Does the Johari-Goldstein β-Relaxation Exist in Polypropylene Glycols?

Secondary relaxations with properties closely related to the α-relaxation have fundamental importance in glass-forming substances including polymers. To distinguish these secondary relaxations from those involving intramolecular degrees of freedom, they are called the Johari-Goldstein (JG) β-relaxations. Acting as the precursor of the α-relaxation, the JG β-relaxation is supposedly ubiquitous in all glass-formers, a thesis supported by experiments on a variety of glass-formers. Notwithstanding, the JG β-relaxation has not been identified definitively in the hydroxyl-terminated polypropylene glycols (PPGs) with various molecular weights, despite these polymers have been intensively studied experimentally in the last several decades. The difficulty of finding the JG β-relaxation is due to the presence of a faster intramolecular -relaxation and a slower relaxation originating from residual water. This is demonstrated in two recent papers by Gainaru et al. Macromolecules 2010, 43, 1907, and Kaminski et al. Macromolecules 2013, 46, 1973. In this paper, we show the presence of the JG β-relaxation in the PPGs from the dielectric relaxation data by using the time honored criterion derived from the coupling model in conjunction with the observed anomalous temperature dependence of the -relaxation caused by merging with the JG β-relaxation, and new experimental data obtained by applying pressure on PPG4000 before and after drying the sample to remove the residual water. From the results, we conclude that the behavior of the PPGs is no different from the other glass-formers as far as the omnipresence of the JG β-relaxation is concerned

Feasibility study of electromechanical cylinder drivetrain for offshore mechatronic systems

Currently, there is an increasing focus on the environmental impact and energy consumption of the oil and gas industry. In offshore drilling equipment, electric motors tend to replace traditionally used hydraulic motors, especially in rotational motion control applications. However, force densities available from linear hydraulic actuators are still typically higher than those of electric actuators. Therefore, usually the remaining source of hydraulic power is thereby the hydraulic cylinder. This paper presents a feasibility study on the implementation of an electromechanical cylinder drivetrain on an offshore vertical pipe handling machine. The scope of this paper is to investigate the feasibility of a commercial off-the-shelf drivetrain. With a focus on the motion performance, numerical modeling and simulation are used when sizing and selecting the components of the considered electromechanical cylinder drivetrain. The simulation results are analyzed and discussed together with a literature study regarding advantages and disadvantages of the proposed solution considering the design criteria of offshore drilling equipment. It is concluded that the selected drivetrain can only satisfy the static motion requirements since the required transmitted power is higher than the recommended permissible power of the transmission screw. Consequently, based on the recommendation of the manufacturer, avoidance of overheating cannot be guaranteed for the drivetrain combinations considered for the case study presented in this paper. Hence, to avoid overheating, the average speed of the motion cycle must be decreased. Alternatively, external cooling or temperature monitoring and control system that prevents overheating could be implemented

More than one dynamic crossover in protein hydration water

Studies of liquid water in its supercooled region have led to many insights into the structure and behavior of water. While bulk water freezes at its homogeneous nucleation temperature of approximately 235 K, for protein hydration water, the binding of water molecules to the protein avoids crystallization. Here we study the dynamics of the hydrogen bond (HB) network of a percolating layer of water molecules, comparing measurements of a hydrated globular protein with the results of a coarse-grained model that has been shown to successfully reproduce the properties of hydration water. With dielectric spectroscopy we measure the temperature dependence of the relaxation time of protons charge fluctuations. These fluctuations are associated to the dynamics of the HB network of water molecules adsorbed on the protein surface. With Monte Carlo (MC) simulations and mean--field (MF) calculations we study the dynamics and thermodynamics of the model. In both experimental and model analyses we find two dynamic crossovers: (i) one at about 252 K, and (ii) one at about 181 K. The agreement of the experiments with the model allows us to relate the two crossovers to the presence of two specific heat maxima at ambient pressure. The first is due to fluctuations in the HB formation, and the second, at lower temperature, is due to the cooperative reordering of the HB network

Revisiting a perovskite-like copper-formate framework NH4[Cu(HCOO)3]: order-disorder transition influenced by Jahn-Teller distortion and above room-temperature switching of the nonlinear optical response between two SHG-active states

Metal-formate frameworks comprising ammonium cations as guests are proven to be a fertile ground to study various phenomena associated with the temperature-induced changes in structural, dielectric, optical, and magnetic properties. In this contribution, we revisit NH4[Cu(HCOO)3], a member of metal formates that distinguishes itself in terms of its phase transition behavior and associated properties. New data on structural dynamics of all phases of NH4[Cu(HCOO)3] have been obtained with the use of variable-temperature Raman measurements. Smooth changes of band positions observed near 220 K attest to the postulated continuous nature of low-temperature phase transition, whereas apparent discontinuities at 355 K confirm the first-order type of transition between orthorhombic (II) and hexagonal (I) phases. Low-temperature Raman data were confronted with diffraction results, pointing to a significant effect of Jahn-Teller distortion on the vibrational properties the CuO6 subnetwork. In the high-temperature range, a significant broadening of bands is observed, confirming that phase I is highly disordered, with the strongest changes of full width at half maximum (FWHM) parameters being observed for bands corresponding to NH4+ cations. Dielectric investigations revealed the symmetric shape of the observed process indicating the Debye-like relaxation. Thus, the dielectric relaxation was characterized in terms of the dipolar relaxation model using the Cole–Cole relaxation function, leading to an Ea value of approximately 0.76 eV. Finally, temperature-resolved second harmonic generation (SHG) measurements unequivocally corroborate the noncentrosymmetric setting of phases II and I, as well as allowed us to realize temperature-induced switching of second-order nonlinear optical (NLO) responses. We demonstrate that NH4[Cu(HCOO)3] serves as a host to uncommon kind of quadratic NLO switching, which takes advantage of two SHG-active states: SHG-high state below Tc, and SHG-low state above Tc. The demonstrated SHG-high – SHG-low temperature-driven bistability stands out from the vast majority of molecular and coordination polymer NLO switches that employ binary SHG-on and SHG-off switching schemes

Piezo1 expression in chondrocytes controls endochondral ossification and osteoarthritis development

Piezo proteins are mechanically activated ion channels, which are required for mechanosensing functions in a variety of cell types. While we and others have previously demonstrated that the expression of Piezo1 in osteoblast lineage cells is essential for bone-anabolic processes, there was only suggestive evidence indicating a role of Piezo1 and/or Piezo2 in cartilage. Here we addressed the question if and how chondrocyte expression of the mechanosensitive proteins Piezo1 or Piezo2 controls physiological endochondral ossification and pathological osteoarthritis (OA) development. Mice with chondrocyte-specific inactivation of Piezo1 (Piezo1Col2a1Cre), but not of Piezo2, developed a near absence of trabecular bone below the chondrogenic growth plate postnatally. Moreover, all Piezo1Col2a1Cre animals displayed multiple fractures of rib bones at 7 days of age, which were located close to the growth plates. While skeletal growth was only mildly affected in these mice, OA pathologies were markedly less pronounced compared to littermate controls at 60 weeks of age. Likewise, when OA was induced by anterior cruciate ligament transection, only the chondrocyte inactivation of Piezo1, not of Piezo2, resulted in attenuated articular cartilage degeneration. Importantly, osteophyte formation and maturation were also reduced in Piezo1Col2a1Cre mice. We further observed increased Piezo1 protein abundance in cartilaginous zones of human osteophytes. Finally, we identified Ptgs2 and Ccn2 as potentially relevant Piezo1 downstream genes in chondrocytes. Collectively, our data do not only demonstrate that Piezo1 is a critical regulator of physiological and pathological endochondral ossification processes, but also suggest that Piezo1 antagonists may be established as a novel approach to limit osteophyte formation in OA

A prospective survey in European Society of Cardiology member countries of atrial fibrillation management: baseline results of EURO bservational Research Programme Atrial Fibrillation (EORP-AF) Pilot General Registry

Aims: Given the advances in atrial fibrillation (AF) management and the availability of new European Society of Cardiology (ESC) guidelines, there is a need for the systematic collection of contemporary data regarding the management and treatment of AF in ESC member countries. Methods and results: We conducted a registry of consecutive in- and outpatients with AF presenting to cardiologists in nine participating ESC countries. All patients with an ECG-documented diagnosis of AF confirmed in the year prior to enrolment were eligible. We enroled a total of 3119 patients from February 2012 to March 2013, with full data on clinical subtype available for 3049 patients (40.4% female; mean age 68.8 years). Common comorbidities were hypertension, coronary disease, and heart failure. Lone AF was present in only 3.9% (122 patients). Asymptomatic AF was common, particularly among those with permanent AF. Amiodarone was the most common antiarrhythmic agent used (~20%), while beta-blockers and digoxin were the most used rate control drugs. Oral anticoagulants (OACs) were used in 80% overall, most often vitamin K antagonists (71.6%), with novel OACs being used in 8.4%. Other antithrombotics (mostly antiplatelet therapy, especially aspirin) were still used in one-third of the patients, and no antithrombotic treatment in only 4.8%. Oral anticoagulants were used in 56.4% of CHA 2DS2-VASc = 0, with 26.3% having no antithrombotic therapy. A high HAS-BLED score was not used to exclude OAC use, but there was a trend towards more aspirin use in the presence of a high HAS-BLED score. Conclusion: The EURObservational Research Programme Atrial Fibrillation (EORP-AF) Pilot Registry has provided systematic collection of contemporary data regarding the management and treatment of AF by cardiologists in ESC member countries. Oral anticoagulant use has increased, but novel OAC use was still low. Compliance with the treatment guidelines for patients with the lowest and higher stroke risk scores remains suboptimal. © The Author 2013