A probabilistic theory on the time to fracture of amorphous crosslinked polymers

The energy probability theory of fracture proposed by Valanis has been extended to apply to the global fracture of a large material region and has been generalized to take into account the probabilistic distribution among bonds of the free energy of the region. In contrast to the theory of fracture initiation of the first author, it is assumed, in the present paper, that global fracture is brought about by the fracture of a critical number N_cr of primary bonds. Whereas this condition alleviates some of the problems encountered in the application of the theory to fracture initiation and propagation—such as determination of the local energy field at the root of a developed crack—it introduces the difficulty that N_cr may, in general, depend on the geometry of the specimen and the directionality of the stress field, though it was found to be relatively insensitive to the rate of deformation, as corroborated in this paper. The theory is used in this work to predict the time of global fracture, under conditions of constant load, constant strain, and constant strain rate.     

On the interaction between retrials and sizing of call centers

This paper models a call center as a Markovian queue with multiple servers, where customer impatience, and retrials are modeled explicitly. The model is analyzed as a continuous time Markov chain. The retrial phenomenon is explored numerically using a real example, to demonstrate the magnitude it can take and to understand its sensitivity to various system parameters. The model is then used to assess the impact of disregarding existing retrials in the staffing of a call center. It is shown that ignoring retrials can lead to under-staffing or over-staffing with respect to the optimal, depending on the forecasting assumptions being made.     

MRI findings of gastric metastases from breast carcinoma

We describe the MR appearance of breast cancer metastases to the stomach. The stomach wall was diffusely thickened with loss of the regular fold pattern best shown on the single shot T2-weighted images and enhanced with moderate mural enhancement on early and late post gadolinium images. The combination of gastric wall thickening and abnormal enhancement should suggest the diagnosis of diffuse mural metastases in a woman with a history of breast cancer.     

An endochronic prediction of the variability in fracture times of polymers

A theory of variability in lifetimes of identical polymer specimens under identical test conditions is formulated, using the theory of fracture of amorphous crosslinked polymers developed previously by the authors. Variability in fracture times follows from the assumption that the critical number N_cr of bonds that must fail in order to cause fracture of a specimen varies from specimen to specimen. A plausible physical explanation for the variation in N_cr may well lie in the variability of the spatial distribution of weak local regions. The scale of locality may vary from molecular to grosser dimensions. The theory is applied to styrene–butadiene rubber (SBR) under creep conditions and fares well in its prediction of observed results. Most notably, it predicts that the shape of the distribution curve of the observed lifetimes remains invariant with changes in the levels of stress and temperature and that the effects of these manifest themselves through shifts of the curve on the logarithmic time axis. The theory also predicts correctly that the fracture process is accelerated if the creep test is interrupted by unloading–reloading cycles at high strain rates. This last result is shown to be a direct consequence of the concept of “the endochronic time to fracture,” previously introduced by the first author.     

Biosynthesis of pentangular polyphenols: deductions from the benastatin and griseorhodin pathways

The benastatins, pradimicins, fredericamycins, and members of the griseorhodin/rubromycin family represent a structurally and functionally diverse group of long-chain polyphenols from actinomycetes. Comparison of their biosynthetic gene clusters (ben, prm, fdm, grh, rub) revealed that all loci harbor genes coding for a similar, yet uncharacterized, type of ketoreductases. In a phylogenetic survey of representative KRs involved in type II PKS systems, we found that it is generally possible to deduce the KR regiospecificity (C-9, C-15, C17) from the amino acid sequence and thus to predict the nature of the aromatic polyketide (e.g., angucycline, anthracycline, benzoisochromanequinones). We hypothezised that the new clade of KRs is characteristic for biosynthesis of polyphenols with an extended angular architecture we termed "pentangular". To test this hypothesis, we demonstrated the biogenetic relationship between benastatin and the structurally unrelated spiro ketal griseorhodin by generating a mutant producing collinone, a pentangular pathway intermediate. The benastatin pathway served as a model to characterize the KR. Gene inactivation of benL resulted in the formation of a series of 19-hydroxy benastatin and bequinostatin derivatives (e.g., benastatin K and benastatin L). These results clearly showed that BenL functions as a C-19 KR in pentangular pathways.     

Neutron Equivalent Dose Rate Measurements of Gypsum-Waste Tire Rubber Layered Structures

The neutron equivalent dose rates (µSv/h) of gypsum, steel-reinforced rubber waste tire, and gypsum-waste tire rubber sandwich composite samples were investigated. Prepared samples were irradiated with ²⁴¹Am-Be neutrons and transmission values were obtained using dose equivalent rates measured with a BF₃ neutron detector. Results were compared to those of concrete, and as a result of neutron shielding, the performance of gypsum, waste tire, and waste tire (steel-reinforced rubber) embedded gypsum samples was higher than that of concrete. This information may be useful for shielding design of nuclear application areas.     

On dynamical behavior for optical solitons sustained by the perturbed Chen–Lee–Liu model

This study investigates the perturbed Chen–Lee–Liu model that represents the propagation of an optical pulse in plasma and optical fiber. The generalized exponential rational function method is used for this purpose. As a result, we obtain some non-trivial solutions such as the optical singular, periodic, hyperbolic, exponential, trigonometric soliton solutions. We aim to express the pulse propagation of the generated solutions, by taking specific values for the free parameters existed in the obtained solutions. The obtained results show that the generalized exponential rational function technique is applicable, simple and effective to get the solutions of nonlinear engineering and physical problems. Moreover, the acquired solutions display rich dynamical evolutions that are important in practical applications.     

Chelation of Theranostic Copper Radioisotopes with S-Rich Macrocycles: From Radiolabelling of Copper-64 to In Vivo Investigation

Copper radioisotopes are generally employed for cancer imaging and therapy when firmly coordinated via a chelating agent coupled to a tumor-seeking vector. However, the biologically triggered Cu²⁺-Cu⁺ redox switching may constrain the in vivo integrity of the resulting complex, leading to demetallation processes. This unsought pathway is expected to be hindered by chelators bearing N, O, and S donors which appropriately complements the borderline-hard and soft nature of Cu²⁺ and Cu⁺. In this work, the labelling performances of a series of S-rich polyazamacrocyclic chelators with [⁶⁴Cu]Cu²⁺ and the stability of the [⁶⁴Cu]Cu-complexes thereof were evaluated. Among the chelators considered, the best results were obtained with 1,7-bis [2-(methylsulfanyl)ethyl]-4,10,diacetic acid-1,4,7,10-tetraazacyclododecane (DO2A2S). DO2A2S was labelled at high molar activities in mild reaction conditions, and its [⁶⁴Cu]Cu²⁺ complex showed excellent integrity in human serum over 24 h. Biodistribution studies in BALB/c nude mice performed with [⁶⁴Cu][Cu(DO2A2S)] revealed a behavior similar to other [⁶⁴Cu]Cu-labelled cyclen derivatives characterized by high liver and kidney uptake, which could either be ascribed to transchelation phenomena or metabolic processing of the intact complex.     

Chain Sliding versus β-Sheet Formation upon Shearing Single α-Helical Coiled Coils

Coiled coils (CCs) are key building blocks of biogenic materials and determine their mechanical response to large deformations. Of particular interest is the observation that CC-based materials display a force-induced transition from α-helices to mechanically stronger β-sheets (αβT). Steered molecular dynamics simulations predict that this αβT requires a minimum, pulling speed-dependent CC length. Here, de novo designed CCs with a length between four to seven heptads are utilized to probe if the transition found in natural CCs can be mimicked with synthetic sequences. Using single-molecule force spectroscopy and molecular dynamics simulations, these CCs are mechanically loaded in shear geometry and their rupture forces and structural responses to the applied load are determined. Simulations at the highest pulling speed (0.01 nm ns⁻¹) show the appearance of β-sheet structures for the five- and six-heptad CCs and a concomitant increase in mechanical strength. The αβT is less probable at a lower pulling speed of 0.001 nm ns⁻¹ and is not observed in force spectroscopy experiments. For CCs loaded in shear geometry, the formation of β-sheets competes with interchain sliding. β-sheet formation is only possible in higher-order CC assemblies or in tensile-loading geometries where chain sliding and dissociation are prohibited.     

Effect of processing consitions on the development of morphology in clay nanoparticle filled nylon 6 fibers

The effect of melt temperature on the phase behavior and preferential orientation development in Nylon 6/montmorillonite nanocomposites were investigated at melt spinning temperatures ranging from 230° to 250°C. The fibers were found to exhibit mostly γ crystalline form that is typical of Nylon 6 filled with montmorillonite nanoparticles. At higher take-up speeds α-crystals begin to appear in the crystalline phase. The presence of nanoparticles was found to impart substantial chain orientation levels even at low to moderate take up speeds reaching a plateau at moderate take up speeds. This was attributed to the increased spin line stress in the presence of nanoparticles that increase the overall viscosity due to their large contact areas with the polymer chains. This increased spinline tension was found to cause fiber breakup at moderate speeds. Increasing melt temperature from 230° to 250°C alleviated this problem.