benzazirines induces the 3′-s ring-expansion reaction to a seven-member cyclic ketenimine, but the 3-a undergoes 2H-azirine ring-opening reaction to triplet nitrene ³ 2-a . Computations demonstrate that 3-a and 3′-s have distinct reaction energy profiles, which explain the different experimental results. The spectroscopic direct measurement of the tunneling of 3-a to ³ 2-a constitutes a unique example of an observation of a species reacting only by nitrogen tunneling. Moreover, the vibrationally-induced sole activation of the most favorable bond-breaking/bond-forming pathway available for 3-a and 3′-s provides pioneer results regarding the selective nature of such processes.     

Enthalpies of reaction of lanthanide trifluoroacetate trihydrate with 2-azacyclononanone to form lanthanide trifluoroacetate-tris 2-azacyclononanone

The condensed phase, acid-base reaction enthalpy for Ln(tfa)·3H₂O (s) + 3aza (s) → Ln(tfa)₃·3aza (s) + 3H₂O; (kJ mol⁻¹) = −33.90 ± 1.54, −2.10 ± 1.25, −9.40 ± 2.10, 0.05 ± 2.27 and 2.46 ± 1.45 for the Pr, Nd, Sm, Eu and Tb compounds, respectively, where tfa, the trifluoroacetate, and aza, the 2-azacyclononanone, were measured by calorimetry.     

Aging investigation of cobalt ferrite nanoparticles in low pH magnetic fluid

In this study, we report on how surface-passivated and nonpassivated cobalt ferrite nanoparticles (8 nm diameter), suspended as ionic magnetic fluids and aged under low pH conditions, revealed different behavior as far as the time evolution of the iron/cobalt cation distribution, crystal quality, coercivity, and saturation magnetization are concerned. Different techniques were used to perform a detailed study regarding the chemical stability, structural stability, and surface and magnetic properties of the suspended nanoparticles as a function of the aging time. Properties of surface-passivated and nonpassivated nanoparticles were investigated by transmission electron microscopy, X-ray diffraction, atomic absorption spectrometry, magnetic measurements, Raman spectroscopy, and M?ssbauer spectroscopy. Our data showed that the employed nanoparticle surface passivation process, besides the formation of an iron-rich surface layer, modifies the nanoparticle core as well, improving the crystal quality while modifying the Fe/Co cation distribution and the nanoparticle dissolution rate profile. Magnetic data showed that the saturation magnetization increases for surface-passivated nanoparticles in comparison to the nonpassivated ones, though coercivity decreases after passivation. These two observations were associated to changes in the cation distribution among the available tetrahedral and octahedral sites.     

Structural determination of Zn and Cd-DTPA complexes: MS, infrared, (13)C NMR and theoretical investigation

The joint application of MS, infrared and (13)C NMR techniques for the determination of metal-DTPA structures (metal=Zn and Cd; DTPA=diethylenetriaminepentacetic acid) is reported. Mass spectrometry allowed determining the 1:1 stoichiometry of the complexes, while infrared analysis suggested that both nitrogen and carboxyl groups are sites for complexation. The (13)C NMR spectrum for the cadmium-containing complex evidenced the existence of free and complexed carboxyl groups, due to a straight singlet at 179.0 ppm (free carboxylic (13)C) and to two broad singlets or a broad doublet at 178.3 ppm (complexed carboxylic (13)C, (2)J(Cd-C(=O))=45.2 Hz). A similar interpretation might be given for the zinc derivative and, with the aid of DFT calculations, structures for both complexes were then proposed.     

Mechanical properties of axons

The mechanical response of PC12 neurites under tension is investigated using a microneedle technique. Elastic response, viscoelastic relaxation, and active contraction are observed. The mechanical model proposed by Dennerll et al. [J. Cell Biol. 109, 3073 (1989).10.1083/jcb.109.6.3073], which involves three mechanical devices--a stiff spring kappa coupled with a Voigt element that includes a less stiff spring k and a dashpot gamma--has been improved by adding a new element to describe the main features of the contraction of axons. This element, which represents the action of molecular motors, acts in parallel with viscous forces defining a global tension response of axons T against elongation rates delta(k). Under certain conditions, axons show a transition from a viscoelastic elongation to active contraction, suggesting the presence of a negative elongation rate sensitivity in the curve T vs delta(k).     

Noise suppression properties of an interferometer-based regenerator for differential phase-shift keying data

We studied the amplitude and phase noise suppression properties of an all-optical regenerator for differential phase-shift keying data. A detailed analytical investigation is performed and compared with numerical simulations for different working points. The results show that both amplitude and phase can be regenerated. However, simultaneous amplitude and phase noise suppression is possible only if the phase degradation is stronger than the amplitude degradation, for instance, due to nonlinear phase noise.