Order/Disorder in Protein and Peptide-Based Biomaterials

Nature utilizes both order and disorder (or controlled disorder) to achieve exceptional materials properties and functions, while synthetic supramolecular materials mostly exploit just supramolecular order, thus limiting the structural diversity, responsiveness and consequent adaptive functions that can be accessed. Herein, we review the emerging field of supramolecular biomaterials where disorder and order deliberately co-exist, and can be dynamically regulated by considering both entropic and enthalpic factors in design. We focus on sequence-structure relationships that govern the (cooperative) assembly pathways of protein and peptide building blocks in these materials. Increasingly, there is an interest in introducing dynamic features in protein and peptide-based structures, such as the remarkable thermo-responsiveness and exceptional mechanical properties of elastin materials. Simultaneously, advances in the field of intrinsically disordered proteins (IDPs) give new insights about their involvement in intracellular liquid-liquid phase separation and formation of disordered, dynamic coacervate structures. These have inspired efforts to design biomaterials with similar dynamic properties. These hybrid ordered/disordered materials employ a combination of intramolecular and supramolecular order/disorder features for construction of assemblies that are dynamically reconfigurable. The assembly of these dynamic structures is mainly entropy-driven, relying on electrostatic and hydrophobic interactions and is mediated in part through the adopted (unstructured) protein conformation or by introducing an oppositely charged guest for peptide building blocks. Examples include design of protein building blocks composed of disordered repeat sequences of elastin-like polypeptides in combination with ordered regions that adopt a secondary structure, the co-assembly of proteins with peptide amphiphiles to achieve reconfigurable, yet highly stable membranes or tyrosine-containing tripeptides with sequence-controlled order/disorder that upon enzymatic oxidation give rise to melanin-like polymeric pigments with customizable properties. The resulting hybrid materials with controlled disorder can be metastable, and sensitive to various external stimuli giving rise to insights that are especially attractive for the design of responsive and adaptive materials.     

Ordering in Ni-Mo alloys—First-principles calculations versus experimental observations

An extensive amount of experimental work has been reported in the literature on the ordering behaviour of Ni-Mo alloys containing 8–33 at% of Mo, which exhibit both short-range and long-range ordering phenomena and a competition among several fcc-based long-range ordered structures. We have used local-density-based tight binding linear muffin-tin orbital (TB-LMTO) method in conjunction with ‘augmented space recursion + orbital peeling’ (ASR + OP) for the determination of ground state energies of these superstructures in terms of effective pair interactions up to the fourth nearest neighbour pairs. The ordering behaviour of the four competing fcc-based superstructures has been studied using the mean-field-based ‘static concentration wave’ (SCW) model in terms of the free energy-order parameter plots (Landau plots) and the free energy-composition plots. The instability domains with respect to concentration fluctuations, both short wavelength (ordering) and long wavelength (clustering) have been identified from these calculations. This information has been used to predict the sequence of transformation events in the Ni-Mo alloys undergoing ordering and/or clustering and the results are compared with those obtained experimentally.     

First-principles calculation of phase equilibria and phase separation of the Fe-Ni alloy system

Theoretical investigation of the phase equilibria of the Fe-Ni alloy has been performed by combining the FLAPW total energy calculations and the Cluster Variation Method through the Cluster Expansion Method. The calculations have proved the stabilization of the LIE phase at 1：3 stoichiometry, which is in agreement with the experimental result, and predicted the existence of L1 0 as a stable phase below 550 K; this L1 0 phase has been missing in the conventional phase diagram. The calculations are extended to the Fe-rich region that is characterized by a wide range phase separation and has drawn considerable attention because of the intriguing Invar property associated with a Fe concentration of 65%. To reveal the origin of the phase separation, a P-V curve in an entire concentration range is derived by the second derivative of free energy functional of the disordered phase with respect to the volume. The calculation confirmed that the phase separation is caused by the breakdown of the mechanical-stability criterion. The newly calculated phase separation line combined with the L1 0 and L12Eorder-disordered phase boundaries provides phase equilibria in the wider concentration range of the system. Furthermore, a coefficient of thermal expansion （CTE） is attempted by incorporating the thermal vibration effect through harmonic approximation of the Debye-Gruneisen model. The Invar behavior has been reproduced, and the origin of this anomalous volume change has been discussed.     

Pb(Mg_(1+x)/3Nb_(2-x)/3)O_3铁电材料中有序-无序相变的理论研究

基于Kikuchi自洽迭代方法,利用有序-无序相变理论,并取最近邻相互作用近似,研究了Pb(Mg_((1+x)/2)Nb_((2-x)/2)O_3晶粒中在x=0.5时有序区形成的原因,提出Mg~(2+)∶Nb~(5+)=1∶1(离子数比)时,形成B位有序排列最为有利,并且弱的空间电荷场不影响这种有序排列的形成,同时给出了温度-组份的有序-无序相图。     

B位离子部分取代和Fe/Nb比改变对Pb(Fe_(1/2)Nb_(1/2))O_3陶瓷介电弛豫性能的影响

对 Pb(Fe_(1/2)/Nb_(1/2))O_3铁电陶瓷进行了 B 位离子部分取代和改变 Fe/Nb 比对介电性能、介电弛豫性能影响的研究,发现当它的 B 位 B_1、B_2离子比偏离于1:1时,其 K_(max)的频率弥散变明显(即△T_(0.1-100kHz)>0°),这可能是在有序-无序基本弛豫极化基础上产生了附加的空间电荷弛豫极化,它对弛豫铁电体的介电弛豫性质起着一定贡献。     

铌铁酸铅PFN的结构无序及介电相变特性

运用高分辨透射电镜显微技术观察到ＰＦＮ中Ｂ位离子呈无序排列，不易形成有序结构，在性能上，ＰＦＮ的介电常数ε和介电损耗ｔｇδ均很大，相变扩散度小；相应时的介电行为，热容和热膨胀的变化比较特殊。     

The effects of heat treatment condition and Si distribution on order-disorder transition in high Si steels

The decomposition and formation of ordered phases in steels with 5 to 6.5 %Si were investigated by a combined analysis of TEM and electrical resistivity measurements in order to determine the optimal heat treatment conditions for removal of ordered phases. TEM diffraction pattern study revealed that B2 ordered phase in 6.5 %Si steel was sufficiently dissolved by heat treatment at 850 °C for 1 h, and then rapidly re-formed during cooling. The critical cooling rate, above which the suppression of B2 phase formation was possible, increased rapidly with Si content higher than 5.6%. DO₃ phase appeared only in the case of as-cast samples containing Si content as high as 6.5%. The measurement of electrical resistivity change during the heat treatment showed that the atomic movement was substantially spurred above 800 °C, resulting in an active order-disorder transition. The removal of solidification segregation is necessary to reduce the amount of B2 ordered phase in the as-cast or hot-rolled state, to lower the heat treatment temperature for dissolution of B2 ordered phase, and to shorten the heat treatment time. This article is based on a presentation made in the 2003 Korea-Japan symposium on the “Current Issues on Phase Transformations”, held at Marriott Hotel, Busan, Korea, November 21, 2003, which was organized by the Phase Transformation Committee of the Korean Institute of Metals and Materials.     

V_8C_7有序-无序相变及衍射消光规律的研究

V8C7有序-无序相变是一类重要的相变。本文通过利用x射线衍射和差热分析研究其相变过程,并计算V8C7、VC0.875衍射消光规律。研究结果表明：V8C7在1200-1300℃之间发生有序一无序相变,相变的温度点为1242℃,（110）、（111）、（210）、（211）、（320）、（421）、（432）晶面产生的衍射超结构线消失。通过对δ-VC1-x和V8C7结构振幅的计算,得到δ-VC1-x衍射消光规律：当h、k、l全为奇数时衍射强度减弱;当h、k、l全为偶数时衍射强度加强;h、k、l为两偶一奇或两奇一偶时完全消光。V8C7衍射消光规律：由于空位有序分布,产生超结构线的晶面为（110）、（111）、（210）、（211）、（320）、（421）、（432）。     

Temperature-Dependent Phase Behaviors in Cylinder-Forming Block Copolymers

We demonstrate that the temperature-dependent phase behaviors of parallel and perpendicular cylinder-forming block copolymers are governed by domain-domain segregation forces inherently present in block copolymer material itself. With increasing temperature, a parallel cylinder-forming block copolymer experienced a parallel cylinder straightening process before the order-disorder transition (ODT) and did not show long-range composition fluctuations near the ODT temperature due to the weak segregation forces between the block domains. A perpendicular cylinder-forming block copolymer with a strong segregation force between the block domains displayed cylinder orientation transition from perpendicular to parallel below the ODT temperature. On the other hand, a perpendicular cylinder-forming block copolymer material with an exceptionally strong segregation force between the block domains maintained its initial perpendicular cylinder orientation up to near the ODT temperature. In both cases of perpendicular cylinder-forming block copolymers, submicrometer-scale long-range composition fluctuations were observed well above the ODT temperature due to their intrinsically strong segregation forces between the block domains.     

Bi_2Co_(0.1)V_(0.9)O_(5.35-δ)中的有序-无序相变研究

采用示差扫描量热法(DSC)、热膨胀曲线法及交流阻抗谱法对Bi2Co0.1V0.9O5.35-δ陶瓷的相变过程进行了研究。研究结果表明,Bi2Co0.1V0.9O5.35-δ陶瓷在420~500℃温度范围内产生了相变,这种相变是温度发生变化时钒氧八面体层内氧空位排列的有序-无序转变引起的。