Homopolymerization of N-pyrimidinyl acrylamide

Homopolymerization of N-pyrimidinyl acrylamide (NPA) was reported for the first time. The polymer (polyNPA) was soluble only in acidic media and fluoroalcohols, and only in fluoroalcohol was homogeneous polymerization of NPA feasible. 1H NMR analysis proved that a 1:1 H-bonding complex could be formed between NPA and α,α-bis(trifluoromethyl)phenyl propan-2-ol (BTMP). Cumyl dithiobenzoate mediated reversible addition-fragmentation chain transfer (RAFT) polymerization of NPA in BTMP was carried out. 1H NMR analyses proved that the molecular weight increased linearly with the monomer conversion. The polymer prepared in conventional solvents was atactic while in protic media the syndiotacticity was slightly enhanced.

L-Lactide Homopolymerization and Copolymerization with ε-Caprolactone by Tetrahydrosalen Stabilized Yttrium Borohydride Complex

L-lactide（LLA） homopolymerization and copolymerization with ε-caprolactone（CL） in toluene initiated by tetrahydrosalen-supported yttrium borohydride complex were systematically investigated. A possible mechanism of LLA homopolymerization was proposed according to the 1H-NMR result. In addition, PCL-b-PLLA copolymers were synthesized by sequential addition of monomers and their structure was characterized by GPC, 1H-NMR and 13C-NMR.

SYNTHESIS AND PROPERTIES OF HOMOPOLYMER AND COPOLYMERS OBTAINED FROM 1-OCTADECENE WITH ZIRCONOCENE CATALYSTS

Studies related to the behavior of different metallocene catalysts for the homopolymerization of 1-octadecene andits copolymerization with ethylene will be presented. The metallocenes: rac-Et(Ind)_2ZrCl_2, rac-Me_2Si(Ind)_2ZrCl_2 andPh_2C(Flu)(Cp)ZrCl_2 were chosen for the homopolymerization study. They show important differences in catalytic activity athigh temperatures (≥70℃), with rac-Et(Ind)_2ZrCl_2 showing the highest activity. At lower temperatures (≤30℃) thedifferences are negligible. For the copolymerization of ethylene with 1-octadecene only the catalysts rac-Et(Ind)_2ZrCl_2 andrac-Me_2Si(Ind)_2ZrCl_2 were studied. The results show that their catalytic activity is just like that for the homopolymerizationof 1-octadecene, with higher activity for the metallocene with the Et-bridged catalyst. ^(13)C-NMR analysis shows that thecomposition of the copolymerization products depends on the catalytic systems. Copolymers obtained with rac-Me_2Si(Ind)_2ZrCl_2 have greater comonomer incorporation. Thermal analysis shows that poly-1-octadecene synthesized withthe catalyst rac-Et(Ind)_2ZrCl_2 is very dependent on the polymerization temperature. The homopolymer obtained at 70℃presents two endothermal peaks at 41℃ and 53℃, as compared with the one obtained at 30℃ which presents one wider peakwith a maximum at 67℃. For the catalyst rac-Me_2Si(Ind)_2ZrCl_2 this trend is not observed. The type of metallocene and thereaction time do not significantly change the intrinsic viscosity, but the polymerization temperature changes it drastically,giving higher values at lower temperature. Viscosity measurements on the copolymers show that an increase of comonomerconcentration in the feed reduces the molecular weight of the copolymer, and it was also found that for homopolymer, themolecular weight is independent of the catalytic systems.

Inferring the Physics of Structural Evolution of Multicomponent Polymers via Machine-Learning-Accelerated Method

Dynamic self-consistent field theory(DSCFT)is a fruitful approach for modeling the structural evolution and collective kinetics for a wide variety of multicomponent polymers.However,solving a set of DSCFT equations remains daunting because of high computational demand.Herein,a machine learning method,integrating low-dimensional representations of microstructures and long short-term memory neural networks,is used to accelerate the predictions of structural evolution of multicomponent polymers.It is definitively demonstrated that the neural-network-trained surrogate model has the capability to accurately forecast the structural evolution of homopolymer blends as well as diblock copolymers,without the requirement of“on-the-fly”solution of DSCFT equations.Importantly,the data-driven method can also infer the latent growth laws of phase-separated microstructures of multicomponent polymers through simply using a few of time sequences from their past,without the prior knowledge of the governing dynamics.Our study exemplifies how the machine-learning-accelerated method can be applied to understand and discover the physics of structural evolution in the complex polymer systems.

Optic and catalytic properties of gold nanoparticles tuned by homopolymers

Gold nanoparticles (GNs) are prepared through in situ reduction using NaBH4 in the presence of homopolymer PDMAEMA. The sizes of the GNs can be adjusted by alternating the molar ratio of gold to DMAEMA. Pure PDMAEMA aqueous solution shows a phase-transition at 50℃ at pH 10 and 25℃ at pH 14, while PDMAEMA-supported GNs aqueous solution shows a phase-transition at 47℃ at pH 10 because of the increasing hydrophobic property resulting from GNs. Due to the pH and tempera-ture-responsible characteristics of PDMAEMA, the resulting PDMAEMA-supported GNs exhibit pH adjustable temperature-responsive characteristics in optic and catalytic aspects. Under an acidic condi-tion (pH 2), the GNs show unchanged surface Plasmon absorbance with a peak of 518 nm in a tem-perature range from 20 to 65℃. Under a basic condition (pH 10), the GNs first show the same absorb-ance with a peak at 518 nm in a temperature range from 20 to 40℃, and then the absorbance red shifts from 518 to 545 nm as temperature increases from 40 to 65℃. When the GNs are used as catalysts to catalyze the reduction of p-nitrophenol, the catalytic activity can be adjusted by changing the permeation of reactants in the PDMAEMA layer at low and high temperatures, respectively.

A homopolymer based on double B←N bridged bipyridine as electron acceptor for all-polymer solar cells

Polymer electron acceptors for all-polymer solar cells （all-PSCs） are usually conjugated copolymers, which contain alternating electron-rich units and electron-deficient units. In this manuscript, we report a conjugated homopolymer （P-BNBP） based on an electron-deficient unit of double B,--N bridged bipyridine, which can be used as electron acceptor for all-polymer solar cells. P-BNBP shows low-lying LUMO energy level of -3.59eV, high absorption coefficient of 1.6 ×10^5Lmo1^-1 cm^-1 at 626nm and moderate electron mobility of 4.37 ×10^-6cm^2V^-1s^-1. AII-PSC devices exhibit power conversion efficiencies of 2.44%-3.04%. These results demonstrate that conjugated homopolymers are promising as electron acceptor materials for alI-PSCs.

Denting Nanospheres with a Short Peptide

Dented n anospheres show promisi ng potential in drug delivery,nano motors,etc.However,it is still challe nging to prepare them by homopolymer self-assembly because of the strict structural requirements of the homopolymer.Herein,we propose a strategy for preparing dented nano spheres from homopolymers by co-assembly with a short peptide.They were co-assembled from poly(2-hydroxy-3-((4-(ethoxycarbonyl)phenyl)amino)propyl methacrylate)(PHBzoMA59)and(S)-2-((S)-2-((((9H-fluoren-9-yl)methoxy)carbonyl)amino)-3-phenylpro-panamido)-3-phenyIpropanoic acid(Fmoc-FF-OH).PHBzoMA homopolymers can only self-assemble into nanospheres without dent,and the addition of a short peptide in troduced hydroge n bondi ng and complementary π-π stacki ng interactions led to the final dented nano sphere morphology.The weight fracti ons of the short peptide can be adjusted to regulate the final morphology.It was con firmed that the radius of curvature of the dent on the surface was related to the organic bubble inside the protospheres prepared at critical aggregation concentration(CAC).The orga nic bubble can be adjusted by altering the kind of orga nic solve nt and solution pH,which allowed control over the dented nano sphere dimension.The use of differe nt orga nic solve nts with various polarities allows adjustment of the interfacial tension,and hence the denting degree.This degree can also be controlled by manipulating the solution pH to(de)protonate the short peptide and homopolymer.Furthermore,the versatility of this method was highlighted by using a differe nt homopolymer and the applicability of the resulting den ted nanospheres was demonstrated by decoration with gold nanoparticles.Overall,this study provided important insights and a new simple strategy to prepare den ted n anospheres in a con trolled fashion.

On the critical behavior of a homopolymer model

We begin with the reference measure P0 induced by simple, symmetric nearest neighbor continuous time random walk on Zd starting at 0 with jump rate 2d and then define, for β≥0, t > 0, the Gibbs probability measure Pβ,t by specifying its density with respect to P0 as dPβ,t/dP0= Zβ,t(0)(-1eβ∫0tδ0(xs)ds),(0.1)where Zβ,t(0)≡E0[eβ∫t0δ0(xs)ds]. This Gibbs probability measure provides a simple model for a homopolymer with an attractive potential at the origin. In a previous paper(Cranston and Molchanov, 2007), we showed that for dimensions d≥3 there is a phase transition in the behavior of these paths from the diffusive behavior for β below a critical parameter to the positive recurrent behavior for β above this critical value. The critical value was determined by means of the spectral properties of the operator△+βδ0, where△ is the discrete Laplacian on Z^d. This corresponds to a transition from a diffusive or stretched-out phase to a globular phase for the polymer. In this paper we give a description of the polymer at the critical value where the phase transition takes place. The behavior at the critical parameter is dimension-dependent.