Tautomerism of uracil probed via infrared spectroscopy of singly hydrated protonated uracil

Tautomerism of the nucleobase uracil is characterized in the gas phase through IR photodissociation spectroscopy of singly hydrated protonated uracil created with tandem mass spectrometric methods in a commercially available Fourier transform ion cyclotron resonance mass spectrometer. Protonated uracil ions generated by electrospray ionization are re-solvated in a low-pressure collision cell filled with a mixture of water vapor seeded in argon. Their structure is investigated by IR photodissociation spectroscopy in the NH and OH stretching region (2500-3800 cm(-1)) with a tabletop IR laser source and in the 1000-2000 cm(-1) range with a free-electron laser. In both regions the IR photodissociation spectrum exhibits well-resolved spectral signatures that point to the presence of two different types of structure for monohydrated protonated uracil, which result from the two lowest-energy tautomers of uracil. Ab initio calculations confirm that no water-catalyzed tautomerization occurs during the re-solvation process, indicating that the two protonated forms of uracil directly originate from the electrospray process.     

Synthesis of Polylactide under Inert Atmosphere and Vacuum

The ring-opening polymerization (ROP) of L- lactide was carried out in bulk using various initiators along with triphenylphosphine (PPh₃) as co-initiator. Equimolar addition of triphenylphosphine increased the molecular masses of polylactide (PLA). The polymerization was carried out at 403.15 K up to 155 hr. Different experiments were carried out over a wide range of monomer to initiator (M_o/I_o) ratios. It was found that maximum molecular weight of polylactide was observed when M_o/I_o ratio was 2500–2700. Polymerization reactions were carried out under two different environments in the reaction vessel, an inert cover and a partial vacuum. The average molecular weight of polylactide was determined by using size exclusion chromatography. The increase of polymerization time increased the weight average molecular weight but after prolonged reaction time, the molecular weight decreased gradually.     

Investigation of the interfacial tension of complex coacervates using field-theoretic simulations

Complex coacervation, a liquid-liquid phase separation that occurs when two oppositely charged polyelectrolytes are mixed in a solution, has the potential to be exploited for many emerging applications including wet adhesives and drug delivery vehicles. The ultra-low interfacial tension of coacervate systems against water is critical for such applications, and it would be advantageous if molecular models could be used to characterize how various system properties (e.g., salt concentration) affect the interfacial tension. In this article we use field-theoretic simulations to characterize the interfacial tension between a complex coacervate and its supernatant. After demonstrating that our model is free of ultraviolet divergences (calculated properties converge as the collocation grid is refined), we develop two methods for calculating the interfacial tension from field-theoretic simulations. One method relies on the mechanical interpretation of the interfacial tension as the interfacial pressure, and the second method estimates the change in free energy as the area between the two phases is changed. These are the first calculations of the interfacial tension from full field-theoretic simulation of which we are aware, and both the magnitude and scaling behaviors of our calculated interfacial tension agree with recent experiments.     

Coordination stability between metal/ligands interaction by modern spectroscopic studies: IR, electronic, EPR and cyclic voltammetry of cobalt(II) complexes with organic skeleton containing cyclic ligands

A comparative investigation of the interaction of two pyrrole-substituted, mixed oxygen and nitrogen donor, macrocycles ligands have been designed and their coordination interaction with cobalt(II) is studied. Cobalt(II) salts combine with a tetradentate and hexadentate macrocyclic nitrogen/oxygen donor ligands and formed novel cobalt(II) complexes which are characterized by elemental analysis, molar conductance, magnetic moments, mass, (1)H NMR, IR, electronic and EPR spectral studies. At the room temperature magnetic moment for cobalt(II) complexes lie in the range 4.70-5.01BM, which is higher than the spin-only value. All the complexes are high-spin type and have three unpaired electrons. Therefore, the electronic confutation and the splitting of the orbital will be t(2g)(5)eg(2). The electrochemical behaviour of the cobalt(II) complexes, the Co(III)/Co(II) couple are observed. Their positive potential indicates that metal in lower oxidation state is strongly bound to these ligands. The difference between the potential of the anodic peak and cathodic peak remains constant in all complexes. Also, the ratio between the cathodic peak current and square root of the scan rate is practically constant for the studied complexes.     

Nickel(II) complexes with different chromospheres containing macrocyclic ligands: spectroscopic and electrochemical studies

The mixed donor tetradentate (L(1)=N(2)O(2)) and pentadentate (L(2)=N(2)O(2)S) ligands have been prepared by the interaction of 1,3-diaminopropane and thiodiglycolic acid with diamine. These ligands possess two dissimilar coordination sites. Different types of complexes were obtained which have different stoichiometry depending upon the type of ligands. Their structural investigation have been based on elemental analysis, magnetic moment and spectral (ultraviolet, infrared, (1)H NMR, (13)C NMR and mass spectroscopy methods). The Ni(II) complexes show magnetic moments corresponding to two unpaired electrons except [Ni(L(1))](NO(3))(2) which is diamagnetic. Ligand field parameters of these complexes were compared. N(2)O(2)S donor ligand complexes show higher values of ligand field parameters, which are used to detect their geometries. The redox properties and stability of the complexes toward oxidation waves explored by cyclic voltammetry are related to the electron-withdrawing or releasing ability of the substituents of macrocyclic ligands moiety. The Ni(II) complexes displayed Ni(II)/Ni(I) couples irreversible waves associated with Ni(III)/Ni(II) process.     

Effect of additional hydrogen peroxide to H2O2...(H2O)n, n=1 and 2 complexes: quantum chemical study

Hydrogen peroxide, H2O2, acts as a particularly strong reactant in aqueous environment. It has been demonstrated earlier that agglomerates with a single peroxide interacting with one and two water molecules manifest in several stable conformers within a narrow energy range. In the present study we seek structural changes brought out by adding an extra H2O2 to these systems at molecular level employing ab initio quantum chemical methods, viz., restricted Hartree-Fock and the second order Moller-Plesset perturbation theory. These clusters exhibit consistent trends in energy hierarchy at both the levels. Further, a many body interaction energy analysis quantifies the strength and cooperativity of hydrogen bonding in the (H2O2)2...(H2O)n, (n=1 and 2) clusters, bringing out structuring/destructuring effects attributed to attachment of water and hydrogen peroxide molecules.     

Is high electric field capable of selectively inducing a covalent-like bond between polar and non-polar molecular species?

It is demonstrated through the present ab initio theoretical investigation that an external electric field can bring about a phenomenal enhancement in the strength of the bond between water and carbon-dioxide molecules from a van der Waals type (binding energy ~0.085 eV), to strong covalent type (binding energy ~7.45 eV), resulting in an exotic molecular complex. The onset of this effect is characterized by an abrupt change in the dipole moment of the composite system at a particular field-value, concomitant with the O–C=O ? O=C–O resonance in the CO₂ moiety of the complex. This field-induced bond formation is further confirmed by the emergence of a characteristic intermolecular stretching mode (~317 cm^?1) in the vibrational response of the system. This exotic bond that exhibits a covalent-like character, which accompanied by a charge-transfer, renders the carbon atom a substantial negative charge.     

Measure free martingales and martingale measures

Let T ⊂ ℝ be a countable set, not necessarily discrete. Let f _t , t ∈ T, be a family of real-valued functions defined on a set Ω. We discuss conditions which imply that there is a probability measure on Ω under which the family f _t , t ∈ T, is a martingale.     

Soft-x-ray harmonic comb from relativistic electron spikes

We demonstrate a new high-order harmonic generation mechanism reaching the "water window" spectral region in experiments with multiterawatt femtosecond lasers irradiating gas jets. A few hundred harmonic orders are resolved, giving μJ/sr pulses. Harmonics are collectively emitted by an oscillating electron spike formed at the joint of the boundaries of a cavity and bow wave created by a relativistically self-focusing laser in underdense plasma. The spike sharpness and stability are explained by catastrophe theory. The mechanism is corroborated by particle-in-cell simulations.     

Enhanced growth of lactobacilli and bioconversion of isoflavones in biotin-supplemented soymilk upon ultrasound-treatment

This study aimed at utilizing ultrasound treatment to further enhance the growth of lactobacilli and their isoflavone bioconversion activities in biotin-supplemented soymilk. Strains of lactobacilli (Lactobacillus acidophilus BT 1088, L. fermentum BT 8219, L. acidophilus FTDC 8633, L. gasseri FTDC 8131) were treated with ultrasound (30 kHz, 100 W) at different amplitudes (20%, 60% and 100%) for 60, 120 and 180 s prior to inoculation and fermentation in biotin-soymilk. The treatment affected the fatty acids chain of the cellular membrane lipid bilayer, as shown by an increased lipid peroxidation (P < 0.05). This led to increased membrane fluidity and subsequently, membrane permeability (P < 0.05). The permeabilized cellular membranes had facilitated nutrient internalization and subsequent growth enhancement (P < 0.05). Higher amplitudes and longer durations of the treatment promoted growth of lactobacilli in soymilk, with viable counts exceeding 9 log CFU/mL. The intracellular and extracellular β-glucosidase specific activities of lactobacilli were also enhanced (P < 0.05) upon ultrasound treatment, leading to increased bioconversion of isoflavones in soymilk, particularly genistin and malonyl genistin to genistein. Results from this study show that ultrasound treatment on lactobacilli cells promotes (P < 0.05) the β-glucosidase activity of cells for the benefit of enhanced (P < 0.05) isoflavone glucosides bioconversion to bioactive aglycones in soymilk.