Self-Organized Dynamical Equilibrium in the Corrosion of Random Solids

Self-organized criticality is characterized by power law correlations in the non-equilibrium steady state of externally driven systems. A dynamical system proposed here self-organizes itself to a critical state with no characteristic size at ``dynamical equilibrium''. The system is a random solid in contact with an aqueous solution and the dynamics is the chemical reaction of corrosion or dissolution of the solid in the solution. The initial difference in chemical potential at the solid-liquid interface provides the driving force. During time evolution, the system undergoes two transitions, roughening and anti-percolation. Finally, the system evolves to a dynamical equilibrium state characterized by constant chemical potential and average cluster size. The cluster size distribution exhibits power law at the final equilibrium state.Comment: 11 pages, 5 figure

Coulombic Energy Transfer and Triple Ionization in Clusters

Using neon and its dimer as a specific example, it is shown that excited Auger decay channels that are electronically stable in the isolated monomer can relax in a cluster by electron emission. The decay mechanism, leading to the formation of a tricationic cluster, is based on an efficient energy-transfer process from the excited, dicationic monomer to a neighbor. The decay is ultrafast and expected to be relevant to numerous physical phenomena involving core holes in clusters and other forms of spatially extended atomic and molecular matter.Comment: 5 pages, 1 figure, to be published in PR

Siegert pseudostates: completeness and time evolution

Within the theory of Siegert pseudostates, it is possible to accurately calculate bound states and resonances. The energy continuum is replaced by a discrete set of states. Many questions of interest in scattering theory can be addressed within the framework of this formalism, thereby avoiding the need to treat the energy continuum. For practical calculations it is important to know whether a certain subset of Siegert pseudostates comprises a basis. This is a nontrivial issue, because of the unusual orthogonality and overcompleteness properties of Siegert pseudostates. Using analytical and numerical arguments, it is shown that the subset of bound states and outgoing Siegert pseudostates forms a basis. Time evolution in the context of Siegert pseudostates is also investigated. From the Mittag-Leffler expansion of the outgoing-wave Green's function, the time-dependent expansion of a wave packet in terms of Siegert pseudostates is derived. In this expression, all Siegert pseudostates--bound, antibound, outgoing, and incoming--are employed. Each of these evolves in time in a nonexponential fashion. Numerical tests underline the accuracy of the method

Copper complexes as chemical nucleases

Redox active mononuclear and binuclear copper(II) complexes have been prepared and structurally characterized. The complexes have planar N-donor heterocyclic bases like 1,10-phenanthroline (phen), dipyridoquinoxaline (dpq) and dipyridophenazine (dppz) ligands that are suitable for intercalation to B-DNA. Complexes studied for nuclease activity have the formulations [Cu(dpq)2(H2O)] (ClO4)2.H2O (1), [CuL(H2O)2(μ-ox)](ClO4)2 (L = bpy,2; phen,3; dpq,4; and dppz,5) and [Cu(L)(salgly)] (L = bpy,6; phen,7; dpq,8; and dppz,9), where salgly is a tridentate Schiff base obtained from the condensation of glycine and salicylaldehyde. The dpq complexes are efficient DNA binding and cleavage active species. The dppz complexes show good binding ability but poor nuclease activity. The cleavage activity of thebis-dpq complex is significantly higher than thebis-phen complex of copper(II). The nuclease activity is found to be dependent on the intercalating nature of the complex and on the redox potential of the copper(II)/copper(I) couple. The ancillary ligand plays a significant role in binding and cleavage activity

Noncovalent Interactions by QMC: Speedup by One-Particle Basis-Set Size Reduction

While it is empirically accepted that the fixed-node diffusion Monte-Carlo (FN-DMC) depends only weakly on the size of the one-particle basis sets used to expand its guiding functions, limits of this observation are not settled yet. Our recent work indicates that under the FN error cancellation conditions, augmented triple zeta basis sets are sufficient to achieve a benchmark level of 0.1 kcal/mol in a number of small noncovalent complexes. Here we report on a possibility of truncation of the one-particle basis sets used in FN-DMC guiding functions that has no visible effect on the accuracy of the production FN-DMC energy differences. The proposed scheme leads to no significant increase in the local energy variance, indicating that the total CPU cost of large-scale benchmark noncovalent interaction energy FN-DMC calculations may be reduced.Comment: ACS book chapter, accepte

A niche-mimicking polymer hydrogel-based approach to identify molecular targets for tackling human pancreatic cancer stem cells.

BACKGROUND: Pancreatic adenocarcinoma (PAAD) is one of the most fatal human cancers, but effective therapies remain to be established. Cancer stem cells (CSCs) are highly resistant to anti-cancer drugs and a deeper understanding of their microenvironmental niche has been considered important to provide understanding and solutions to cancer eradication. However, as the CSC niche is composed of a wide variety of biological and physicochemical factors, the development of multidisciplinary tools that recapitulate their complex features is indispensable. Synthetic polymers have been studied as attractive biomaterials due to their tunable biofunctionalities, while hydrogelation technique further renders upon them a diversity of physical properties, making them an attractive tool for analysis of the CSC niche. METHODS: To develop innovative materials that recapitulate the CSC niche in pancreatic cancers, we performed polymer microarray analysis to identify niche-mimicking scaffolds that preferentially supported the growth of CSCs. The niche-mimicking activity of the identified polymers was further optimized by polyethylene glycol (PEG)-based hydrogelation. To reveal the biological mechanisms behind the activity of the optimized hydrogels towards CSCs, proteins binding onto the hydrogel were analyzed by liquid chromatography with tandem mass spectrometry (LC-MS/MS), and the potential therapeutic targets were validated by looking at gene expression and patients' outcome in the TCGA database. RESULTS: PA531, a heteropolymer composed of 2-methoxyethyl methacrylate (MEMA) and 2-(diethylamino)ethyl methacrylate (DEAEMA) (5.5:4.5) that specifically supports the growth and maintenance of CSCs was identified by polymer microarray screening using the human PAAD cell line KLM1. The polymer PA531 was converted into five hydrogels (PA531-HG1 to HG5) and developed to give an optimized scaffold with the highest CSC niche-mimicking activities. From this polymer that recapitulated CSC binding and control, the proteins fetuin-B and angiotensinogen were identified as candidate target molecules with clinical significance due to the correlation between gene expression levels and prognosis in PAAD patients and the proteins associated with the niche-mimicking polymer. CONCLUSION: This study screened for biofunctional polymers suitable for recapitulation of the pancreatic CSC niche and one hydrogel with high niche-mimicking abilities was successfully fabricated. Two soluble factors with clinical significance were identified as potential candidates for biomarkers and therapeutic targets in pancreatic cancers. Such a biomaterial-based approach could be a new platform in drug discovery and therapy development against CSCs, via targeting of their niche

Fusion of 6^{6}Li with 159^{159}Tb} at near barrier energies

Complete and incomplete fusion cross sections for $^{6}$Li+$^{159}$Tb have been measured at energies around the Coulomb barrier by the $\gamma$-ray method. The measurements show that the complete fusion cross sections at above-barrier energies are suppressed by $\sim$34% compared to the coupled channels calculations. A comparison of the complete fusion cross sections at above-barrier energies with the existing data of $^{11,10}$B+$^{159}$Tb and $^{7}$Li+$^{159}$Tb shows that the extent of suppression is correlated with the $\alpha$-separation energies of the projectiles. It has been argued that the Dy isotopes produced in the reaction $^{6}$Li+$^{159}$Tb, at below-barrier energies are primarily due to the $d$-transfer to unbound states of $^{159}$Tb, while both transfer and incomplete fusion processes contribute at above-barrier energies.Comment: Phys. Rev. C (accepted

Nonfactorization and the decays Ds+→ϕπ+,ϕρ+D_s^+ \to \phi \pi^+, \phi \rho^+ and ϕl+νl\phi l^+ \nu_l

In six chosen scenarios for the $q^2$ dependence of the form factors involved in $D_s^+ \rightarrow \phi$ transition, we have determined the allowed domain of $x = A_2(0) / A_1(0)$ and $y = V(0)/A_1(0)$ from the experimentally measured ratios $R_{sl} = \Gamma(D_s^+ \rightarrow \phi l^+ \nu_l)/\Gamma(D_s^+ \rightarrow \phi \pi^+)$ and $R_h = \Gamma(D_s^+ \rightarrow \phi \rho^+)/\Gamma(D_s^+ \rightarrow \phi \pi^+)$ in a scheme that uses the $N_c =3$ value of the phenomenological parameter $a_1$ and includes nonfactorized contribution. We find that the experimentally measured values of $x$ and $y$ from semileptonic decays of $D_s^+$ favor solutions which have significant nonfactorized contribution, and, in particular, $R_{sl}$ favors solutions in scenarios where $A_1(q^2)$ is either flat or decreasing with $q^2$.Comment: 15 pages, Latex, four figure (available on request)