附加压力与分散系统的稳定性

较详细地讨论了附加压力与分散系统稳定性间的关系,指出分散相附加压力的降低是分散系统趋向稳定的根本原因。以乳状液为例,附加压力降低不仅减少了液滴间相互碰撞的概率,而且更重要的是,它与液滴表面形成牢固的保护膜密切相关。只有当液滴的附加压力趋近0时,分散系统才达到热力学上稳定的状态,此时乳状液已变成了微乳状液。上述讨论也基本适用于固/液分散系统。     

Synthesis and liquid crystalline behavior of bulky poly(methacrylamide)s

N‐(Bis(4‐(2‐ethylhexyloxy)phenyl)(phenyl)‐methyl)methacrylamide was synthesized and polymerized via reversible addition‐fragmentation chain‐transfer (RAFT) polymerization. The chain‐transfer agent (4‐cyano‐4‐(phenylcarbonothioylthio) pentanoic acid (CPADB)), combined with a chiral additive, and a radical initiator yielded polymers with dispersities between 1.2 and 1.4. At low concentrations, the polymers are soluble in hexanes and chloroform while at higher concentrations they swell in these solvents. Characterization of the polymers by wide‐angle X‐ray scattering (WAXS) revealed an interplanar distance of 19.0 Å. The WAXS data combined with polarized optical microscopy support a lamellar crystallization and lyotropic liquid crystalline behavior in hexanes and chloroform. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2563–2568     

Synthesis of tertiary amine‐based pH‐responsive polymers by RAFT Polymerization

Well‐defined tertiary amine‐based pH‐responsive homopolymers and block copolymers were synthesized via reversible addition‐fragmentation chain transfer (RAFT) polymerization using 4‐cyanopentanoic acid dithiobenzoate (CPAD) as the RAFT agent for homopolymers and a poly(ethylene glycol) (PEG) macro‐RAFT agent for the block copolymers. ¹H NMR and gel permeation chromatography results confirmed the successful synthesis of these homopolymers and block copolymers. Kinetics studies indicated that the formation of both the homopolymers and the block copolymers were well defined. The pKa titration experiments suggested that the homopolymers and the related block copolymers have a similar pKa. The dynamic light scattering investigation showed that all of the block copolymers underwent a sharp transition from unimers to micelles around their pKa and the hydrodynamic diameter (D_h) was not only dependent on the molecular weight but also on the composition of the block copolymers. The polymer solution of PEG‐b‐PPPDEMA formed the largest micelle compare to the PEG‐b‐PDPAEMA and PEG‐b‐PDBAEMA with a similar molecular weight. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1010–1022     

Molecular dynamic study of dielectric polarization and ferroelectricity in a model polar polymer

Molecular dynamics simulations are used to explore the polarization response of a lamellar crystal consisting of folded chains of a highly simplified model polar polymer. The system is based on a united atom model of polyethylene with constrained bond lengths and bond angles, and it is endowed with artificial partial charges placed on the united atoms to give it a simple polar character. Simulations performed with various temperatures, electric field directions, and electric field application histories reveal a complicated sequence of reorientation processes, including pronounced ferroelectric behavior. The sequence includes a weak, temperature‐independent prompt response, and a slow‐rising delay regime with stretched exponential behavior and thermally‐activated reorientation parameters consistent with trans‐gauche (TG) barrier crossings in the amorphous phase. When the delay regime has progressed sufficiently, a primary large‐amplitude response due to organized rotation of large subsegments in the crystalline phase occurs in a rapid manner that requires relatively few TG barrier crossings. A final, extremely slow rise in residual polarization completes the sequence. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 740–759     

Effect of chemical parameters on pyrene degradation in soil in a pulsed discharge plasma system

Degradation of pyrene in soil in a net-to-net pulsed discharge plasma (PDP) system was reviewed. Effect of main chemical parameters, including air flow rate, pyrene concentration, initial pH and soil moisture content on pyrene degradation was examined. The obtained results show that 87.9% of pyrene could be removed under the condition of 60 min reaction; increasing of air flow rate within 1 L min⁻¹ was favorable for degradation; pyrene removal was decreased with the increase of initial pyrene concentration; oxidation of pyrene was more evident in acidic soil; enhancement of soil moisture content has no benefit on pyrene degradation.     

Crosslinkable high dielectric constant polymer dielectrics for low voltage organic field‐effect transistor memory devices

I n this study, we successfully synthesized water/methanol soluble random copolymers with a high dielectric constant, poly(n‐(hydroxymethyl) acrylamide‐co‐5‐(9‐(5‐(diethylamino)pentyl)?2‐(4‐vinylphenyl)?9H‐fluorene(P(NMA‐co‐F6NSt)), which contained chemical crosslinkable segment (NMA) and hole trapping building block (F6NSt). The feeding molar ratios of two monomers (NMA:F6NSt) were set as 100:0, 95:5, 80:20, and 67:33 for the copolymers of P1 , P2 , P3, and P4 , respectively. The crosslinked P(NMA‐co‐F6NSt) thin film could serve as both dielectric and charge storage layers in organic field‐effect transistor (OFET) memory device and exhibited high k (i.e., 4.91–6.47) characteristics, leading to a low voltage operation and a small power consumption. Devices based on the P1 ‐ P4 dielectrics showed excellent insulating properties and good charge storage performance under a low operating voltage in a range of ±5V because of tightly network structures and well‐dispersed trapping cites. In particular, P3 ‐based memory device exhibited a large memory window of 4.13 V with stable data retention stability over 10⁴ s, a large on/off ratio of 10⁴, and good endurance characteristics as high as 200 cycles. The above results suggested that a high‐performance OFET memory device could be facilely achieved using the novel crosslinkable high‐k copolymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3224–3236     

Molecular dynamics simulation of DNA‐directed assembly of nanoparticle superlattices using patterned templates

DNA‐directed assembly is a well developed approach in constructing desired nano‐architectures. On the other hand, E‐beam lithography is widely utilized for high resolution nano‐scale patterning. Recently, a new technique combining these two methods was developed to epitaxially grow DNA‐mediated nanoparticle superlattices on patterned substrates. However, defects are observed in epitaxial layers which restricts this technique from building large‐scale superlattices for real applications. Here we use molecular dynamics simulations to study and predict defect formation on adsorbed superlattice monolayers. We demonstrate that this epitaxial growth is energetically driven by maximizing DNA hybridization between the epitaxial layer and the substrate and that the shape anisotropy of the DNA‐mediated template posts leads to structural defects. We also develop design rules to dramatically reduce defects on epitaxial layers. Ultimately, with the assist of the computational study, this technique will open the door to constructing well‐ordered, three‐dimensional novel nanomaterials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1687–1692     

Highly Selective Zeolite Topologies for Flue Gas Separation

The separation of carbon dioxide from flue gas is essential for the reduction of greenhouse gas emissions. In adsorptive methods, the challenge lies in the choice of suitable porous materials. Among all zeolite topologies, a number of adsorbents with pore dimensions in the range of the guest molecules were identified to allow an excellent separation by diffusion, and MRE and AFO zeolite topologies appear to be the best candidates based on equilibrium adsorption. Also, it was found that the behavior of this gas mixture in DFT and APD zeolites differed from the normal behavior.     

Intermolecular Stetter reaction of aromatic aldehydes with (E)-(2-nitrovinyl)cyclohexane induced by N-heterocyclic carbene and thiourea

Intermolecular Stetter reaction of aromatic aldehydes with (E)-(2-nitrovinyl)cyclohexane catalyzed by thiazolium A has been developed. The reaction rate and efficiency are profoundly impacted by the presence of thiourea B. The reaction affords moderate to good yields of the Stetter product. Some factors influencing yield were discussed.     

Butylated hydroxytoluene enediyne: access to diradical and electrophilic quinone methide intermediates

A theoretical study was carried out on the unimolecular reaction of an enediyne with a fused butylated hydroxytoluene to internally scavenge the p‐benzyne diradical sites formed after the Bergman cyclization. The calculations revealed that the conversion of the p‐benzyne diradical (2‐tert‐butyl‐4‐methyl‐5,8‐didehydro‐1‐naphthalenol) to p‐quinone methide is favored over the conversion to a phenoxy/benzene diradical 4 in an approximate 95:5 ratio. Based on this model, the Bergman cyclization leads in a bifunctional manner to intermediates for competing reactivity with intermolecular H‐atom abstraction. Copyright © 2015 John Wiley & Sons, Ltd.