Critical role of lattice vacancies in pressure-induced phase transitions of baroplastic diblock copolymers.

Baroplastic diblock copolymers exhibit order-disorder transitions and melt upon compression at low temperatures, in some cases even at ambient temperatures. Their unique low-temperature processability makes them promising candidates for sustainable polymeric materials. Despite their potential, however, the molecular mechanisms governing the pressure-induced phase transitions of these copolymers remain largely unexplored. This study develops a compressible self-consistent field theory for baroplastic copolymers based on a simple lattice vacancy model that explicitly incorporates voids to account for compressibility. The theory shows that the selective presence of voids in compressible domains stabilizes the ordered phase, while a reduction of voids under compression leads to the order-disorder transition. In addition, this work demonstrates for the first time the critical role of gas absorption rates in each segment in the pressure-induced order-disorder transition of baroplastic diblock copolymers. These findings have significant implications for the rational design of baroplastic polymers with tailored low-temperature processability.

Comparison of gels synthesized by controlled radical copolymerization and free radical copolymerization: molecular dynamics simulation.

The structures of gels synthesized by controlled radical copolymerization (CRP) and conventional free radical copolymerization (FRP) were studied by a coarse-grained molecular dynamics simulation. It was confirmed that the CRP gel has a larger number of elastically effective chains and fewer cyclic structures and entanglements than the FRP gel, i.e., the network structure of the CRP gel is more uniform than that of the FRP gel. However, the difference in the shear modulus between the two gels was small due to the opposing changes in the number of elastically effective chains and that of entanglements. The relatively uniform structure of the CRP gel is attributed to the suppression of intramolecular cross-linking by the fast initiation and slow propagation, and the development of cross-linked structures in the post-gel region due to the limited termination. The effects of these CRP characteristics were studied in detail. From the results, it was found that all of these characteristics of CRP cooperatively act to improve the homogeneity of the structure of the CRP gel.

Engine performance and emissions evaluation of surfactant-free B30 biodiesel-diesel/water emulsion as alternative fuel.

Malaysia is one of the top exporters of palm oil, and although currently facing fierce resistance towards palm oil imports in some parts of the globe, one of the ways to utilize this commodity is by increasing palm biodiesel content in local commercial diesel. However, due to the oxygen-rich nature of biodiesel, its utilization suffers from increased nitrogen oxides (NOx) emission compared to conventional diesel. To mitigate this issue and improve diesel engine performance and emissions using biodiesel-diesel blends, this study attempted to investigate implementation of a real-time non-surfactant emulsion fuel supply system (RTES) which produces water-in-diesel emulsion as fuel without surfactants. NOx reducing capability of water-in-diesel produced by RTES has been well documented. Therefore, in this study, 30% biodiesel-diesel (B30) was used as the base fuel while B30-derived emulsions consisting of 10 wt%, 15 wt% and 20 wt% water content were supplied into a 100 kVA, 5.9-L common rail turbocharged diesel engine electric generator. Fuel consumption and exhaust emissions were measured and compared with commercially available Malaysian low grade diesel fuel (D2M). Evidence suggested that emulsified B30 biodiesel-diesel produced by RTES was able to increase brake thermal efficiency (BTE) up to a maximum of 36% and reduce brake specific fuel consumption (BSFC) up to 8.70%. Furthermore, B30 biodiesel-diesel emulsions produced significantly less NOx, carbon monoxide and smoke at high engine load. In conclusion, B30 biodiesel-diesel emulsions can be readily utilized in current diesel engines without compromising on performance and emissions.

Deep-Sea-Inspired Chemistry: A Hitchhiker's Guide to the Bottom of the Ocean for Chemists.

The ocean constitutes approximately 70% of Earth's surface. Its average depth is 3688 m, of which depths beyond 200 m are classified as the deep sea. The deep sea is distinct from the surface of the ocean in terms of pressure, temperature, and sunlight. The unique physicochemical processes under the extreme environment of the deep sea and the specialized biochemical mechanisms developed by organisms to survive in the deep sea can serve as a vast source of inspiration for scientific and technological advancements. In this Perspective, we discuss three examples of deep-sea-inspired chemistry: (1) soft materials that respond to high pressures such as those observed in the deep sea; (2) molecular self-assembly inspired by the chemistry of hot and compressed water in deep-sea hydrothermal vents; and (3) nanobiotechnology and biomimetics inspired by survival strategies of deep-sea organisms. Finally, we provide an outlook on deep-sea-inspired chemistry. This Perspective aims to promote the sustainable utilization of the ocean based on knowledge, as opposed to the conventional utilization of the ocean solely based on resources. We hope that this Perspective will encourage chemists to harness their inspiration gleaned from the deep sea.

Molecular Simulation and Theoretical Analysis of Slide-Ring Gels under Biaxial Deformation.

Slide-ring (SR) gels, a new type of gels that have cross-links moving along the chains, are known to have unique mechanical characteristics. In the case of biaxial deformations, it has been experimentally shown that the stress-strain (S-S) relationships of SR gels can be well described by the neo-Hookean (NH) model. This behavior is quite different from that of conventional chemical gels, where the S-S curves deviate from the NH model. To understand the molecular mechanism of such peculiar elastic properties of SR gels, we studied the effects of movable cross-links by using molecular simulations and theoretical analysis. We calculate the S-S relationships in biaxial deformation for two types of models: slip model, where the cross-links can slide along chains representing SR gels, and non-slip model, which corresponds to conventional chemical gels. In the theoretical analysis, we calculate the S-S relationships by using the models with the Gaussian and the Langevin chains to investigate the nonlinear stretching effect of the chain in the slip and non-slip models. As a result, we found that the peculiar elastic behaviors of SR gels in biaxial deformations are well explained by the effect of movable cross-links suppressing the nonlinear stretching of the chain.

Relationship between nutrition and reproduction.

BACKGROUND: Recently, the relationship between nutrition and reproduction is being studied. In particular, when older women receive reproductive treatment, egg aging causes greater problems than organic factors. METHODS: This study investigated the relationship between nutrition and reproduction with a focus on factors that cause aging, including oxidation, glycation, and chronic inflammation. A large volume of data concerning each nutrient's relationship with reproductive medicine was collected from a number of observational studies. MAIN FINDINGS: The results showed that refined carbohydrates should be avoided and care should be taken to achieve proper intake of omega-3 fatty acids. Folic acid and vitamin D were also effective. For men, antioxidant measures are especially effective. The effects of antioxidants are related to insulin resistance, which causes chronic inflammation. CONCLUSION: Recent research has shown that rather than meal content, meal intervals are more important for improving insulin resistance. Future research should examine lifestyle-related nutrition factors and their relationships to reproductive treatment.

Theory of transient networks with a well-defined junction structure.

The present study constructs a theory of physical gels consisting of bifunctional molecules, f-functional molecules, and solvent. This theory considered the formation of loops (i.e., the smallest cycles). First, the association state in the equilibrium state was investigated. Unlike the previous theory proposed by the authors, the present theory was able to describe the effect of functionality on the association state. Second, the dynamics of gelation was studied. As a result, the authors found two regimes: one where the characteristic time of gelation is governed by the association of associative groups and another where it is governed by the dissociation of them. Finally, theoretical results and the existing experimental results were compared in terms of gelation time and the time development of elasticity. With parameters set reasonably, the theory succeeded in the quantitative description of the experimental results.

Molecular simulation of structures and mechanical properties of nanocomposite networks consisting of disk-shaped particles and polymers.

We study the structures and the mechanical properties of nanocomposite networks consisting of disk-shaped particles and polymers by a coarse-grained molecular dynamics simulation. The disk-shaped particles and the polymers form tightly cross-linked network structures by the polymer adsorption on the disk-shaped particles and show high mechanical strength. We confirm the significance of the high polymerization degree for the large fracture elongations. Under the uniaxial elongation, at low elongation ratios, the networks maintain the cross-linked structures and indicate the sharp increase of the stress with the elongation. At large elongation ratios, the number of bridge chains decreases by the peeling of the adsorbed polymers from the disk-shaped particles. The decline of the bridge chains suppresses the increment of the stress. The orientation of the disk-shaped particles saturates prior to that of the polymers because of the slow orientation of the non-bridge chains. These results are consistent with reported experimental results.

Theoretical Analysis of Critical Flowable Physical Gel Cross-Linked by Metal Ions and Polyacrylamide-Derivative Associating Polymers Containing Imidazole Groups.

When the polymer chains are cross-linked by physical bonds having a finite lifetime, the relaxation time and viscosity do not diverge at the gel point though percolation occurs. These undivergent quantities are related to the finite-sized "largest relaxed cluster," which can relax before it breaks. Its size is the key rheological parameter characterizing of the critical physical gels. In order to evaluate this characteristic size, we propose here a generalized phenomenological model for the viscoelasticity of critical physical gels. We apply the theory to the previously reported experimental result for the physical gel consisting of polyacrylamide-derivative associating polymers containing imidazole groups cross-linked by coordination bonds with Ni ions. We successfully estimate the size of the largest relaxed cluster and the fractal dimension. The size is in good agreement with that estimated from the mean-square displacement of probe particles at the gel point by microrheological measurement. We also compare this system with the poly(vinyl alcohol) hydrogel cross-linked by borate ions, and show that the difference in the cluster structures is originating from the differences of precursor chain properties such as overlap concentration and radius of gyration and of the cross-linking states in these systems.

Theoretical Study of Network Formation and Mechanical Properties of Physical Gels with a Well-Defined Junction Structure.

A statistical-mechanical theory of thermoreversible gelation considering loops for the system consisting of bifunctional polymer units carrying A functional groups and trifunctional units carrying B functional groups at their ends is constructed. We obtain the sol-gel transition line and the properties of the post-gel region as functions of the polymer concentration, temperature, association constant, and loop parameter using the present theory. In this article, we calculate the number concentration of elastically effective chains in the gel region and obtain the shear modulus by an application of the phantom network theory. The shear modulus obtained by this theory is lower than that obtained by conventional theory because of loop formation. We find that these theoretical results are in good agreement with the experimental data.

Exclusion of impurity particles during grain growth in charged colloidal crystals.

We examine the spatial distribution of fluorescent-labeled charged polystyrene (PS) particles (particle volume fraction ϕ = 0.0001 and 0.001, diameter d = 183 and 333 nm) added to colloidal crystals of charged silica particles (ϕ = ϕ(s) = 0.035-0.05, d = 118 nm). At ϕ(s) = 0.05, the PS particles were almost randomly distributed in the volume-filling polycrystal structures before the grain growth process. Time-resolved confocal laser scanning microscopy observations reveal that the PS particles are swept to the grain boundaries of the colloidal silica crystals owing to grain boundary migration. PS particles with d = 2420 nm are not excluded from the silica crystals. We also examine influences of the impurities on the grain growth laws, such as the power law growth, size distribution, and existence of a time-independent distribution function of the scaled grain size.

Hydration, phase separation and nonlinear rheology of temperature-sensitive water-soluble polymers.

The collapse of a poly(N-isopropylacrylamide) (PNIPAM) chain upon heating and the phase diagrams of aqueous PNIPAM solutions with a very flat lower critical solution temperature (LCST) phase separation line are theoretically studied on the basis of cooperative dehydration (simultaneous dissociation of bound water molecules in a group of correlated sequence), and compared with the experimental observation of temperature-induced coil-globule transition by light scattering methods. The transition becomes sharper with the cooperativity parameter σ of hydration. The reentrant coil-globule-coil transition and cononsolvency in a mixed solvent of water and methanol are also studied from the viewpoint of competitive hydrogen bonds between polymer-water and polymer-methanol. The downward shift of the cloud-point curves (LCST cononsolvency) with the mol fraction of methanol due to the competition is calculated and compared with the experimental data. Aqueous solutions of hydrophobically modified PNIPAM carrying short alkyl chains at both chain ends (telechelic PNIPAM) are theoretically and experimentally studied. The LCST of these solutions is found to shift downward along the sol-gel transition curve as a result of end-chain association (association-induced phase separation), and separate from the coil-globule transition line. Associated structures in the solution, such as flower micelles, mesoglobules, and higher fractal assembly, are studied by ultra small-angle neutron scattering with theoretical modeling of the scattering function. Dynamic-mechanical modulus, nonlinear stationary viscosity, and stress build-up in start-up shear flows of the associated networks are studied on the basis of the affine and non-affine transient network theory. The molecular conditions for thickening, strain hardening, and stress overshoot are found in terms of the nonlinear amplitude A of the chain tension and the tension-dissociation coupling constant g.

Stress buildup under start-up shear flows in self-assembled transient networks of telechelic associating polymers.

The nonaffine transient network theory is used to study the time development of the shear and normal stresses under start-up shear flows in networks formed by self-assembled telechelic, hydrophobically modified water-soluble polymers. The initial slope, strain hardening, and overshoot of the shear stress are studied in detail in relation to the nonlinear tension-elongation curve of the elastically active chains in the network. The condition for the occurrence of strain hardening (upward deviation of the stress from the reference curve defined by the linear moduli) is found to be gamma > gammac(A), where gamma is the shear rate, gamma(c) is its critical value for strain hardening, and A is the amplitude of the nonlinear term in the tension of a chain. The critical shear rate gamma(c) is calculated as a function of A. It is approximately 6.3 (in the time unit of the reciprocal thermal dissociation rate) for a nonlinear chain with A = 10. The overshoot time t(max) when the stress reaches a maximum and the total deformation gamma(max) = gamma(t max) accumulated before the peak time are obtained in terms of the molecular parameters of the polymer chain. The maximum deformation gamma(max) turns out to depend weakly upon the shear rate gamma. The first and second normal stress differences are also studied on the basis of the exact numerical integration of the theoretical model by paying special attention to their overshoot, undershoot, and sign change as a function of the shear rate. These theoretical results are compared with recent rheological experiments of the solutions of telechelic hydrophobically modified poly(ethylene oxide)s carrying short branched alkyl chains (2-decyl-tetradecyl) at both ends.

Temperature-responsive polymers in mixed solvents: competitive hydrogen bonds cause cononsolvency.

If two good solvents become poor for a polymer when mixed, the solvent pair is called a cononsolvent pair. The sharp reentrant coil-to-globule-to-coil transition of a poly(N-isopropylacrylamide) chain observed in the mixed solvent of water and methanol is shown to be caused by the competitive hydrogen bonding by water and methanol molecules onto the polymer chain. On the basis of a new statistical-mechanical model for competitive hydrogen bonds, the mean square end-to-end distance is theoretically calculated and compared with experiment. The chain sharply collapses at the molar fraction xm approximately 0.2 of methanol, stays collapsed up to xm approximately 0.4, and finally recovers the swollen state at xm approximately 0.6. Such a reentrant coil-globule transition takes place because the total number of hydrogen bonds along the chain exhibits a similar square-well-type depression as a result of the competition.

Fetal aortic distension waveforms for evaluating cardiac function and changes in blood pressure: fetal lamb validation.

AIM: To investigate which part of the fetal aortic distension waveform is mainly influenced by changes in fetal cardiac contractility and aortic blood pressure. METHODS: In acute preparation, aortic distension waveforms were recorded using an echo-tracking system, and aortic and left ventricular pressure waveforms were obtained from six late-gestation catheterized fetal lambs. Dobutamine and angiotensin II were separately infused and the correlations between the maximum value in the first derivative of left ventricle pressure waveforms (Max dP/dt) and fetal blood pressure, and the parameters obtained from aortic distension waveforms were analyzed using linear regression analysis. RESULTS: With a change in cardiac contractility, the maximum value of first derivative of the systolic rising slope in the aortic distension waveform had a positive correlation with Max dP/dt (r = 0.93, P < 0.0001). With changes in fetal blood pressure, both the amplitude and the ratio of increase from the end diastolic diameter obtained from the aortic distension waveform had a significant positive correlation with aortic blood pressure amplitude (r = 0.60, P < 0.01; r = 0.61, P < 0.01, respectively). CONCLUSION: The maximum first derivative of the systolic rising slope in the aortic distension waveform and the amplitude in the aortic distension waveform enable us to non-invasively substitute for fetal cardiac contractility and aortic blood pressure amplitude, respectively.

Multicanonical Monte Carlo simulations on intramolecular micelle formation in copolymers.

The formation of intramolecular micelles in copolymers with periodic sequence, where hydrophobic units (stickers) are periodically placed along the chain, is studied by using multicanonical Monte Carlo computer simulations for an off-lattice bead-rod model in three dimensions. With decreasing the temperature, a transition from random-coil conformations to micelles occurs and flower-type micelles are formed via the transition. The number of stickers forming a micelle core is limited by the excluded-volume effect of loop chains around micelle cores. By this effect, two intramolecular micelles are formed for long polymer chains with 60 bonds via the coil-to-micelle transition. By further decreasing the temperature, we find that another transition, i.e., a micelle-to-micelle transition, takes place. At this transition point, the two intramolecular micelles merge into one micelle. Furthermore, we extend the multicanonical MC method to study elastic properties of single polymer chains with strong attractive interactions under external force fields, and study how the intramolecular micellization affects the elastic property of single polymer chains.

Noninvasive measurement of isovolumetric contraction time during hypoxemia and acidemia: Fetal lamb validation as an index of cardiac contractility.

OBJECTIVES: The objectives of this study are firstly to clarify how the Doppler isovolumetric contraction time (ICT) is influenced by arterial oxygen pressure (PaO2) or pH, and secondly to confirm the relationship between the Doppler ICT and myocardial contractility during hypoxemia and/or acidemia in the fetal lamb. MATERIAL AND METHODS: In 12 pregnant ewes, fetal hypoxemia and acidemia were induced by giving ewes a variable mixture of gases for 120 min. The chronological change of fetal PaO2, pH, Doppler ICT and maximum first derivative of the left ventricular pressure waveform (Max dp/dt) was recorded every 30 min. RESULTS: Doppler ICT and PaO2 had no significant regression. On the other hand, Doppler ICT and pH demonstrated a significant negative regression. Moreover, one critical given pH point was indicated with statistical significance at 7.20 and the prolongation of the Doppler ICT was found more markedly in the range below the pH of 7.20 compared with the range above 7.20. A significant negative linear regression was found between the Doppler ICT and the Max dp/dt. CONCLUSION: The measurement of Doppler ICT enables us to predict severe acidosis and a decrease of myocardial contractility in the fetus.

Jamming concepts in cold polymeric glasses.

The purpose of the present paper is to propose an idea to construct the volume function W for polymer glasses and calculate the volume of polymer glasses as a function of the compactivity X utilizing a statistical-mechanical method developed for semiflexible polymers. We also discuss the analogue for glasses of "tapping" experiments which show the validity of statistical mechanics and the entropy concept in powders.

Prenatal diagnosis of slow-rate ventricular tachycardia using fetal electrocardiography.

OBJECTIVES: We report a case in which fetal ventricular tachycardia (VT) could be diagnosed, in utero, using a transabdominal fetal electrocardiogram (fECG) with motion-mode (M-mode) echocardiography. METHODS: The fetus was referred at 32 weeks' gestation due to tricuspid atresia. The fetal cardiotocogram demonstrated paroxysmal tachycardia with a ventricular rate of 155 to 160 bpm within the confines of normal sinus rhythm. RESULTS: M-mode echocardiography showed atrioventricular dissociation with a rather slow ventricular rate. To identify the level of the ectopic focus for tachyarrhythmias, we attempted to detect the electrical signals of the fetal heart and succeeded in recording the fECG. Morphological assessment of the fECG allowed for the extraction of both the normal QRS complex and apparently dissimilar ectopic QRS beat, which has a different polarity despite a relatively similar width. CONCLUSION: Consequently, the case proved to have VT at a slow rate, probably originating from the focus near the atrioventricular junction inside the ventricle.

A new ultrasound technique to measure the isovolumetric contraction time as an index of cardiac contractility: fetal lamb validation.

OBJECTIVE: We developed a noninvasive Doppler technique for measuring fetal cardiac isovolumetric contraction time (ICT). The purpose of this study was to determine how well our method reflects real cardiac performance using fetal lamb as an instrumented model. METHODS: The true ICT was measured by simultaneous recording of the pressure waves of the left ventricle and ascending aorta. The maximum first derivative of the left ventricular pressure wave (Max dp/dt) was calculated. The Doppler ICT was measured in the appropriately filtered Doppler cardiac signals. Positive and negative inotropic agents were administered to change the cardiac contractility. RESULTS: There was an inverse relationship between the Doppler ICT and the Max dp/dt. Excellent linear correlation was found an absolute value and changes from control value between the true ICT and the Doppler ICT (r = 0.959, r = 0.962). CONCLUSIONS: The Doppler ICT measurement provides useful information about changes in ventricular performance.