Bonding of macromolecular hydrogels using perturbants

This work describes a method to bond patterned macromolecular gels into monolithic structures using perturbants. Bonding strengths for a variety of solutes follow a Hofmeister ordering; this result and optical measurements indicate that bonding occurs by reversible perturbation of contacting gels. The resulting microfluidic gels are mechanically robust and can serve as scaffolds for cell culture.     

Variational calculation of second-order reduced density matrices by strong N-representability conditions and an accurate semidefinite programming solver

The reduced density matrix (RDM) method, which is a variational calculation based on the second-order reduced density matrix, is applied to the ground state energies and the dipole moments for 57 different states of atoms, molecules, and to the ground state energies and the elements of 2-RDM for the Hubbard model. We explore the well-known N-representability conditions (P, Q, and G) together with the more recent and much stronger T1 and T2(') conditions. T2(') condition was recently rederived and it implies T2 condition. Using these N-representability conditions, we can usually calculate correlation energies in percentage ranging from 100% to 101%, whose accuracy is similar to CCSD(T) and even better for high spin states or anion systems where CCSD(T) fails. Highly accurate calculations are carried out by handling equality constraints and/or developing multiple precision arithmetic in the semidefinite programming (SDP) solver. Results show that handling equality constraints correctly improves the accuracy from 0.1 to 0.6 mhartree. Additionally, improvements by replacing T2 condition with T2(') condition are typically of 0.1-0.5 mhartree. The newly developed multiple precision arithmetic version of SDP solver calculates extraordinary accurate energies for the one dimensional Hubbard model and Be atom. It gives at least 16 significant digits for energies, where double precision calculations gives only two to eight digits. It also provides physically meaningful results for the Hubbard model in the high correlation limit.     

Application of quorum response and information entropy to animal collective motion modeling

“Quorum response” is a type of social interaction in which an individual's chance of choosing an option is a nonlinear function of the number of other individuals already committing to it. This interaction has been widely used to characterize collective decision‐making in animal groups. Here, we first implement it in 1D and 2D models of collective animal movement, and find that the resulting group motion shows the characteristic behaviors which were observed in previous experimental and modeling studies. Further, the analytic form of quorum response renders us an opportunity to propose a mean field theory in 1D with globally interacting particles, so we can estimate the average time period between changes in the group direction (mean switching time). We find that the theoretical results provide an upper bound to the simulation results when the interaction radius grows from local to global. Information entropy, a concept widely used to quantify the uncertainty of a random variable, is introduced here as a new order parameter to study the evolution of systems of two cases in 2D models. The explicitly formulated probability of a particle's dynamic state in the framework of quorum response makes information entropy directly computable. We find that, besides the global order, information entropy can also capture the structural features of local order of the system which previous order parameters such as alignment cannot. © 2016 Wiley Periodicals, Inc. Complexity 21: 584–592, 2016     

Mode shaping in multicore fibers

We propose a novel multicore fiber design strategy for obtaining a flat in-phase supermode that optimizes utilization of the active medium inversion in the multiple cores. The spatially flat supermode is achieved by engineering the fiber so that the total mutual coupling between neighboring active cores is equal. Different designs suitable for different fabrication processes, such as stack-and-draw and drilling, are proposed. An important improvement over previous methods is the design simplicity and better tolerance to perturbations.     

Hexacoordinated phosphates: how to teach old chiral anions new asymmetric tricks

Chemical reactions and processes often involve chiral, yet racemic, cationic reagents, intermediates, or products. To afford instead nonracemic or enantiopure compounds, an asymmetric ion pairing of the cations with enantiopure anions can be considered--the counter ions behaving as asymmetric auxiliaries, ligands, or reagents. Detailed herein is a short review of our approach toward gaining reliable and predictable control over stereoselective ion pairing phenomena through the synthesis and use of novel configurationally stable hexacoordinated phosphate anions.     

Analytical performance of the AtheNA MultiLyte® ANA II assay in sera from lupus patients with multiple positive ANAs

The purpose of this study was to evaluate the precision and accuracy of a commercial multiplexed kit for the measurement of 9 anti-nuclear antibodies (ANAs; anti-SS/A, anti-SS/B, anti-Sm, anti-RNP, anti-Jo-1, anti-Scl-70, anti-dsDNA, anti-Centromere B, and anti-Histone), and to compare these results to a subset of ANAs measured by enzyme-linked immunosorbent assays (ELISA) and immunodiffusion (ID). Sera were obtained from 22 systemic lupus erythematosus (SLE) patients, twelve controls and five others (commercial source) with various autoimmune diseases. ANA results from the AtheNA MultiLyte ANA II Assay (AtheNA) were compared to ELISA results (controls) and patients (ID). The AtheNA interassay coefficients of variation (CVs, N = 39, performed in duplicate; replicated 3x) ranged from 6.2% to 16.7% (mean = 9.8%), while the intra-assay CVs ranged from 5.8% to 14.3% (mean = 10.8%). Compared to results for SLE cases and controls, the sensitivity of AtheNA ranged from 85.7% to 100% (mean = 97.1%), while diagnostic specificity ranged from 16.7% to 100% (mean = 71.6%). There was significant agreement (P values ranging from 0.0001 to 0.03) when analytes coanalyzed by AtheNA and ELISA/ID were evaluated using Cohen's kappa (kappa values ranging from 0.376 to 1.000). No false positive ANA results were observed for either the control or commercial source autoimmune disease sera. These results indicate that the AtheNA assay is a precise and accurate alternative for performing multiple ELISAs or IDs in the diagnosis of autoimmune diseases, especially when the number of sera to be tested is large, such as in clinical screening or epidemiologic studies. It also appears that the AtheNA assay identifies positive ANA specificities which are missed by ID techniques, suggesting that it may have greater analytical sensitivity for some ANAs.     

Access to Vinyl Ethers and Ketones with Hypervalent Iodine Reagents as Oxy-Allyl Cation Synthetic Equivalents

We report an Umpolung strategy of enol ethers to generate oxy-allyl cation equivalents based on the use of hypervalent iodine reagents. Under mild basic conditions, the addition of nucleophiles to aryloxy-substituted vinylbenziodoxolone (VBX) reagents, easily available in two steps from silyl alkynes, resulted in the stereoselective formation of substituted aryl enol ethers. The reaction was most efficient with phenols as nucleophiles, but preliminary results were also achieved for C- and N- nucleophiles. In absence of external nucleophiles, the 2-iodobenzoate group of the reagent was transferred. The obtained aryl enol ethers could then be transformed into α-difunctionalized ketones by oxidation. The described “allyl cation”-like reactivity contrast with the well-established “vinyl-cation” behavior of alkenyl iodonium salts.     

Population models with diffusion, strong Allee effect, and nonlinear boundary conditions

We consider a population model with diffusion, a strong Allee effect per capita growth function, and constant yield harvesting. In particular, we focus our study on a population living in a patch, Ω⊆Rⁿ with n≥1, that satisfies a certain nonlinear boundary condition. We establish our existence results by the method of sub-supersolutions.     

Antibody capture by mixed-mode chromatography: a comprehensive study from determination of optimal purification conditions to identification of contaminating host cell proteins

We evaluated mixed mode chromatography for the capture of recombinant antibodies from CHO cell culture supernatants. We studied PPA HyperCel, HEA HyperCel, MEP HyperCel and Capto adhere resins, which all contain hydrophobic and cationic groups. A microplate approach combined with DoE modeling allowed the exploration of the complex behaviors of these mixed mode resins. Optimal conditions for antibody purification and host cell proteins (HCPs) elimination were determined and then directly up-scaled to laboratory columns. Then we used mass spectrometry to identify the major HCPs potentially coeluted with the antibody. Differences between the four resins in terms of amount, complexity and identity of the HCPs present in the elution fractions were investigated.