Synthesis of Heat-resistant Polymers by Thiol–Ene Reaction of N-Allylmaleimide Copolymers Using Glycoluril Crosslinkers with Rigid Molecular Structures

We carried out the thermal curing of the copolymers of N-allylmaleimide (AMI) and 2-ethylhexyl acrylate (2EHA) using 1,3,4,6-tetra(2-mercaproethyl)glycoluril ( G1 ), 1,3,4,6-tetra(3-mercaptopropyl)glycoluril ( G2 ), 1,3,4,6-tetraallylglycoluril ( G3 ), triallylisocyanurate (TAIC), and pentaerythritol tetrakis(3-mercaptobutyrate) (PEMB) as the crosslinkers. Based on the results for the analysis of thiol–ene reactions monitored by IR spectroscopy, it was confirmed that the curing rate significantly depended on the combination of the used crosslinkers. The insoluble fraction after curing was more than 90% for the systems using the glycoluril crosslinkers, while the conversion of the allyl groups was suppressed due to the rigid structure of these crosslinkers. The heat resistance and the mechanical properties of the crosslinked polymers were investigated by thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and mechanical tensile tests. For the products cured using the glycoluril crosslinkers, the glass transition temperature (T_g) and the maximum temperature of thermal decomposition (T_max) were 54–59 °C and 395–409 °C, respectively, being higher than those for the cured product prepared with PEMB and TAIC as the conventional crosslinkers. The elasticity (75–139 MPa), the maximum strength (3.0–4.1 MPa), and the adhesion strength (6.7–10.7 MPa) for the polymers cured with the glycoluril crosslinkers, determined by the mechanical tensile and single lap-shear adhesion tests, were higher than those for cured materials produced with PEMB. Thus, the thermal and mechanical properties of the maleimide copolymers were efficiently enhanced by crosslinking using the rigid glycoluril compounds. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 923–931     

Reversible Ultra-Slow Crystal Growth of Mixed Lead Bismuth Perovskite Nanocrystals: The Presence of Dynamic Capping

An ultra-slow crystal growth over a period of 24 h of a newly synthesized CH₃NH₃Pb_1/2Bi_1/3I₃ perovskite (MPBI) nanocrystal in non-polar toluene medium is reported here. From several spectroscopic techniques as well as from TEM analysis we found that the size of nanocrystals changes continuously with time, in spite of being capped by the ligands. Using a single molecular spectroscopic technique, we also found that this size change is not due to the stacking of nanocrystals but due to crystal growth. The notable temperature dependence and reversible nature of the nanocrystals growth is explained by the dynamic nature of the capping. The observed temperature-dependent ultra-slow growth is believed to be a pragmatic step towards controlling the size of perovskite NC in a systematic manner.     

Solid-State Dynamics and High-Pressure Studies of a Supramolecular Spiral Gear

The structures and solid-state dynamics of the supramolecular salts of the general formula [(12-crown-4)₂ ⋅ DABCOH₂](X)₂ (where DABCO=1,4-diazabicyclo[2.2.2]octane, X=BF₄, ClO₄) have been investigated as a function of temperature (from 100 to 360 K) and pressure (up to 3.4 GPa), through the combination of variable-temperature and variable-pressure XRD techniques and variable-temperature solid-state NMR spectroscopy. The two salts are isomorphous and crystallize in the enantiomeric space groups P3₂2₁ and P3₁2₁. All building blocks composing the supramolecular complex display dynamic processes at ambient temperature and pressure. It has been demonstrated that the motion of the crown ethers is maintained on lowering the temperature (down to 100 K) or on increasing the pressure (up to 1.5 GPa) thanks to the correlation between neighboring molecules, which mesh and rotate in a concerted manner similar to spiral gears. Above 1.55 GPa, a collapse-type transition to a lower-symmetry ordered structure, not attainable at a temperature of 100 K, takes place, proving, thus, that the pressure acts as the means to couple and decouple the gears. The relationship between temperature and pressure effects on molecular motion in the solid state has also been discussed.     

Enantioselective Synthesis of α-Thiocarboxylic Acids by Nitrilase Biocatalysed Dynamic Kinetic Resolution of α-Thionitriles

The enantioselective synthesis of α-thiocarboxylic acids by biocatalytic dynamic kinetic resolution (DKR) of nitrile precursors exploiting nitrilase enzymes is described. A panel of 35 nitrilase biocatalysts were screened and enzymes Nit27 and Nit34 were found to catalyse the DKR of racemic α-thionitriles under mild conditions, affording the corresponding carboxylic acids with high conversions and good-to-excellent ee. The ammonia produced in situ during the biocatalytic transformation favours the racemization of the nitrile enantiomers and, in turn, the DKR without the need of any external additive base.     

Hydrogen-Bond Catalysis of Imine Exchange in Dynamic Covalent Systems

The reversibility of imine bonds has been exploited to great effect in the field of dynamic covalent chemistry, with applications such as preparation of functional systems, dynamic materials, molecular machines, and covalent organic frameworks. However, acid catalysis is commonly needed for efficient equilibration of imine mixtures. Herein, it is demonstrated that hydrogen bond donors such as thioureas and squaramides can catalyze the equilibration of dynamic imine systems under unprecedentedly mild conditions. Catalysis occurs in a range of solvents and in the presence of many sensitive additives, showing moderate to good rate accelerations for both imine metathesis and transimination with amines, hydrazines, and hydroxylamines. Furthermore, the catalyst proved simple to immobilize, introducing both reusability and extended control of the equilibration process.     

New Supercage Metal–Organic Framework Based on Allopurinol Ligands Showing Acetylene Storage and Separation

To develop efficient adsorbent materials for storage and separation of C₂H₂, an unprecedented supercage MOF, [Me₂NH₂]⋅[Zn₃(ALP)(TDC)_2.5]⋅3.5DMF⋅2 H₂O ( 1 ) was constructed through medicinal molecule allopurinol (ALP) and S-containing 2,5-thiophenedicarboxylic acid (H₂TDC). 1 contains a novel linear trinuclear cluster that is composed by ALP and carboxylates and forms a final uncommon 5-connected yfy topological framework. The framework possesses three types of interlinked cages decorated by rich functional sites, and reveals not only high adsorption capacity for C₂H₂ but also excellent selective separation for C₂H₂/CO₂ and C₂H₂/CH₄ at 298 K. Dynamic breakthrough experiments on C₂H₂/CO₂ (1:1) mixture and C₂H₂/CH₄ (1:1) mixture also demonstrated the potential of the material to separate C₂H₂ from CO₂ or CH₄ mixtures. Molecular simulations were also studied to identify the different CO₂- and C₂H₂- binding sites in 1 , such as carboxylate groups, S atoms and carbonyl groups.     

Exhaustive search of the configurational space of heat-shock protein 90 with its inhibitor by multicanonical molecular dynamics based dynamic docking

Multicanonical molecular dynamics based dynamic docking was used to exhaustively search the configurational space of an inhibitor binding to the N-terminal domain of heat-shock protein 90 (Hsp90). The obtained structures at 300 K cover a wide structural ensemble, with the top two clusters ranked by their free energy coinciding with the native binding site. The representative structure of the most stable cluster reproduced the experimental binding configuration, but an interesting conformational change in Hsp90 could be observed. The combined effects of solvation and ligand binding shift the equilibrium from a preferred loop-in conformation in the unbound state to an α-helical one in the bound state for the flexible lid region of Hsp90. Thus, our dynamic docking method is effective at predicting the native binding site while exhaustively sampling a wide configurational space, modulating the protein structure upon binding.     

通过不对称氢转移/动态动力学拆分合成碳环N^3-嘌呤核苷

N^3-嘌呤核苷由于可能同时被嘌呤和嘧啶代谢酶识别,因而有望作为双靶点药物应用于抗病毒治疗.报道了一种以α-(N^3-嘌呤)取代的环烷酮为原料,通过不对称氢转移反应实现动态动力学拆分,高收率高立体选择性地合成系列碳环N^3-嘌呤核苷化合物.该催化体系也适用于α-嘧啶取代的环烷酮底物,且产物通过进一步衍生,合成了2’-F-,Ac S-,N^3-修饰的碳环嘧啶核苷.     

非齐次动力学方程的一种精细积分单步方法

针对非齐次动力学方程■,结合精细积分法和微分求积法,利用同阶的显式龙格-库塔法对计算过程中待求的v_(k+i/s)(i=1,2,…,s)进行预估,提出了一种避免状态矩阵求逆的高效精细积分单步方法。该方法采用精细积分法计算e~(Ht),而Duhamel积分项采用s级s阶的时域微分求积法,计算格式统一且易于编程,可灵活实现变阶变步长。仿真结果表明,与其他单步法及预估校正-辛时间子域法进行数值比较,该方法具有高精度、高效率及良好的稳定性,在求解大规模动力系统时间响应问题中具有较大的优势。     

连续梁在周期荷载下的动力稳定性简化分析方法

对于一般任意支撑的连续梁结构动力稳定性问题，已有的计算方法求解过程都很复杂，给工程设计带来极大的不便．本文提出了一个简化的分析方法，利用现有的商业软件，只需求得连续梁的自然频率及静力屈曲（失稳）荷载，就可容易得到结构的动力失稳区域，当考虑结构阻尼对不稳定区域的影响时，可将阻尼矩阵表达为Rayleigh阻尼的形式．研究结果表明：采用本文计算方法与已有的理论计算方法得到的连续梁主参数共振的不稳定边界非常吻合，而本文计算方法更为简单，计算结果可靠，计算精度高，可满足工程设计的需要．