Synchronization by nonlinear frequency pulling

We analyze a model for the synchronization of nonlinear oscillators due to reactive coupling and nonlinear frequency pulling motivated by the physics of arrays of nanoscale oscillators. We study the model for the mean field case of all-to-all coupling, deriving results for the onset of synchronization as the coupling or nonlinearity increase, and the fully locked state when all the oscillators evolve with the same frequency.     

The effect of Hartmann-Hahn mismatching on polarization inversion spin exchange at the magic angle

The effect of the Hartmann-Hahn mismatch delta = omega(eff)-omega(1S) during polarization inversion spin exchange at the magic angle (PISEMA) has been investigated, where omega(eff) and omega(1S) represent the amplitudes of the 1H effective spin-locking field at the magic angle and the 15N RF spin-locking field, respectively. During the PISEMA evolution period, the exact Hartmann-Hahn match condition (i.e., delta = 0) yields a maximum dipolar scaling factor of 0.816 for PISEMA experiments, while any mismatch results in two different effective fields for the first and second half of each frequency switched Lee-Goldburg (FSLG) cycle. The mismatch effect on the scaling factor depends strongly on the transition angle from one effective field to the other within each FSLG cycle as well as on the cycle time. At low RF spin-lock amplitudes in which the FSLG cycle time is relatively long, the scaling factor rapidly becomes smaller as omega(1S) becomes greater than omega(eff). On the other hand, when omega(1S) < omega(eff), there is relatively little effect on the scaling factor with variation in delta. As a result, the presence of RF inhomogeneities may significantly broaden the line-width in the dipolar dimension because of the mismatch effect. Higher RF spin-lock amplitudes result in a relatively small variation for the scaling factor. Furthermore, ramped amplitude of the 15N RF spin-lock field in synchronization with the flip-flop of the FSLG sequence minimizes the transition angle between the two effective fields within the FSLG cycle. It is shown experimentally that such a ramped amplitude not only gives rise to the same scaling factor but also results in a narrower dipolar line-width in comparison with the rectangular amplitude.     

Crystallographic characterization of Kr@C60 in (0.09Kr@C60/0.91C60). (NiII(OEP)).2C6H6

A sample of C60 containing ca. 9% Kr@C60 has been used to form crystalline (0.09Kr@C60/0.91C60).(NiII(OEP)).2C6H6 whose X-ray crystal structure reveals that the Kr atom is centered within the carbon cage and does not produce a detectable change in the size of the fullerene.     

Crystal engineering of microporous 'Chinese-lantern' compounds to improve their ability to reversibly adsorb sulfur dioxide

Three new 'Chinese lantern' complexes [XMn(mu-dppO2)4MnX](2+)2X-.4MeOH.Me2CO [X = Cl, Br, I; dppO2 = 1,3-bis(diphenylphosphinoyl)propane], have been structurally characterised using single-crystal X-ray diffraction and shown to have increasing affinity for SO2 across the series Cl < Br < I via thermogravimetric measurements.     

Examining the kinetics of the thermal polymerization of commercial aromatic bis‐benzoxazines

Three commercial bis‐benzoxazine monomers based on the aniline derivatives of bisphenol A (BA‐a), bisphenol F (BF‐a), and 3,3′‐thiodiphenol (BT‐a) are examined using a variety of spectroscopic, chromatographic, and thermomechanical techniques. The kinetics of the polymerization of BA‐a were found to be well described using an autocatalytic model for which values of n = 1.39 and m = 2.49 were obtained for the early and later stages of reaction respectively (activation energy = 81–88 kJ/mol.). Following recrystallization the same monomer yielded values of n = 1.80, m = 0.92, and E_a = 94–97 kJ/mol. BF‐a and BT‐a were also found to be well described using an autocatalytic model for which values of n = m = 2.11 (BF‐a) and n = 2.10, m = 1.47 (BT‐a) were obtained for the early and later stages of reaction (activation energy = 80–84 kJ/mol. for BF‐a and 88–95 kJ/mol. for BT‐a). The kinetic data are compared with parallel studies involving chemically initiated benzoxazine monomers. Molecular simulation is used to examine the rotational freedom of the central bridging units and this is related to the degree of conversion achieved. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2068–2081     

Failure of the free non-Markovian heat energy relation under a bath temperature change

We investigate the free energy relation for a system contacting with a non-Markovian heat bath and find that the validity of the relation sensitively depends on the non-Markovian memory effect, which is especially related to the initial preparation effect. This memory effect drives the statistical distribution of the system out of the initial preparation, even if the system starts from an equilibrium state. This leads to the violation of the free energy relation. A possible way of eliminating this memory effect is proposed.     

Relation between viscoelasticity and shear-thinning behaviour in liquids

Summary The shear-thinning behaviour of a liquid is represented in terms of a relaxation time, defined by the ratio ₀/G₀ of initial viscous and elastic constants. The relationship provides a very simple basis for the evaluation of andG ₀ from viscosity/shear data. Results are compared with relaxation times and moduli from primary normal-stress measurement, from stress relaxation and from direct measurement of recoverable shear strain. Good agreement is found but there is experimental evidence the recoverable shear strain _e is related to normal stressN ₁ and shear stress by _e = N₁/3, which does not agree with the theoretical prediction of eitherWeissenberg orLodge.

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Zusammenfassung Das Scherentzähungsverhalten einer Flüssigkeit wird mittels einer Relaxationszeit beschrieben, die durch das Verhältnis der Anfangswerte von Viskosität und Elastizitätsmodul ₀/G₀ definiert ist. Diese Beziehung eröffnet eine einfache Methode zur Bestimmung von undG ₀ aus Scherviskositätsmessungen. Die damit erhaltenen Ergebnisse werden mit Relaxationszeiten und Moduln verglichen, die durch Messung der ersten Normalspannungsdifferenz, der Spannungsrelaxation und der Scherdehnungsrückstellung (recoverable shear strain) gewonnen worden sind. Es wird eine gute Übereinstimmung gefunden, zugleich aber wird der experimentelle Nachweis geführt, daß die Scherdehnungsrückstellung _e mit der ersten NormalspannungsdifferenzN ₁ und der Schubspannung durch die Beziehung _e = N₁/3 verknüpft ist, was sowohl zu der theoretischen Voraussage vonWeissenberg als auch zu derjenigen vonLodge im Widerspruch steht.

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With 10 figures and 1 table     

Medical Uses for Polyelectrolyte Complexes

Polyelectrolyte complexes (PEC) are ionically bonded hydrogels. The resin is synthesized by coreacting linear, water-soluble ionic polymers of opposite electrical charge under carefully controlled conditions. The resulting material is insoluble in water, electrolytes, organic, or common solvents, but soluble in special ternary solvents. Optically clear membranes or shaped articles can be prepared by employing simple solvent casting and drying techniques upon resin dissolution. The equilibrium gel water content of typical, homogeneous complexes can be made to range from 30 to 90% by weight by changing the initial polyanion to polycation ratio. For almost any given charge ratio the water content can be varied from 30 to 90% by initial adjustment of the solvent composition. As the gel water content of a membrane is raised the dialytic, oxygen, and water transport increase. High water content membranes with and without glass reinforcement were shown to be extremely permeable materials. Because these hydrated complexes appeared to be chemically inert and could be tailored to be rich in either polyanion or polycation charged groups, their biocompatability was studied. Extraction, toxicity, tissue compatability, carcinogenicity, and blood contact studies on various polyelectrolyte complexes were carried out.     

Signal amplification by sensitive control of bifurcation topology

We describe a novel amplification scheme based on inducing dynamical changes to the topology of a bifurcation diagram of a simple nonlinear dynamical system. We have implemented a first bifurcation-topology amplifier using a coupled pair of parametrically driven high-frequency nanoelectromechanical systems resonators, demonstrating robust small-signal amplification. The principles that underlie bifurcation-topology amplification are simple and generic, suggesting its applicability to a wide variety of physical, chemical, and biological systems.