Chain‐Growth Click Polymerization of AB2 Monomers for the Formation of Hyperbranched Polymers with Low Polydispersities in a One‐Pot Process

Hyperbranched polymers are important soft nanomaterials but robust synthetic methods with which the polymer structures can be easily controlled have rarely been reported. For the first time, we present a one‐pot one‐batch synthesis of polytriazole‐based hyperbranched polymers with both low polydispersity and a high degree of branching (DB) using a copper‐catalyzed azide–alkyne cycloaddition (CuAAC) polymerization. The use of a trifunctional AB₂ monomer that contains one alkyne and two azide groups ensures that all Cu catalysts are bound to polytriazole polymers at low monomer conversion. Subsequent CuAAC polymerization displayed the features of a “living” chain‐growth mechanism with a linear increase in molecular weight with conversion and clean chain extension for repeated monomer additions. Furthermore, the triazole group in a linear (L) monomer unit complexed Cu^I, which catalyzed a faster reaction of the second azide group to quickly convert the L unit into a dendritic unit, producing hyperbranched polymers with DB=0.83.     

An Efficient Labelling Approach to Harness Backbone and Side‐Chain Protons in 1H‐Detected Solid‐State NMR Spectroscopy

¹H‐detection can greatly improve spectral sensitivity in biological solid‐state NMR (ssNMR), thus allowing the study of larger and more complex proteins. However, the general requirement to perdeuterate proteins critically curtails the potential of ¹H‐detection by the loss of aliphatic side‐chain protons, which are important probes for protein structure and function. Introduced herein is a labelling scheme for ¹H‐detected ssNMR, and it gives high quality spectra for both side‐chain and backbone protons, and allows quantitative assignments and aids in probing interresidual contacts. Excellent ¹H resolution in membrane proteins is obtained, the topology and dynamics of an ion channel were studied. This labelling scheme will open new avenues for the study of challenging proteins by ssNMR.     

摩托车传动用滚子链磨损特性的研究

道路行驶磨损试验结果表明，摩托车传动用滚子链套筒和销轴零件的主要磨损形式是磨粒磨损，并伴随有疲劳磨损的特征．由微观分析和链条的磨损伸长量可知：套筒和销轴的初始表面硬度较高，有利于改善其磨损表面形貌状态和耐磨性；在磨粒磨损机制下，套筒和销轴零件的表面硬度较低，容易产生“犁切”，表面层的循环硬化现象比较明显，磨损严重；在油池润滑条件下，套筒和销轴零件的表面硬度较高，裂纹的扩展速率较快，循环软化现象也较明显，当表面硬度较低时发生循环硬化．循环软化与循环硬化是导致磨损严重的原因之一．     

Non-linear stochastic response of a shallow cable

The paper considers the stochastic response of geometrical non-linear shallow cables. Large rain-wind induced cable oscillations with non-linear interactions have been observed in many large cable stayed bridges during the last decades. The response of the cable is investigated for a reduced two-degrees-of-freedom system with one modal coordinate for the in-plane displacement and one for the out-of-plane displacement. At first harmonic varying chord elongation at excitation frequencies close to the corresponding eigenfrequencies of the cable is considered in order to identify stable modes of vibration. Depending on the initial conditions the system may enter one of two states of vibration in the static equilibrium plane with the out-of-plane displacement equal to zero, or a whirling state with the out-of-plane displacement different from zero. Possible solutions are found both analytically and numerically. Next, the chord elongation is modelled as a narrow-banded Gaussian stochastic process, and it is shown that all the indicated harmonic solutions now become instable with probability one. Instead, the cable jumps randomly back and forth between the two in-plane and the whirling mode of vibration. A theory for determining the probability of occupying either of these modes at a certain time is derived based on a homogeneous, continuous time three states Markov chain model. It is shown that the transitional probability rates can be determined by first-passage crossing rates of the envelope process of the chord wise component of the support point motion relative to a safe domain determined from the harmonic analysis of the problem.     

Simple Torsion of Isotropic, Hyperelastic, Incompressible Materials with Limiting Chain Extensibility

The purpose of this research is to investigate the simple torsion problem for a solid circular cylinder composed of isotropic hyperelastic incompressible materials with limiting chain extensibility. Three popular models that account for hardening at large deformations are examined. These models involve a strain-energy density which depends only on the first invariant of the Cauchy–Green tensor. In the limit as a polymeric chain extensibility tends to infinity, all of these models reduce to the classical neo-Hookean form. The main mechanical quantities of interest in the torsion problem are obtained in closed form. In this way, it is shown that the torsional response of all three materials is similar. While the predictions of the models agree qualitatively with experimental data, the quantitative agreement is poor as is the case for the neo-Hookean material. In fact, by using a global universal relation, it is shown that the experimental data cannot be predicted quantitatively by any strain-energy density which depends solely on the first invariant. It is shown that a modification of the strain energies to include a term linear in the second invariant can be used to remedy this defect. Whether the modified strain-energies, which reflect material hardening, are a feasible alternative to the classic Mooney–Rivlin model remains an open question which can be resolved only by large strain experiments. This revised version was published online in August 2006 with corrections to the Cover Date.     

影响含硫化物的地下工程围岩中锚固体系侵蚀的主要因素研究(英文)

采用复合式衬砌的隧道及地下工程,锚喷支护系统的耐久性直接影响结构的稳定性和运营年限。锚杆主体属于钢构件,极易遭受侵蚀。从采用复合式衬砌的隧道及地下工程的结构特点可知,对于一定形式的锚杆,所遭受的侵蚀作用主要取决于锚杆与来自围岩的侵蚀性地下水的相互作用。本文探讨了含硫化物围岩中影响锚杆侵蚀的主要因素,描述了侵蚀性地下水的形成,以及锚杆侵蚀作用的物理化学机理,并提出了基于此机理的含硫化物围岩中锚杆使用年限的估算方法。     

Coupled Orientation and Stretching of Chains in Mesoscale Models of Polydisperse Linear Polymers in Startup of Steady Shear Flow Simulations

Polydisperse linear polymers are studied in startup of steady shear flow simulations using dissipative particle dynamics. The results show that with an increase in polydispersity the stress overshoot declines while the steady‐state stress increases. Various physical characteristics of the systems are studied including frequency of nonbonded interactions, gyration radius data, flow alignment angles, and average bond lengths. The patterns in the data suggest higher forces are necessary to orient and stretch long chain fractions in the flow direction. Relaxation modulus data prove the broad range of relaxation mechanisms in polydisperse systems. Linear viscoelasticity theory is used to quantify the relaxation spectrum. The results indicate an increase in the longest relaxation time in systems with higher polydispersity. The steady‐state shear viscosity results show higher viscosities with an increase in polydispersity at all shear‐rates. The good agreement of the characteristic behaviors of modeled polydisperse polymers with experiments is encouraging for future work.

     

Shaping the Light: The Key Factors Affecting the Photophysical Properties of Fluorescent Polymer Nanostructures

To manipulate the functions of nanomaterials more precisely for diverse applications, the controllability and critical influencing factors of their properties must be thoroughly investigated. In this work, the macroscopic and microscopic effects are studied on the photophysical properties of various pyrene‐ended poly(styrene‐block‐methyl methacrylate) nanostructures. Fluorescent polymer nanospheres, nanorods, and nanotubes are prepared by different template‐based methods using anodic aluminum oxide membranes. Chain arrangements and conformations are determined as the key factors affecting the photophysical properties of the fluorescent polymer nanostructures. This work not only gives a deeper understanding of the effects on the photophysical properties of polymer nanomaterials influenced by morphologies, chain arrangements, and chain conformations, but also provides a reference for designing proper fluorescent nanostructures for specific applications.

     

Influence of one CO molecule on structural and electronic properties of monatomic Cu chain

By using first-principles calculations, we have systematically investigated the structural and electronic properties of an infinite linear monatomic Cu chain with an adsorbed CO molecule. We find that the bridge geometry is energeticabsally favored not only when the Cu–Cu bond below the molecule is unstretched, but also for a wide range of d_Cu–Cu up to about 4.20 Å, while the substitutional geometry is favored only in the hyperstretched situation d_Cu–Cu>4.80 Å. Charge density differences point out the electron transfer is from the Cu atoms to the adsorbed CO molecule. The binding mechanism of CO to Cu chain can be described by the Blyholder’s model, in terms of σ-donation of electron density from the nonbonding CO-5σ orbital into empty metal orbitals and π-backdonation from the occupied metal d orbitals to empty CO-2π^⁎ orbital. The donation/backdonation process leads to the formation of bonding/antibonding pairs, 5σ_b/5σ_a and 2π_b^⁎/2π_a^⁎, with the 5σ_a lying above E_f and the 2π_b^⁎ below E_f.     

Stochastic comparison of aggregate claim amounts between two heterogeneous portfolios and its applications

The aggregate claim amount in a particular time period is a quantity of fundamental importance for proper management of an insurance company and also for pricing of insurance coverages. In this paper, we show that the proportional hazard rates (PHR) model, which includes some well-known distributions such as exponential, Weibull and Pareto distributions, can be used as the aggregate claim amount distribution. We also present some conditions for the use of exponentiated Weibull distribution as the claim amount distribution. The results established here complete and extend the well-known result of Khaledi and Ahmadi (2008).