MOLECULAR CLOSE-PACKING METHOD AND ITS APPLICATION TO CRYSTAL STRUCTURE DETERMINATION OF DESHEXAPEPTIDE (B25--B30) INSULIN

Based on the molecule-packing theory, we defined a molecule-packing function express-ing the compatibility of packing among the symmetry-related molecules in a unit cell. Acomputer program imitating the close-packing of molecules in the objective crystal latticeand giving the function value of each rotation and translation of the molecule in the unitcell was performed, and it therefore made the close-packing of molecules expressquantitatively. This method not only could judge a correct solution from several peaks ofthe rotation or translation function but it may also independently, quantitatively and quicklysolve some specific problems of rotation and translation. Using known structure of despenta-peptide (B26--B30) insulin as an example, the effectiveness of this method and its programwas inspected, and this method was successfully applied to solving the translation problem ofthe unknown structure of deshexapeptide (B25--B30) insulin. The molecular close-packingmethod proved by the results of R--search and electron density maps is relatively independ-ent of the molecular replacement method, though an effective complement of it.

Simple Model of Transformation of a Crystal Structures

A simple model of the closely packed structure for system of hard-sphere particles interacting via the long-range Newtonian type attraction is suggested. Based on density functional theory, the exact equation of state is obtained and the mutual transformations of the crystal structures in such systems are studied. The description takes into account the fact impossibility of hard-sphere particles which have the same spatial occupation place.

Solid−solid phase transition of tungsten induced by high pressure:A molecular dynamics simulation

The phase transition of tungsten(W)under high pressures was investigated with molecular dynamics simulation.The structure was characterized in terms of the pair distribution function and the largest standard cluster analysis(LSCA).It is found that under 40−100 GPa at a cooling rate of 0.1 K/ps a pure W melt first crystallizes into the body-centred cubic(BCC)crystal,and then transfers into the hexagonal close-packed(HCP)crystal through a series of BCC−HCP coexisting states.The dynamic factors may induce intermediate stages during the liquid−solid transition and the criss-cross grain boundaries cause lots of indistinguishable intermediate states,making the first-order BCC−HCP transition appear to be continuous.Furthermore,LSCA is shown to be a parameter-free method that can effectively analyze both ordered and disordered structures.Therefore,LSCA can detect more details about the evolution of the structure in such structure transition processes with rich intermediate structures.

High-pressure Raman study of osmium and rhenium up to 200 GPa and pressure dependent elastic shear modulus C_(44)

High-pressure Raman scattering from hexagonal close-packed(HCP) metals Os and Re have been extended up to 200 GPa, and the pressure-dependent shear modulus C_(44)has been deduced from the Raman-active mode E_(28), which is generated from the adjacent vibration of atoms in hexagonal planes, providing the valuable information about the elastic properties for HCP metals under high pressure. Combined with the available data of HCP metals from previous works,a further study indicates that the C_(44)/C_(44)ratio would be close to a constant value, 0.01, with increasing atomic number of metals. The results obtained from high-pressure Raman scattering will allow us to probe the elastic anisotropy of the HCP metals at very high pressure.

Breaking the lithium storage limit via independent bilayer units within 2D layer materials

Lithium intercalation into graphite contributes a theoretical capacity of 372 m Ah g-1and thus leads to an earthshaking change for energy storage[1].Lithium intercalation behaviors have been investigated via X-ray diffraction(XRD),Raman,Fourier transform infrared spectroscopy(FTIR)and X-ray absorption fine structure (XAFS)with the aid of in-situ electrochemical characterization technologies.

Interaction of Point Defects with Twin Boundaries in Copper

The interaction between small vacancy clusters and twin boundaries in copper is studied by using many-body potential developed by Ackland et aL for fcc metals. The interaction energies of single-, di- and tri-vacancy clusters with （111） and （112） twin boundaries are computed using well established simulation techniques. For （111） twins the vacancy clusters are highly repelled when they are on the adjacent planes, and are attracted when they are away from the boundary. In the case of （112） twins, vacancy clusters are more attracted to the boundary when they are near the boundary as compared to away from it. Vacancy clusters on both the sides of the boundary are also investigated, and it is observed that the clusters energetically prefer to lie on the off-mirror sites as compared to the mirror position across the twin.

Analytical Bond-order Potential for hcp-Y

The lattice parameters, elastic constants, cohesive energy, structural energy differences, as well as the properties of point defects and planar defects of hexagonal closepacked yttrium （hcpY） have been studied with ab initio density functional theory for constructing an ex tensive database. Based on an analytical bondorder poial scheme, empirical manybody interatomic potential for hcpY has been developed. The model is fitted to some properties of Y, e.g., the lattice parameters, elastic constants, bulk modulus, cohesive energy, vacancy formation energy, and the structural energy differences. The present potential has ability to reproduce defect properties including the selfinterstitial atoms formation energies, vacancy formation energy, divacancy binding energy, as well as the bulk properties and the thermal dynamic properties.

Equivalent model of close-packed film cooling holes in nickel-based single crystal cooled blade based on crystallographic theory

The mechanical properties of nickel-based single crystal thin-walled plate with close-packed film cooling holes were studied based on the equivalent solid material concept. The effective plastic parameters inversion method based on crystallographic theory were proposed. A simplification method for close-packed film cooling hole plates with square and triangular penetration patterns was presented. A large number of finite element analysis results covering different ligament efficiencies and penetration patterns were provided to verify the feasibility of the plastic equivalent principle and simplification method. The results show that the stress–strain curve and resolved shear stresses of simplification models are in consistence with the plate models with close-packed film cooling holes. The equivalent errors of yield strength are all within the error band and the values of equivalent errors are all less than 10%. In addition, the equivalent errors of the positions where maximum resolved shear stress occurs are all less than 15°, indicating the accuracy of plastic equivalent model and simplification method.

Full quantum mechanics calculation of the total energy for the hexagonal close-packed structure of metallic hydrogen

Metallic hydrogen could be not only high-efficiency fuel for nuclear fusion and high explosive but also a high-temperature superconductor. The study of metallic hydrogen is of great help to solving some important problems in the field of geophysics and astrophysics, such as the electronic and magnetic properties of the giant planets (Jupiter and Saturn) and their evolution, processes. So the study of metallic hydrogen is of momentous significance both theoretically and practically. In 1935 Wigner and Huntington pro-

Entropy versus enthalpy in hexagonal-close-packed highentropy alloys

The addition of hexagonal-close-packed(hcp)non-rare-earth elements Zr,Ti and Co,to the 10-component hep rare-earth-based high-entropy alloys(HEAs)with a composition of ScYLaNdGdTbDyHoErLuX(X=Zr,Co and Ti)was investigated.The enthalpy of mixing between elements was found to have a significant effect on the formation of phases.The addition of Co combines with elements that had a strong chemical affinity to form intermetallic compounds by the effect of enthalpy.Ti was added with all elements with poor chemical affinity and exhibited rejection to form a phase alone.These were the two terminal manifestations of the role of enthalpy over entropy.Part of Zr was soluble in the matrix under the action of entropy,while the other part had a greater affinity for Sc than the other elements to form a precipitate under the action of enthalpy.This was the result of the local balance between the effect of enthalpy and entropy.The solid solution of the elements had different degrees of strengthening effect,among which Zr had the most excellent strengthening effect from 185 to 355 MPa,so the solid solution strengthening model and precipitation strengthening model were proposed to predict the strength of the alloy with the addition of Zr effectively.

Constitutive Model for the Thermo-viscoplastic Behavior of Hexagonal Close-Packed Metals with Application to Ti-6A1-4V Alloy

In this paper, a new physically based constitutive model is developed for hexagonal close-packed metals, especially the Ti-6Al-4V alloy, subjected to high strain rate and different temperatures based on the microscopic mechanism of plastic deformation and the theory of thermally activated dislocation motion. A global analysis of constitutive parameters based on the Latin Hypercube Sampling method and the Spearman＇s rank correlation method is adopted in order to improve the identification efficiency of parameters. Then, an optimal solution of constitutive parameters as a whole is obtained by using a global genetic algorithm composed of an improved niche genetic algorithm, a global peak determination strategy and the local accurate search techniques. It is concluded that the proposed constitutive modal can accurately describe the Ti-6Al-4V alloy＇s dynamic behavior because the prediction results of the model are in good agreement with the experimental data.

NiFe alloy nanoparticles with hexagonal close-packed crystal structure stimulate superior OER electrocatalytic activity

With the support by the National Natural Science Foundation of China and the Chinese Academy of Sciences,the research team led by Prof.Wang QiangBin(王强斌)at the CAS Key Laboratory of Nano-Bio Interface,Division of Nanobiomedicine and i-Lab,Suzhou Institute of Nano-Tech and Nano-Bionics,Chinese Academy of Sciences,revealed the role of metal alloy crystal structure in oxygen evolution reaction,which was recently published in Angew Chem Int Ed(2019,58(18):6099—6103).

The crystal structure of deshexapeptide(B25-B30)insulin at 0.25 nm resolution

The determination of deshexapeptide(B25-B30)insulin(DHI)was divided into two steps.At the first step,the rough structure model of DHI molecule was determined by using the molecularreplacement method associated with the molecular close-packing method at 0.30 nm resolution based on the re-flection data collected on four-cycle diffractometer.At the second step,the DHI model was adjusted and re-fined at 0.25nm resolution based on the data collected on Area Detector.40 water molecules were determinedduring the refinement,the final R-factor is 0.185 with R.M.S.deviation of 0.002nm for bond lengths and 1.9°for bond angles.The differences in conformation and function of DHI with other insulin analogues werecompared and discussed.

Preternatural Hexagonal High-Entropy Alloys: A Review

Recently,various topics on high-entropy alloys have been reported and great amounts of excellent properties have been investigated,including high strength,great corrosion resistance,great thermal stability,good fatigue and fracture properties,etc.Among all these research activities,high-entropy alloys tend to form face-centered-cubic(FCC)or body-centeredcubic(BCC)solid solutions due to their high-entropy stabilization effect,while the hexagonal structures are rarely reported.Up to now,the reported hexagonal high-entropy alloys are mainly composed of rare-earth elements and transitional elements.Their phase transformation and magnetic properties have also aroused wide concern.This study summarizes the above results and provides the forecast to the future.

FCC-to-HCP Phase Transformation in CoCrNi_x Medium-Entropy Alloys

A hybrid first-principles/Monte Carlo simulation is combined with experiments to study the structure and elastic properties of CoCrNi_x(x=1-0.5)alloys.The experimental X-ray diffraction patterns show that the structures have changed from the single-phase face-centered cubic(FCC)structure at x=1-0.8 to the coexistence of FCC and the hexagonal close-packed structures at x=0.7-0.5,which is further confirmed by calculations on mixing energies.The elastic moduli by calculation are basically in agreement with experiments.Room-temperature tension shows that the six alloys have a certain plasticity,the strength and plasticity of the alloys have a linear decrease with the decrease in Ni contents,and the plasticity of the alloys drops from 84 to 23%.Furthermore,first-principles density function theory calculations were employed to reveal the electronic and magnetic structures of alloys.The electron density of states for all alloys is asymmetrical,which illustrates that the alloys are ferromagnetism.It is found that Cr atoms can suppress the ferromagnetism of alloys,since Cr atoms have both positive and negative magnetic moments in all alloys.

Microstructural Instability of an Experimental Nickel-Based Single-Crystal Superalloy

Microstructural instability with the precipitation of topologically close-packed(TCP)phases of an experimental nickel-based single-crystal superalloy has been investigated.A significant amount of σ phases are distinguished in the interdendritic region of the as-cast samples after thermal exposure at 900℃ for 1000 h.Theσphases are preferentially precipitated at the periphery of coarse γ/γ′eutectic,and their morphological evolution from needles to granules is observed.Microstructural analysis suggests that the local segregation of Cr and Ti at the periphery of coarse γ/γ′eutectic accounts for the formation ofσphases in the as-cast samples.After heat treatment with low solution temperature and short holding time,the dendritic segregation of alloying elements(i.e.,W,Re,Ti and Ta)and the volume fraction of γ′phase in the interdendritic region are similar to that of the as-cast samples.However,no TCP phases are present in the interdendritic region of the heat-treated samples after thermal exposure,which is primarily ascribed to the elimination of local segregation of Cr and Ti near the coarse γ/γ′eutectic.Moreover,small quantities ofμphases are precipitated in the secondary dendrite arm near the interdendritic region after thermal exposure,due to the increased volume fraction ofγ′phase and the concomitant enrichment of W and Re in theγmatrix.

Impact of nanocrystallinity segregation on the growth and morphology of nanocrystal superlattices

A colloidal solution of 5 nm Au tetradecanethiol-coated nanoparticles is syn-thesized. After fast evaporation of one drop, ordered monolayers both composed of single domain and polycrystalline nanocrystals are obtained. On increasing the amount of materials and the evaporation time, nanocrystal films with irregular outlines are produced together with close-packed 3D superlattices exhibiting a truncated-tetrahedral shape. Using low-frequency micro-Raman scattering spectroscopy and electron microscopy the building block nanocrystallinity is characterized. Spontaneous nanocrystallinity segregation is revealed： the truncated-tetrahedral supracrystals are shown to mainly contain single domain building blocks while the supracrystalline films are composed of a mixture of single domain and polycrystalline nanocrystals. This observation points out the correlation between the nanocrystallinity segregation involved in the growth of the nanocrystal superlattices and their morphology.

Rationally Leveraging Polymer Chain-Length Heterogeneity for Robust Structural Engineering

The inherent uncertainty of chain length in synthetic polymers casts doubt on the explicit understanding of fundamental principles.This study quantitatively assesses the critical role of chain-length distribution in the self-assembly process,aiming to identify the point at which discernible discrepancies begin to emerge.By blending discrete diblock copolymers of varying sizes,chain-length nonuniformity can be precisely regulated while the average composition remains constant.Introducing a minor heterogeneity leads to an expansion of lattice dimension,while a phase transition occurs as the difference exceeds a threshold.Interestingly,a transition from the Frank–Kasperσphase to the body-centered cubic phase was triggered by enlarging the size difference of the corona block,while introducing heterogeneity in the core block stabilized the hexagonally close-packed spheres.A self-consistent field theory calculation reveals that the synergy between the long and short chains effectively releases packing frustration,leading to substantial changes in the free-energy landscape and stabilizing unconventional phases otherwise inaccessible.This work calls particular attention to the importance of chain-length heterogeneity and provides a robust approach to finely tuning the phase behavior and physical properties of block copolymers without altering their chemical composition.