Analysis method of the angiotensin-I converting enzyme inhibitory activity based on micellar electrokinetic chromatography.

A micellar electrokinetic chromatography (MEKC) method was developed for estimating the angiotensin-I converting enzyme (ACE) inhibitory activity by separating the hippuric acid liberated in the ACE reaction mixture in the presence of an inhibitor, captopril. The hippuric acid was successfully separated and detected by MEKC with a 25 mM sodium dodecyl sulfate solution in a 25 mM phosphate-50 mM borate buffer at pH 7.0; the total analysis took about 5 min. A good linear relationship was observed between the inhibitor and the peak area of hippuric acid release. No significant difference in the ACE inhibitory activity (IC50) of captopril (an antihypertensive medicine) or autolyzed-mushrooms (functional foods) was observed between the conventional method and the MEKC method. The MEKC method was found to be a useful technique for a rapid assay of the ACE inhibitory activity.     

Buckling-driven morphological transformation of droplets of a mixed colloidal suspension during evaporation-induced self-assembly by spray drying

Morphological transformation during evaporation-induced self-assembly of a mixed colloidal suspension in micrometric droplets has been investigated. It has been demonstrated that a buckling-driven shape transition of drying droplets of mixed colloidal suspension takes place during evaporation-induced self-assembly. Further, it is also shown that the distortion modulations get significantly amplified with enhancement in volume fraction of anisotropic soft colloidal component of the mixed colloids. It has been argued that the reduction in elastic modulus of formed shell, at the boundary of a drying droplet, and the anisotropic nature of one of the colloidal components facilitate the deformation process. Hierarchical structures of these assembled colloidal grains have been probed using electron microscopy and scattering techniques.     

Solute transport and composition profile during direct metal deposition with coaxial powder injection

Direct metal deposition (DMD) with coaxial powder injection allows fabrication of three-dimensional geometry with rapidly solidified microstructure. During DMD, addition of powder leads to the interaction between laser and powder, and also the redistribution of solute. The concentration distribution of the alloying element is very important for mechanical properties of the deposited clad material. The evolution of concentration distribution of carbon and chromium in the molten pool is simulated using a self-consistent three-dimensional model, based on the solution of the equations of mass, momentum, energy conservation and solute transport in the molten pool. The experimental and calculated molten pool geometry is compared for model validation purposes.     

The Generalized Second Law of Thermodynamics of?the?Universe Bounded by the Event Horizon and?Modified Gravity Theories

In this paper, we investigate the validity of the generalized second law of thermodynamics of the universe bounded by the event horizon. Here we consider homogeneous and isotropic model of the universe filled with perfect fluid in one case and in another case holographic model of the universe has been considered. In the third case the matter in the universe is taken in the form of non-interacting two fluid system as holographic dark energy and dust. Here we study the above cases in the Modified gravity, f(R) gravity.     

Thermodynamics of Lema$$\hat{i}$$ tre−Tolman−Bondi Model

Here we consider our universe as inhomogeneous spherically symmetric Lema [^(i)]{\hat{i}} tre−Tolman−Bondi Model and analyze the thermodynamics of this model of the universe. The trapping horizon is calculated and is found to coincide with the apparent horizon. The Einstein field equations are shown to be equivalent with the unified first law of thermodynamics. Finally assuming the first law of thermodynamics validity of the generalized second law of thermodynamics is examined at the apparent horizon for the perfect fluid and at the event horizon for holographic dark energy.     

Conformational and electronic consequences in crafting extended, π-conjugated, light-harvesting macrocycles

The synthesis of a new series of free‐base, Ni^II and Zn^II 2,3,12,13‐tetra(ethynyl)‐5,10,15,20‐tetraphenyl porphyrins is described. Upon heating, two of the four ethynyl moieties undergo Bergman cyclization to afford the monocyclized 2,3‐diethynyl‐5,20‐diphenylpiceno[10,11,12,13,14,15‐jklmn]porphyrin in 30 %, 10 %, and trace yields, respectively. The structures of all products were investigated by using quantum chemical calculations and the free‐base analogue was isolated and crystallized; all compounds show significant deviation from the idealized planar structure. No fully‐cyclized bispiceno[20,1,2,3,4,5,10,11,12,13,14,15‐fghij]porphyrin was isolated from the reaction mixture. To understand why only two of the four enthynyl groups undergo Bergman cyclization, the reaction coordinates were examined by using DFT at the PWPW91/cc‐pVTZ(‐f) level coupled to a continuum solvation model. The barrier to cyclization of the second pair of ethynyl groups was found to be 5.5 kcal mol^?1 higher than the first, suggesting a negative cooperative effect and significantly slower rate for the second cyclization. Cyclization reactions for model porphyrin–enediynes with ethene‐ and H‐functionality substitutions at the meso‐phenyl rings were also examined, and found to have a similar barrier to diradical formation for the second cyclization event as for the first in these highly planar molecules. By enforcing an artificial 30° cant in two of the pyrrole rings of the porphyrin, the second barrier was increased by 2 kcal mol^?1 in the ethene model system; this suggests that the disruption of the π conjugation of the extended porphyrin structure is the cause of the increased barrier to the second cyclization event.     

Exploring nucleoside hydrolase catalysis in silico: molecular dynamics study of enzyme-bound substrate and transition state

The mechanism of action of inosine-uridine nucleoside hydrolase has been investigated by long-term molecular dynamics (MD) simulation in TIP3P water using stochastic boundary conditions. Five MD studies have been performed with enzyme substrate complex (E.S), enzyme substrate complex with protonated His241 (EH.S), enzyme transition state complex (E.TS), enzyme transition state complex with protonated His241 (EH.TS), and His241Ala transition state complex E(H241A).TS. Special attention has been given to the role of His241, which has been considered as the general acid catalyst to assist departure of the leaving nucleobase on the basis of its location in the active site in the X-ray crystal structure (). Yet on the basis of the location in the active site, Tyr229 is closer to the aniline ring of pAPIR as compared to His241. On initiation of MD simulations, His241 does not approach the nucleobase in the structures of EH.S, E.S, EH.TS, and E.TS. In the solvated enzyme, Tyr229, which is a member of the hydrogen bonding network inosine O2'.Asp14.His241.Tyr229.inosine N7, serves as a proton source to the leaving nucleobase. The loss of significant activity of His241Ala mutant is shown to be related to the disruption of the above hydrogen bonded network and the distancing of Tyr229 from inosine N7. The structures of the enzyme complexes with substrate or TS are not visibly altered on protonation of His241, a most unusual outcome. The bell-shaped pH dependence upon pK(app)'s of 7.1 and 9.1 may be attributed to the necessity of the dissociation of Asp10 or Asp15 and the acid form of Tyr229, respectively. In TS, the residue Ile81 migrated closer, whereas Arg233 moved away from the nucleobase. The probability of ribooxocarbenium ion stabilization by Asn168 and Asp14 is discussed. The Asp14-CO(2)(-) is hydrogen bonded to the ribose 2'-OH for 96% of the MD simulation time. Nucleophilic addition of water138 to ribooxocarbenium ion is suggested to be assisted by the proton shuttle from water138 --> Asp10 --> Asp15 --> water pool. An anticorrelation motion between Tyr229-OH and Asn168-OD1 in EH.S and E.S is observed. The relationship of this anticorrelated motion to mechanism, if any, deserves further exploration, perhaps the formation of a near attack conformation.     

Control of buckling in colloidal droplets during evaporation-induced assembly of nanoparticles

Micrometric grains of anisotropic morphology have been achieved by evaporation-induced self-assembly of silica nanoparticles. The roles of polymer concentration and its molecular weight in controlling the buckling behavior of drying droplets during assembly have been investigated. Buckled doughnut grains have been observed in the case of only silica colloid. Such buckling of the drying droplet could be arrested by attaching poly(ethylene glycol) on the silica surface. The nature of buckling in the case of only silica as well as modified silica colloids has been explained in terms of theory of homogeneous elastic shell under capillary pressure. However, it has been observed that colloids, modified by polymer with relatively large molecular weight, gives rise to buckyball-type grains at higher concentration and could not be explained by the above theory. It has been demonstrated that the shell formed during drying of colloidal droplet in the presence of polymer becomes inhomogeneous due to the presence of soft polymer rich zones on the shell that act as buckling centers, resulting in buckyball-type grains.