Brittle fracture and spinnability of viscous materials

Conclusion In both cases, brittle fracture and dropping breakdown, only very little deformation or elongation was observed in the experiments mentioned above, and limiting conditions were obtained reproducibly with respect to rate of extension and temperature. The brittle limits give the condition where the viscous resistance due to locally concentrated stress, i. e. the grip effect (5) exceeds cohesion of the materials, and development of the surface of separation is followed. At the dropping limits, the viscosities of the liquids may be too small to resist shrinking by surface tension with respect to the rate of extension. Although the theory of spinnability proposed here may be only tentative, it can be pointed out that surface tension plays some important role in spinning of viscous liquids of lower molecules. Concerning higher molecules, rubber-like elasticity as well as viscosity may become more important (6).

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Zusammenfassung Für beide Fälle, spröden Bruch und stufenweiser Bruch, wurde nur sehr geringe Deformation oder Verlängerung beobachtet und Grenzbedingungen hinsichtlich Dehnungsgeschwindigkeit und Temperatur reproduzierbar erhalten. Die Bruchgrenzen geben die Bedingungen, bei denen der viskose Widerstand entsprechend den lokalen Spannungskonzentrationen, d. h. entsprechend den grip-Effekt die Kohäsion des Materials übersteigt, und die Entwickelung der Trennfläche wird verfolgt. Bei der Grenzbelastung für das Absinken der Spannung mag die Viskosität der Flüssigkeiten zu gering sein, um dem Schrumpfen durch Oberflächenspannung im Vergleich mit der Dehnungsgeschwindigkeit entgegen zu wirken. Obgleich die Theorie der Spinnbarkeit, hier vorgeschlagen, nur einen Versuch darstellt, kann behauptet werden, daß die Oberflächenspannung beim Spinnen viskoser Flüssigkeiten mit kleineren Molekülen eine wichtige Rolle spielt. Für höhermolekulare Substanzen wird neben der Viskosität auch die Gummielastizität ausschlaggebend.

     

Metric packing for K 3+K 3

In this paper, we consider the metric packing problem for the commodity graph of disjoint two triangles K ₃+K ₃, which is dual to the multiflow feasibility problem for the commodity graph K ₃+K ₃. We prove a strengthening of Karzanov’s conjecture concerning quarterintegral packings by certain bipartite metrics.     

Sorption of water vapor into polyelectrolyte complex of poly(styrenesulfonic acid)/poly(4-vinyl-N-ethylpyridinium bromide)

Successive differential and integral sorptions of water vapor into the polyelectrolyte complex of poly (sty renesulfonic acid) / poly(4-vinyl-N-ethylpyridinum bromide) have been measured; films of stoichiometric (1/1 molar ratio) and nonstoichiometric (2/1 molar ratio) complex were employed in the experiments. Sorption isotherms have been also determined by using the values obtained from integral sorption experiments. The sorption data have suggested the following. (i) The rearrangement of polymer chains plays a relatively unimportant role in sorption of water. (ii) The relaxation motion of network chains is suppressed. (iii) The change of morphological structure caused by vapor sorption is obscure. (iv) The ionic character of the 1/1 complex is higher than that of 2/1 complex. (v) A small amount of water can be dispersed on specific polymer sites, but the sorption of a large amount of water is accompanied by an expansion of network structure. Points (i)-(v) have been consistently interpreted on the basis of the network structure and ionic character of this complex.     

Synthesis of dendritic bisphosphonates as bone targeting ligands

A dendritic bisphosphonate carrying three bisphosphonate (BP) units in close proximity was designed as a ligand to conjugate large therapeutic molecules for their bone selective delivery. The Bu₃P-catalyzed conjugate addition of nitromethane to vinylidene bisphosphonate was effective to construct a quaternary carbon center carrying BP units. Owing to multivalent interactions, the dendritic bisphosphonate showed considerable affinity for the bone mineral hydroxyapatite even in the presence of a competitor, demonstrating potential as a bone targeting ligand.     

Temperature-controlled photosensitization properties of benzophenone-conjugated thermoresponsive copolymers

We previously found that a copolymer, poly(NIPAM- co-BP), consisting of N-isopropylacrylamide (NIPAM) and benzophenone (BP) units, behaves as a photosensitizer showing temperature-controlled oxygenation activity by singlet oxygen ( (1)O 2) in water ( J. Am. Chem. Soc. 2006, 128, 8751-8753 ). This polymer shows a heat-induced oxygenation enhancement at <20 degrees C, while showing suppression at >20 degrees C. This is driven by a heat-induced phase transition of the polymer from coil to micelle and then to globule state, controlling the stability and diffusion of (1)O 2 and the location of substrate. In the present work, effects of polymer concentration and BP content of the polymer on the oxygenation activity were studied at 5-35 degrees C. Increase in the polymer concentration leads to activity decrease at >20 degrees C due to strong polymer aggregation, suppressing incident light absorption of the BP units. With a decrease in BP content of the polymer, heat-induced oxygenation enhancement at <20 degrees C is more pronounced because formation of small size micelles accelerates (1)O 2 oxygenation. The obtained findings reveal that the polymer with low BP content, when used at high concentration, shows clear-cut off- on- off activity change against the temperature window: very low activity at <5 degrees C and >25 degrees C, and very high activity at middle temperature range.     

Fe(III)- and Hg(II)-selective dual channel fluorescence of a rhodamine-azacrown ether conjugate

A rhodamine-azacrown ether conjugate (1) demonstrates Fe(III)-selective green fluorescence, while showing Hg(II)-selective orange fluorescence. This is the first example of rhodamine-based fluorescent probe that shows dual channel fluorescence for two different metal cations.     

A fluorescent molecular switch driven by the input sequence of metal cations: an azamacrocyclic ligand containing bipolar anthracene fragments

An azamacrocyclic ligand (L) containing two anthracene (AN) fragments connected through two triethylenetetramine bridges has been synthesized, in which each of the bridges can coordinate with one metal cation. The effects of pH and metal cations (Zn2+ and Cd2+) on the emission properties of L were studied in water. Without metal cations, L does not show any emission at basic pH values. The addition of Zn2+ leads to the production of excimer emission, which is due to a static excimer formed by direct excitation of the intramolecular ground-state dimer of the bipolar AN fragments that approach each other by Zn2+ binding. In contrast, Cd2+ addition does not result in excimer emission because the Cd2+-AN pi complex, formed by donation of a pi electron of the AN fragments to the adjacent Cd2+, suppresses pi-stacking interactions of the AN fragments. The most notable feature is the appearance of excimer emission controlled by the input sequence of metal cations: Zn2+-->Cd2+ sequential addition (each one equivalent) allows excimer emission, whereas the reverse sequence (Cd2+-->Zn2+) does not. In the Zn2+-->Cd2+ sequence, Cd2+ coordination is structurally restricted by the first Zn2+ coordination with the other polyamine bridge, leading to the formation of a weak Cd2+-AN pi complex. In contrast, for the reverse sequence, the first Cd2+ coordination forms a stable Cd2+-AN pi complex, which is not weakened by sequential Zn2+ coordination, resulting in no excimer emission.     

Temperature-controlled changeable oxygenation selectivity by singlet oxygen with a polymeric photosensitizer

A polymeric photosensitizer, poly(NIPAM-co-RB), consisting of N-isopropylacrylamide and rose bengal units, demonstrates a temperature-controlled changeable oxygenation selectivity by singlet oxygen in water.