Using a virtual skeleton to increase printability of topology optimized design for industry-class applications

This article broadens the scheme previously developed to associate topology optimization with additive manufacturing through the use of a virtual skeleton, consisting in solving the same physical problem with a discrete approach and then with a continuum one. This procedure for 3D designs is applied to various domain geometries, to demonstrate its pertinence on high-resolution industrial cases. An algorithm searching for the best printing direction, exploring the solid angle, is also described and validated; the surface-shaped presentation of the result allows immediate understanding of the influence of the discrete problem parameters, while its running time is much lower than a unique continuum optimization simulation, which proves the attractiveness of the method. In the three examples studied, the procedure outputs exhibit greater printability than the ones produced by traditional methods in each of the printing direction tested, albeit responsibility is left to the final user to choose his best trade-off. Furthermore, the unprintable zones are readily displayed to be either reworked or supported. Explanations about increase of convergence likelihood on discrete structures despite the geometry complexity of an industrial application are also provided and demonstrated.     

The effect of alcohol structures on the interaction mode with the hexameric capsule of resorcin[4]arene

After more than a century of research on resorcin[4]arenes (1) it is clear that such systems form spontaneously [1(6)(H(2)O)(8)]-type hexameric capsules in wet, non-polar, organic solvents. However, the interactions of these hexameric capsules with alcohols are far from being solved. Here we provide the results of an extensive study on the interaction of different alcohols with the hexameric capsules of resorcin[4]arene 1a by focusing on the exchange of magnetization manifested in diffusion NMR measurements of such capsular systems. We found that some alcohols such as 2-octyl-1-dodecanol and 1-octadecanol do not interact with the hexamers of 1a, whereas other alcohols such as 3-ethyl-3-pentanol, 2-ethyl-1-butanol and more act as simple guests and are simply encapsulated in the hexamers. Others alcohols such as 3-pentanol, 2-methyl-1-butanol and others, are part of the hexameric structure where they can exchange magnetization with alcohols in the bulk. The bulkier alcohols, due to an increase of the chain length or in branching, have a higher tendency to be encapsulated rather than being part of the hexameric capsule superstructure. This study demonstrate the unique information that diffusion NMR spectroscopy can provide on supramolecular systems in solution and on the precaution that should be exercised when analyzing diffusion NMR data of such dynamic supramolecular capsules.     

Feedback between node and network dynamics can produce real-world network properties

Real-world networks are characterized by common features, including among others a scale-free degree distribution, a high clustering coefficient and a short typical distance between nodes. These properties are usually explained by the dynamics of edge and node addition and deletion.     

Stability of singular spectral types under decaying perturbations

We look at invariance of a.e. boundary condition spectral behavior under perturbations, W, of half-line, continuum or discrete Schrödinger operators. We extend the results of del Rio, Simon, Stolz from compactly supported W's to suitable short-range W. We also discuss invariance of the local Hausdorff dimension of spectral measures under such perturbations.     

Protein-A-mediated Targeting of Bacteriochlorophyll-IgG to Staphylococcus aureus: A Model for Enhanced Site-Specific Photocytotoxicity

Abstract— A model for studying the efficiency of photodynamic action with a photosensitizer placed exclusively on the bacterial cell wall has been used. Bacteriochlorophyllide molecules, conjugated to rabbit immunoglobulin G (IgG), were synthesized. The conjugated pigment bacteriochlo-rophyll (Bchl)-IgG bound with high specificity to protein-A residues naturally exposed on the cell wall of the bacterium Staphylococcus aureus Cowan I. In bacterial suspensions the phototoxicity of the targeted conjugates (0.5-2.5 pigment per IgG molecule) was dose dependent (LD₅₀= 1.7 μ M ) in the presence of light (Λ > 550 nm) and inhibited by native IgG but not by ovalbumin, suggesting selective interaction with protein-A on the bacterial cell wall. No dark toxicity was noticed even with the highest conjugate concentration tested. In contrast, the photocytotoxicity of bacteriochlorophyll-serine (Bchl-Ser, LD₅₀= 0.07 μ M ) used as a nontargeted control was not inhibited by IgG. In spite of its lower apparent potency, Bchl-IgG was found to be 30 times more efficacious than Bchl-Ser: At LD₅₀, only 66000 Bchl-IgG molecules were bound per bacterium compared to 1900 000 molecules of Bchl-Ser. The higher efficacy of Bchl-IgG is explained by its exclusive position on the bacterial cell wall. Consequently, photogeneration of oxidative species is confined to the cell wall and its vicinity, a seemingly highly susceptible domain for photodynamic action. In considering the design of cell-specific sensitizers for bacterial and cancer therapies, it would be beneficial to identify the more discretely sensitive subcellular domains as targets.     

The microenvironment effect on the generation of reactive oxygen species by Pd-bacteriopheophorbide

Generation of reactive oxygen species (ROS) is the hallmark of important biological processes and photodynamic therapy (PDT), where ROS production results from in situ illumination of certain dyes. Here we test the hypothesis that the yield, fate, and efficacy of the species evolved highly depend on the dye's environment. We show that Pd-bacteriopheophorbide (Pd-Bpheid), a useful reagent for vascular targeted PDT (VTP) of solid tumors, which has recently entered into phase II clinical trials under the code name WST09 (trade name TOOKAD), forms appreciable amounts of hydroxyl radicals, superoxide radicals, and probably hydrogen peroxide in aqueous medium but not in organic solvents where singlet oxygen almost exclusively forms. Evidence is provided by pico- and nanosecond time-resolved spectroscopies, ESR spectroscopy with spin-traps, time-resolved singlet oxygen phosphorescence, and chemical product analysis. The quantum yield for singlet oxygen formation falls from approximately 1 in organic solvents to approximately 0.5 in membrane-like systems (micelles or liposomes), where superoxide and hydroxyl radicals form at a minimal quantum yield of 0.1%. Analysis of photochemical products suggests that the formation of oxygen radicals involves both electron and proton transfer from (3)Pd-Bpheid at the membrane/water interface to a colliding oxygen molecule, consequently forming superoxide, then hydrogen peroxide, and finally hydroxyl radicals, with no need for metal catalysis. The ability of bacteriochlorophyll (Bchl) derivatives to form such radicals upon excitation at the near infrared (NIR) domain opens new avenues in PDT and research of redox regulation in animals and plants.     

Self-recognition, structure, stability, and guest affinity of pyrogallol[4]arene and resorcin[4]arene capsules in solution

In the present study, we used diffusion NMR to probe the structures and characteristics of the products obtained from the self-assembly of resorcin[4]arenes 1a and 1b and pyrogallol[4]arenes 2a and 2b in CDCl(3) solutions. It was found that all four molecules self-assemble into hexameric capsules. The hexameric capsules of pyrogallol[4]arenes 2a and 2b were found to be more stable than the capsules of resorcin[4]arenes 1a and 1b in polar media. We also studied the role of water molecules in the self-assembly of the different capsules and found that water molecules are part of the hexameric capsules of resorcin[4]arenes 1a and 1b but not in the capsules of pyrogallol[4]arenes 2a and 2b. It was found that the self-assembly process between the resorcin[4]arenes and pyrogallol[4]arenes proceeds with self-recognition. When mixing two macrocycles of different types in a chloroform solution, no heterohexamers are formed, only the capsule constructed from the same macrocycle is detected. However, when two resorcin[4]arenes (i.e., 1a and 1b) or two pyrogallol[4]arenes (i.e., 2a and 2b) are mixed, heterohexamers are formed over time. In addition, we found that resorcin[4]arenes and pyrogallol[4]arenes differ significantly in their guest affinity. The capsules of 1a and 1b can accommodate both the tertiary alkylamines and their respective ammonium salts, while the capsules of 2a and 2b encapsulate only the neutral tertiary alkylamines.     

Spontaneous formation of hexameric resorcinarene capsule in chloroform solution as detected by diffusion NMR

NMR diffusion measurements provide unequivocal proof that the resorcinarene 1b self-assembles spontaneously into a stable hexamer capsule in chloroform solution by encapsulating several chloroform molecules, which occupy different chemical positions. Although the affinity of tetrahexylammonium bromide (2a) toward the cavity of the hexamer is much higher than that of the chloroform molecules, it was found that the same amount of DMSO is needed to disrupt the two hexamers, thus suggesting similar stabilities for these two supramolecular capsules.