Determination of Very Slow Diffusion of Paramagnetic Ions by NMR Spectroscopy

In this paper, we propose a new method of measuring the very slow paramagnetic ion diffusion coefficient using a commercial high-resolution spectrometer. If there are distinct paramagnetic ions influencing the hydrogen nuclear magnetic relaxation time differently, their diffusion coefficients can be measured separately. A cylindrical phantom filled with Fricke xylenol gel solution and irradiated with gamma rays was used to validate the method. The Fricke xylenol gel solution was prepared with 270 Bloom porcine gelatin, the phantom was irradiated with gamma rays originated from a ⁶⁰Co source and a high-resolution 200 MHz nuclear magnetic resonance (NMR) spectrometer was used to obtain the phantom ¹H profile in the presence of a linear magnetic field gradient. By observing the temporal evolution of the phantom NMR profile, an apparent ferric ion diffusion coefficient of 0.50 μm²/ms due to ferric ions diffusion was obtained. In any medical process where the ionizing radiation is used, the dose planning and the dose delivery are the key elements for the patient safety and success of treatment. These points become even more important in modern conformal radio therapy techniques, such as stereotactic radiosurgery, where the delivered dose in a single session of treatment can be an order of magnitude higher than the regular doses of radiotherapy. Several methods have been proposed to obtain the three-dimensional (3-D) dose distribution. Recently, we proposed an alternative method for the 3-D radiation dose mapping, where the ionizing radiation modifies the local relative concentration of Fe²⁺/Fe³⁺ in a phantom containing Fricke gel and this variation is associated to the MR image intensity. The smearing of the intensity gradient is proportional to the diffusion coefficient of the Fe³⁺ and Fe²⁺ in the phantom. There are several methods for measurement of the ionic diffusion using NMR, however, they are applicable when the diffusion is not very slow.     

Identification of potential trypanothione reductase inhibitors among commercially available $$\upbeta $$-carboline derivatives using chemical space,lead-like and drug-like filters,pharmacophore models and molecular docking

American trypanosomiasis or Chagas disease caused by the protozoan Trypanosoma cruzi (T. cruzi) is an important endemic trypanosomiasis in Central and South America. This disease was considered to be a priority in the global plan to combat neglected tropical diseases, 2008–2015, which indicates that there is an urgent need to develop more effective drugs. The development of new chemotherapeutic agents against Chagas disease can be related to an important biochemical feature of T. cruzi: its redox defense system. This system is based on trypanothione (\(N^{1}\),\(N^{8}\)-bis(glutathyonil)spermidine) and trypanothione reductase (TR), which are rather unique to trypanosomes and completely absent in mammalian cells. In this regard, tricyclic compounds have been studied extensively due to their ability to inhibit the T. cruzi TR. However, synthetic derivatives of natural products, such as \(\upbeta \)-carboline derivatives (\(\upbeta \)-CDs), as potential TR inhibitors, has received little attention. This study presents an analysis of the structural and physicochemical properties of commercially available \(\upbeta \)-CDs in relation to compounds tested against T. cruzi in previously reported enzymatic assays and shows that \(\upbeta \)-CDs cover chemical space that has not been considered for the design of TR inhibitors. Moreover, this study presents a ligand-based approach to discover potential TR inhibitors among commercially available \(\upbeta \)-CDs, which could lead to the generation of promising \(\upbeta \)-CD candidates.     

Controllable propagation of light pulses in Er-doped fibers with saturable absorption

We report controllable (slow or fast) propagation of low-intensity probe-light pulses through erbium-doped fiber periodically saturated by the synchronized master-pulse sequence. These two pulse sequences could have significantly different carrier wavelengths within the fundamental absorption spectrum 1470-1570 nm of Er(+3) ions. The effect of fractional delay or advancement grew with the fiber optical absorption at the probe wavelength and could be significantly stronger than that at the saturating wavelength. The probe-pulse advancement was observed in the case when the saturating and probe waves were modulated approximately in antiphase. The observed effects are explained in the framework of a simple model of a periodically saturated homogeneously broadened absorption line.     

Effect of Concentration on the Photophysics of Dyes in Light‐Scattering Materials.

Photoactive materials based on dye molecules incorporated into thin films or bulk solids are useful for applications as photosensitization, photocatalysis, solar cell sensitization and fluorescent labeling, among others. In most cases, high concentrations of dyes are desirable to maximize light absorption. Under these circumstances, the proximity of dye molecules leads to the formation of aggregates and statistical traps, which dissipate the excitation energy and lower the population of excited states. The search for enhancement of light collection, avoiding energy wasting requires accounting the photophysical parameters quantitatively, including the determination of quantum yields, complicated by the presence of light scattering when particulate materials are considered. In this work we summarize recent advances on the photophysics of dyes in light‐scattering materials, with particular focus on the effect of dye concentration. We show how experimental reflectance, fluorescence and laser‐induced optoacoustic spectroscopy data can be used together with theoretical models for the quantitative evaluation of inner filter effects, fluorescence and triplet formation quantum yields and energy transfer efficiencies.     

Pressure-induced two-color photoluminescence in MnF(2) at room temperature

A novel two-color photoluminescence (PL) is found in MnF(2) at room temperature under high pressure. Contrary to low-temperature PL, PL at room temperature is unusual in transition-metal concentrated materials like MnF(2), since the deexcitation process at room temperature is fully governed by energy transfer to nonradiative centers. We show that room-temperature PL in MnF(2) originates from two distinct Mn(2+) emissions in the high-pressure cotunnite phase. The electronic structure and the excited-state dynamics are investigated by time-resolved emission and excitation spectroscopy at high pressure.     

Organozinc Pivalate Reagents: Segregation,Solubility, Stabilization,and Structural Insights

The pivalates RZnOPiv?Mg(OPiv)X?n LiCl (OPiv=pivalate; R=aryl; X=Cl, Br, I) stand out amongst salt‐supported organometallic reagents, because apart from their effectiveness in Negishi cross‐coupling reactions, they show more resistance to attack by moist air than conventional organometallic compounds. Herein a combination of synthesis, coupling applications, X‐ray crystallographic studies, NMR (including DOSY) studies, and ESI mass spectrometric studies provide details of these pivalate reagents in their own right. A p‐tolyl case system shows that in [D₈]THF solution these reagents exist as separated Me(p‐C₆H₄)ZnCl and Mg(OPiv)₂ species. Air exposure tests and X‐ray crystallographic studies indicate that Mg(OPiv)₂ enhances the air stability of aryl zinc species by sequestering H₂O contaminants. Coupling reactions of Me(p‐C₆H₄)ZnX (where X=different salts) with 4‐bromoanisole highlight the importance of the presence of Mg(OPiv)₂. Insight into the role of LiCl in these multicomponent mixtures is provided by the molecular structure of [(THF)₂Li₂(Cl)₂(OPiv)₂Zn].     

Electro-Mechanochemical Atom Transfer Radical Cyclizations using Piezoelectric BaTiO3

The formation and regeneration of active Cu^I species is a fundamental mechanistic step in copper-catalyzed atom transfer radical cyclizations (ATRC). Typically, the presence of the catalytically active Cu^I species in the reaction mixture is secured by using high Cu^I catalyst loadings or the addition of complementary reducing agents. In this study it is demonstrated how the piezoelectric properties of barium titanate (BaTiO₃) can be harnessed by mechanical ball milling to induce electrical polarization in the strained piezomaterial. This strategy enables the conversion of mechanical energy into electrical energy, leading to the reduction of a Cu^II precatalyst into the active Cu^I species in copper-catalyzed mechanochemical solvent-free ATRC reactions.     

Diels-Alder reaction mechanisms of substituted chiral anthracene: A theoretical study based on the reaction force and reaction electronic flux

Quantum chemical calculations were used to study the mechanism of Diels-Alder reactions involving chiral anthracenes as dienes and a series of dienophiles. The reaction force analysis was employed to obtain a detailed scrutiny of the reaction mechanisms, it has been found that thermodynamics and kinetics of the reactions are quite consistent: the lower the activation energy, the lower the reaction energy, thus following the Bell-Evans-Polanyi principle. It has been found that activation energies are mostly due to structural rearrangements that in most cases represented more than 70% of the activation energy. Electronic activity mostly due to changes in σ and π bonding were revealed by the reaction electronic flux (REF), this property helps identify whether changes on σ or π bonding drive the reaction. Additionally, new global indexes describing the behavior of the electronic activity were introduced and then used to classify the reactions in terms of the spontaneity of their electronic activity. Local natural bond order electronic population analysis was used to check consistency with global REF through the characterization of specific changes in the electronic density that might be responsible for the activity already detected by the REF. Results show that reactions involving acetoxy lactones are driven by spontaneous electronic activity coming from bond forming/strengthening processes; in the case of maleic anhydrides and maleimides it appears that both spontaneous and non-spontaneous electronic activity are quite active in driving the reactions.     

Multi-scale simulation reveals that an amino acid substitution increases photosensitizing reaction inputs in Rhodopsins

Evaluating the availability of molecular oxygen (O₂) and energy of excited states in the retinal binding site of rhodopsin is a crucial challenging first step to understand photosensitizing reactions in wild-type (WT) and mutant rhodopsins by absorbing visible light. In the present work, energies of the ground and excited states related to 11-cis-retinal and the O₂ accessibility to the β-ionone ring are evaluated inside WT and human M207R mutant rhodopsins. Putative O₂ pathways within rhodopsins are identified by using molecular dynamics simulations, Voronoi-diagram analysis, and implicit ligand sampling while retinal energetic properties are investigated through density functional theory, and quantum mechanical/molecular mechanical methods. Here, the predictions reveal that an amino acid substitution can lead to enough energy and O₂ accessibility in the core hosting retinal of mutant rhodopsins to favor the photosensitized singlet oxygen generation, which can be useful in understanding retinal degeneration mechanisms and in designing blue-lighting-absorbing proteic photosensitizers.