Molecular dynamics simulation of the structural and mechanical property changes in the Brill transition of nylon 10/10 crystal

In order to confirm the structural features in the Brill transition of aliphatic nylons, molecular dynamics calculation has been performed at the various temperatures for nylon 10/10 crystal as a model. With an increase in temperature, the torsional motions around the methylene-amide and methylene-methylene bonds were activated. These motions became more remarkable above 420 K and the interconversion between trans and gauche forms occurred frequently, resulting in the disordered conformation of the methylene sequences and the pseudo-hexagonal packing of these parts. During such a drastic structural disordering, however, the hydrogen bonds were kept alive although the bond strength became weaker. These calculations were found to be consistent with the experimental results by the temperature-dependent X-ray diffraction and infrared spectral measurements. The Young's modulus along the chain axis was also calculated as a function of temperature: it decreased remarkably from 250 GPa at 0 K to 180 GPa at 300 K due to a small contraction of the skeletal chain by only about 0.2-0.5% through the torsional motion of the skeletal chains, and the modulus decreased furthermore to 80 GPa at 550 K because of the larger conformational disordering of the skeletal chains. The Young's modulus in the direction perpendicular to the chain axis was also found to decrease remarkably in parallel to the change of the chain packing mode.     

Structural change in the Brill transition of Nylon m/n (1) Nylon 10/10 and its model compounds

Structural changes in the Brill transitions of Nylon 10/10 and its model compounds have been investigated by carrying out the temperature-dependent measurements of X-ray diffraction and infrared spectra along with the DSC measurement. The crystal structure at room temperature was found to be the so-called α form with the all-trans zigzag methylene segments. When the samples were heated, the infrared progression bands of the methylene segments, which are sensitive to the length of all-trans segmental parts, were found to change their spectral patterns in the transition temperature region: the progression bands decreased in intensity and disappeared above the transition region. At the same time several new bands were observed to appear, which were found to correspond to the progression bands of (CH₂)₇-(CH₂)₅trans-zigzag segments. These spectral changes indicate that the methylene segments were conformationally disordered by an invasion of some gauche bonds and as a result the effective length of trans-zigzag segments became shorter. This conformational disordering was found to occur more remarkably in the methylene segment of NH-(CH₂)₁₀-NH part than the CO-(CH₂)₈-CO part. At the same time the infrared bands of amide groups, in particular the bands sensitive to the twisting angles about the CH₂-amide bonds were found to show the remarkable change, indicating the local conformational change from planar-zigzag to twisted form in the CH₂-amide moiety. The frequency shift of amide A band (NH stretching mode) indicated a weakening of intermolecular hydrogen bonds, which however, did not disappear up to the melting region. From these data combined with the X-ray diffraction data, the structural disordering in the Brill transition phenomena was deduced concretely.     

Structural change in the Brill transition of Nylon m/n (2) conformational disordering as viewed from the temperature-dependent infrared spectral measurements

The structural changes in the Brill transition of aliphatic Nylons m/n have been investigated by carrying out the temperature-dependent infrared spectral measurement for Nylon 6/10 -[-NH-(CH₂)₆-NHCO-(CH₂)₈-CO-]_n-, Nylon 6/12 -[-NH-(CH₂)₆-NHCO-(CH₂)₁₀-CO-]_n- and Nylon 10/10 -[-NH-(CH₂)₁₀-NHCO-(CH₂)₈-CO-]_n-. They took the crystal structure of α-form at room temperature. By heating the samples up to the Brill transition temperature region, the conformation of the methylene segments was found to change remarkably from the all trans-zigzag form to the disordered conformation constructed by shorter trans-zigzag segments combined with some gauche bonds. At the same time, the twisting motion was found to occur around the CH₂-amide bonds. During this order-to-disorder transition of molecular conformation, the intermolecular hydrogen bonds were kept alive although they were weaker gradually with increasing temperature. The methylene segments sandwiched by NH groups [NH(CH₂)_mNH] were found to be disordered more remarkably than those of CO(CH₂)_nCO sequence due to the difference in torsional energy barriers around the CH₂-NH and CH₂-CO bonds.     

Phase transition in nylon 6/clay nanocomposites on annealing

The γ→α crystalline phase transition in nylon 6/clay nanocomposite prior to melting was investigated by X-ray diffraction. The phase transition in the nanocomposite took place at 160 °C, 40 °C higher than that of nylon 6 at 120 °C. The transition extent in the nanocomposite was lower than that in nylon 6. This could be caused by the strongly confined spaces between layers, and the favorable environment for the formation of the γ phase in the existence of clay. Besides, the less grown crystallites of the α phase transformed from the γ phase in the nanocomposite began to melt at much lower temperature than its normal melting temperature.     

Structural study of a series of ethylene-tetrafluoroethylene copolymers with various ethylene contents, Part 2: Phase transition behavior investigated by temperature dependent measurements of X-ray fiber diagrams

Phase transitional behavior has been investigated for a series of ethylene (E) and tetrafluoroethylene (TFE) two-component copolymers on the basis of the temperature dependent measurement of X-ray fiber diagrams taken for the uniaxially-oriented samples. The usage of such uniaxially-oriented samples has allowed us to clarify the structural changes more definitely than before. So far, the crystalline transition from the low-temperature phase to the high-temperature phase had been assumed to occur continuously, but the detailed analysis of the X-ray reflections at higher scattering angles revealed for the first time that the transition is of the thermodynamically-discontinuous first-order type between the monoclinic and the pseudohexagonal phases. This phase transition temperature shifted toward lower temperature side as the TFE content became higher. The analysis of the X-ray reflection profile allowed us to imagine that low-temperature shift of the transition point is considered to occur due to the easier thermal motion of the planar-zigzag chains around the chain axis because of looser packing of chains containing higher population of bulky CF₂CF₂ groups. From these experimental data a phase diagram has been built up to show the phase transition behaviors of a series of E/TFE copolymers in a systematic manner. The characteristic features of the structural disordering including trans-gauche conformational exchange have been also discussed on the basis of the data of polarized infrared and Raman spectra combined with the X-ray diffuse scatterings.     

热拉伸对PGLA(90/10)纤维降解性能的影响

利用热拉伸获得不同性能与结构形态的PGLA(GA/LA摩尔比=90/10)纤维,并进行体外降解实验。在降解过程中,采用DSC、傅里叶红外光谱、扫描电镜等测试手段对PGLA(90/10)纤维的性能与形态变化进行研究。结果表明,热拉伸显著改变PGLA(90/10)纤维的降解特征。     

Determination of the width of the transition layer between the crystalline and amorphous zones in nylon 1010 by SAXS

The width of the transition layer between the crystalline and amorphous zones in nylon 1010 was determined by SAXS with point collimation and long-slit collimation, respectively. The width of the transition layer, E, was found to be 1.7 nm. The results show that the width of the transition layer is independent of crystallinity.     

Mesophase structure discovered through in-situ X-ray measurement in drawing process of poly(ethylene 2,6-naphthalene dicarboxylate) fiber

The structure development in the continuous laser-heated drawing process of poly(ethylene 2,6-naphthalene dicarboxylate) (PEN) fiber was analyzed by in-situ X-ray diffraction measurement. Because of the rapid and uniform laser heating, and the resultant steady-state nature of the necking-drawing, the structure development after the on-set of necking could be measured in the time resolution of several hundred microseconds. We found for the first time the temporal appearance of meridional (001′) diffraction at several milliseconds after the on-set of necking indicating that the mesophase structure similar to the one reported for poly(ethylene terephthalate) was also formed in the initial stage of fiber structure development of PEN. The d-spacing of the (001′) diffraction 1.230 ± 0.003 nm was shorter than the c-axis lengths of both α and β crystals.     

Equivalent processing time analysis of glass transition development in epoxy/carbon fiber composite systems

The cure kinetics and glass transition development of a commercially available epoxy/carbon fiber prepreg system, DMS 2224 (Hexel F584), was investigated by isothermal and dynamic‐heating experiments. The curing kinetics of the model prepreg system exhibited a limited degree of cure as a function of isothermal curing temperatures seemingly due to the rate‐determining diffusion of growing polymer chains. Incorporating the obtained maximum degree of cure to the kinetic model development, the developed kinetic equation accurately described both isothermal and dynamic‐heating behavior of the model prepreg system. The glass transition temperature was also described by a modified DiBeneditto equation as a function of degree of cure. Finally, the equivalent processing time (EPT) was used to investigate the development of glass transition temperature for various curing conditions envisioning the internal stress buildup during curing and cooling stages of epoxy‐based composite processing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 144–154, 2002; DOI 10.1002/app.10282     

Application of nanoindentation testing to study of the interfacial transition zone in steel fiber reinforced mortar

The characteristics of the profiles of elastic modulus and hardness of the steel fiber-matrix and fiber-matrix-aggregate interfacial zones in steel fiber reinforced mortars have been investigated by using nanoindentation and Scanning Electron Microscopy (SEM), where two sets of parameters, i.e. water/binder ratio and content of silica fume were considered. Different interfacial bond conditions in the interfacial transition zones (ITZ) are discussed. For sample without silica fume, efficient interfacial bonds across the steel fiber-matrix and fiber-matrix-aggregate interfaces are shown in low water/binder ratio mortar; while in high water/binder ratio mortar, due to the discontinuous bleeding voids underneath the fiber, the fiber-matrix bond is not very good. On the other hand, for sample with silica fume, the addition of 10% silica fume leads to no distinct presence of weak ITZ in the steel fiber-matrix interface; but the effect of the silica fume on the steel fiber-matrix-aggregate interfacial zone is not obvious due to voids in the vicinity of steel fiber.     

Effect of moisture on the thermoelectric properties in expanded graphite/carbon fiber cement composites

A kind of dry mixing and pressing process was introduced to prepare expanded graphite/carbon fiber cement composites (EG-CFRC). Significant effect of moisture on the thermoelectric properties of EG-CFRC was observed. The higher the moisture content is, the greater the absolute Seebeck coefficient. The maximum of absolute Seebeck coefficient 11.59 μV/°C was obtained with moisture of 14.98% at 33 °C. Simultaneously, the maximum of electrical conductivity 0.78 S cm⁻¹ was got with moisture of 11.44%. Furthermore, the largest power factor 7.85×10⁻⁴ µW m⁻¹ K⁻² was calculated at 33 °C with moisture of 11.44%. The carrier scattering, polarization effects and high density defects interface of EG-CFRC are attributed to the enhancement of thermoelectric properties in the case of higher moisture content.     

A kinetic interpretation of a negative time constant in impedance equivalent circuits for the dissolution/passive transition

A theoretical impedance function is proposed for the active/passive transition of nickel in an acid sulphate medium. It is considered that passivating species progressively covers the electrode surface. This approximated model predicts the appearance of negative time constants in the impedance spectra when coverage coefficient θ values for passive species are greater than 0.5.     

Mechanical modeling of the transcrystalline interphase behavior in commingled PBT/glass fiber composites

In a previous work, a mechanical model was proposed to predict the reinforcement of amorphous polymers by particulates as well as by unidirectional fibers over wide ranges of volume fractions of fillers and temperatures (or frequencies). This model is based on both the definition of a representative morphological pattern (RMP), accounting for the presence of fiber clusters, and a quantitative morphology analysis, based on the percolation concept. In this work, such an approach is extended to describe the viscoelastic properties of a semicrystalline polymer, poly(butylene terephthalate), commingled with 30 and 50 vol % of unidirectional glass fibers. It is found that aggregates constituted by both fiber clusters and a transcrystalline region (TCR) can act as the continuous phase. Based on the use of a mechanical model in a reverse mode, the actual viscoelastic behavior of this TCR is extracted and compared to that displayed by the unfilled polymer. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2513–2524, 2000     

Hydrothermal transformation of the calcium aluminum oxide hydrates CaAl2O4·10H2O and Ca2Al2O5·8H2O to Ca3Al2(OH)12 investigated by in situ synchrotron X-ray powder diffraction

The hydrothermal transformation of calcium aluminate hydrates were investigated by in situ synchrotron X-ray powder diffraction in the temperature range 25 to 170 °C. This technique allowed the study of the detailed reaction mechanism and identification of intermediate phases. The material CaAl₂O₄·10H₂O converted to Ca₃Al₂(OH)₁₂ and amorphous aluminum hydroxide. Ca₂Al₂O₅·8H₂O transformed via the intermediate phase Ca₄Al₂O₇·13H₂O to Ca₃Al₂(OH)₁₂ and gibbsite, Al(OH)₃. The phase Ca₄Al₂O₇·19H₂O reacted via the same intermediate phase to Ca₃Al₂(OH)₁₂ and mainly amorphous aluminum hydroxide. The powder pattern of the intermediate phase is reported.     

Exploring the Catalytic Mechanism of the RNA Cap Modification by nsp16-nsp10 Complex of SARS-CoV-2 through a QM/MM Approach

The inhibition of key enzymes that may contain the viral replication of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) have assumed central importance in drug discovery projects. Nonstructural proteins (nsps) are essential for RNA capping and coronavirus replication since it protects the virus from host innate immune restriction. In particular, nonstructural protein 16 (nsp16) in complex with nsp10 is a Cap-0 binding enzyme. The heterodimer formed by nsp16-nsp10 methylates the 5′-end of virally encoded mRNAs to mimic cellular mRNAs and thus it is one of the enzymes that is a potential target for antiviral therapy. In this study, we have evaluated the mechanism of the 2′-O methylation of the viral mRNA cap using hybrid quantum mechanics/molecular mechanics (QM/MM) approach. It was found that the calculated free energy barriers obtained at M062X/6-31+G(d,p) is in agreement with experimental observations. Overall, we provide a detailed molecular analysis of the catalytic mechanism involving the 2′-O methylation of the viral mRNA cap and, as expected, the results demonstrate that the TS stabilization is critical for the catalysis.     

Axial variation of the oxidation state of Pt-Rh/Al2O3 during partial methane oxidation in a fixed-bed reactor: An in situ X-ray absorption spectroscopy study

Probing the structure of materials in situ is of central importance in heterogeneous catalysis. Mostly, this is done in an integral manner, that is without spatial resolution. However, at high conversion in a catalyst bed prominent concentration and/or temperature profiles may exist which can result in significant spatial variation of the catalyst structure. In the present study, X-ray absorption spectroscopy combined with on-line mass spectrometry was used to monitor the structural changes of a Pt-Rh/Al₂O₃ catalyst in a fixed-bed reactor during partial oxidation of methane. The reaction ignited at 310 °C and integral X-ray absorption spectroscopy showed that the Rh-Pt-particles were reduced at the same time. However, monitoring with a beam of 1 mm × 0.6 mm size along the axial position of the catalyst bed uncovered that Rh and Pt were still in oxidized state in the entrance region, whereas they were in reduced state in the zone at the end of the catalyst bed. The gradual transition from the reduced to the oxidized state was found to shift towards the bed entrance if the temperature was slightly increased.An erratum to this article can be found at .     

A Comparative Study of the Explosion Characteristics of IPN and IPN/JP‐10 Mixtures in Air Aerosols

This article presents a comparison of the explosion characteristics of mixtures of isopropyl nitrate (IPN, (CH₃)₂CHONO₂) and JP‐10 (C₁₀H₁₆, tricycle [5.2.1.0^2,6] decane) in air aerosols. The explosion pressure, flame temperature, maximum rate of pressure rise, maximum rate of temperature rise, and lower flammability limits (LFLs) were measured for two sets of IPN and mixed IPN/JP‐10 in air aerosols at different concentrations and Sauter mean diameters (SMDs) of 19 μm and 34 μm, respectively, and the values were compared with the experimental results of JP‐10/air aerosols with SMDs of 20 μm and 35 μm (from our previous research). Experiments were also performed to study various concentrations at various ignition energies for the IPN/air aerosols and the explosions of binary mixture aerosols with various mass ratios of IPN and JP‐10. The experimental results indicated that for the IPN/air and JP‐10/air aerosols with a mean SMD of ∼34 μm, the maximum peak pressure and maximum peak temperature of the IPN/air aerosols were greater than those of the JP‐10/air aerosols. The maximum rate of pressure rise of the IPN/air aerosols reached a maximum value of 395.3 MPa/s at a mean SMD of ∼34 μm, and the pressure increased more abruptly in the IPN/air aerosols than in the JP‐10/air aerosols. The LFLs of the IPN/air aerosols occurred with a total concentration of 197 g/m³ at a mean SMD of 19 μm and a total concentration of 233 g/m³ at a mean SMD of 34 μm, whereas the LFLs for the JP‐10/air aerosols with SMDs of 20 μm and 35 μm were less than 47 g/m³ and 40 g/m³, respectively. The experimental results presented here also showed that the maximum peak pressure was 1.07 MPa at a binary liquid mass ratio of IPN:JP‐10 (%) of 72 : 28 and a mean SMD of ∼34 μm.     

The Amino Acid Transporter Mct10/Tat1 Is Important to Maintain the TSH Receptor at Its Canonical Basolateral Localization and Assures Regular Turnover of Thyroid Follicle Cells in Male Mice

Cathepsin K-mediated thyroglobulin proteolysis contributes to thyroid hormone (TH) liberation, while TH transporters like Mct8 and Mct10 ensure TH release from thyroid follicles into the blood circulation. Thus, thyroid stimulating hormone (TSH) released upon TH demand binds to TSH receptors of thyrocytes, where it triggers Gα_q-mediated short-term effects like cathepsin-mediated thyroglobulin utilization, and Gα_s-mediated long-term signaling responses like thyroglobulin biosynthesis and thyrocyte proliferation. As reported recently, mice lacking Mct8 and Mct10 on a cathepsin K-deficient background exhibit excessive thyroglobulin proteolysis hinting towards altered TSH receptor signaling. Indeed, a combination of canonical basolateral and non-canonical vesicular TSH receptor localization was observed in Ctsk^−/−/Mct8^−/y/Mct10^−/− mice, which implies prolonged Gα_s-mediated signaling since endo-lysosomal down-regulation of the TSH receptor was not detected. Inspection of single knockout genotypes revealed that the TSH receptor localizes basolaterally in Ctsk^−/− and Mct8^−/y mice, whereas its localization is restricted to vesicles in Mct10^−/− thyrocytes. The additional lack of cathepsin K reverses this effect, because Ctsk^−/−/Mct10^−/− mice display TSH receptors basolaterally, thereby indicating that cathepsin K and Mct10 contribute to TSH receptor homeostasis by maintaining its canonical localization in thyrocytes. Moreover, Mct10^−/− mice displayed reduced numbers of dead thyrocytes, while their thyroid gland morphology was comparable to wild-type controls. In contrast, Mct8^−/y, Mct8^−/y/Mct10^−/−, and Ctsk^−/−/Mct8^−/y/Mct10^−/− mice showed enlarged thyroid follicles and increased cell death, indicating that Mct8 deficiency results in altered thyroid morphology. We conclude that vesicular TSH receptor localization does not result in different thyroid tissue architecture; however, Mct10 deficiency possibly modulates TSH receptor signaling for regulating thyrocyte survival.     

SMA-10 Is a Non-Canonical Member of the TGF-β Sma/Mab Pathway and Immunity Regulator via the DAF-2 Insulin Receptor in Caenorhabditis elegans

Transforming growth factor β (TGF-β) signalling pathways are highly conserved across metazoa and play essential roles not only during development but also in adult tissue maintenance. Alterations of these pathways usually result in a plethora of pathologies. In the nematode Caenorhabditis elegans, the TGF-β Sma/Mab (small/male abnormal) pathway regulates various worm phenotypes such as body size, immune response, ageing, matricide and reproductive span. SMA-10 has been described as a positive modulator of worm body size through the TGF-β Sma/Mab pathway. To better understand if SMA-10 is a core component of the pathway, we use gene epistatic analysis to assess the contribution of SMA-10 to various phenotypes regulated by TGF-β Sma/Mab. We confirm that SMA-10 controls body size and find that it also affects the matricide and reproductive span of the nematodes. However, neither male tail formation (previously reported) nor ageing appeared altered. Lastly, although null sma-10 worms are more susceptible to Pseudomonas aeruginosa infections than wild-types, this response does not depend on TGF-β Sma/Mab but on the insulin receptor DAF-2. We also show that the expression of sma-10 in either hypodermis or intestine fully rescues the wild-type immune response. Our results contribute to understanding the role of SMA-10 as a context-dependent component of TGF-β Sma/Mab, and reveal a function of SMA-10 in immunity in association to the Insulin/insulin-like growth factor signalling (IIS) pathway.