不同变质程度煤的高分辨率透射电镜分析

利用高分辨率透射电子显微镜(HRTEM)分析了三种不同变质程度煤样的结构特征。基于傅里叶-反傅里叶变换方法,并结合Matlab、Arcgis和Auto CAD软件,通过图像分析技术,获得了HRTEM照片的晶格条纹参数。结果表明,三种煤样的晶格条纹呈现不同特征,按条纹长度分别归属于1×1-8×8共计八个类型。以3×3为临界点,在1×1和2×2中,ML-8中芳香层片的比例高于DP-4和XM-3;在3×3-8×8中,ML-8中芳香层片的比例低于DP-4和XM-3。对比HRTEM和XRD参数d002发现,随着镜质组反射率的增加d002都呈现递减趋势。     

Enhancement of Light Absorption Ability of Synthetic Chlorophyll Derivatives by Conjugation with a Difluoroboron Diketonate Group

The enhancement of the light absorption ability of synthetic chlorophyll derivatives is demonstrated. Chlorophyll derivatives directly conjugated with a difluoroboron 1,3‐diketonate group at the C3 position were synthesized from methyl pyropheophorbide‐d through Barbier acylmethylation of the C3‐formyl moiety, oxidation of the C3‐carbinol, and difluoroboron complexation of the diketonate. Electronic absorption spectra in a diluted solution showed that the synthetic conjugates gave an absorption band at λ=400–500 nm, with a Qy band shifted to a longer wavelength of λ≈700 nm. DFT calculations demonstrated that the absorption bands and redshifts were ascribable to the coupling of the LUMO of chlorin with that of the difluoroboron diketonate moiety. The introduction of a pyrenyl group at the C3³‐position of the conjugate afforded an additional charge‐transfer band over λ=500 nm, producing a pigment that bridged the green gap in standard chlorophylls.     

Synthesis and characterization of double hydrophilic block copolymers containing semi-rigid and flexible segments

3-Methyl-(E)-stilbene (3MSti) and 4-(diethylamino)-(E)-stilbene (DEASti) monomers are synthesized and polymerized separately with maleic anhydride (MAn) in a strictly alternating fashion using reversible addition-fragmentation chain transfer (RAFT) polymerization techniques. The optimal RAFT chain transfer agents (CTAs) for each copolymerization affect the reaction kinetics and CTA compatibilities. Psuedo-first order polymerization kinetics are demonstrated for the synthesis of poly((3-methyl-(E)-stilbene)-alt-maleic anhydride) (3MSti-alt-MAn) with a thiocarbonylthio CTA (methyl 2-(dodecylthiocarbonothioylthio)−2-methylpropionate, TTCMe). In contrast, a dithioester CTA (cumyl dithiobenzoate, CDB) controls the synthesis of poly((4-(diethylamino)-(E)-stilbene)-alt-maleic anhydride) (DEASti-alt-MAn) with pseudo-first order polymerization kinetics. DEASti-alt-MAn is chain extended with 4-acryloylmorpholine (ACMO) to synthesize diblock copolymers and subsequently converted to a double hydrophilic polyampholyte block copolymers (poly((4-(diethylamino)-(E)-stilbene)-alt-maleic acid))-b-acryloylmorpholine) (DEASti-alt-MA)-b-ACMO) via acid hydrolysis. The isoelectric point and dissociation behavior of these maleic acid-containing copolymers are determined using ζ-potential and acid–base titrations, respectively. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 219–227     

Experimental Performance of a Solid Heat Exchanger with Tree-Like Flow Passages

System performance of a solid single-fluid compact heat exchanger with tree-like flow passages has been experimentally examined. The results, presented in the form of commonly defined dimensionless parameters, demonstrate that system performance can be characterized in a mode similar to traditional compact heat exchanger designs. Pressure forces were found to dominate inertia forces at low Reynolds numbers. Correlations of the Euler number, Nusselt number, Colburn factor, and friction factor as a function of Reynolds number were utilized to compare system performance to traditional two-fluid compact heat exchangers.     

Bio‐Inspired Transition Metal–Organic Hydride Conjugates for Catalysis of Transfer Hydrogenation: Experiment and Theory

Taking inspiration from yeast alcohol dehydrogenase (yADH), a benzimidazolium (BI⁺) organic hydride‐acceptor domain has been coupled with a 1,10‐phenanthroline (phen) metal‐binding domain to afford a novel multifunctional ligand ( L ^BI+) with hydride‐carrier capacity ( L ^BI++H^?? L ^BIH). Complexes of the type [Cp*M( L ^BI)Cl][PF₆]₂ (M=Rh, Ir) have been made and fully characterised by cyclic voltammetry, UV/Vis spectroelectrochemistry, and, for the Ir^III congener, X‐ray crystallography. [Cp*Rh( L ^BI)Cl][PF₆]₂ catalyses the transfer hydrogenation of imines by formate ion in very goods yield under conditions where the corresponding [Cp*Ir( L ^BI)Cl][PF₆] and [Cp*M(phen)Cl][PF₆] (M=Rh, Ir) complexes are almost inert as catalysts. Possible alternatives for the catalysis pathway are canvassed, and the free energies of intermediates and transition states determined by DFT calculations. The DFT study supports a mechanism involving formate‐driven Rh?H formation (90 kJ mol^?1 free‐energy barrier), transfer of hydride between the Rh and BI⁺ centres to generate a tethered benzimidazoline (BIH) hydride donor, binding of imine substrate at Rh, back‐transfer of hydride from the BIH organic hydride donor to the Rh‐activated imine substrate (89 kJ mol^?1 barrier), and exergonic protonation of the metal‐bound amide by formic acid with release of amine product to close the catalytic cycle. Parallels with the mechanism of biological hydride transfer in yADH are discussed.     

Fabrication and microstructural characterization of functionally graded porous acrylonitrile butadiene styrene and the effect of cellular morphology on creep behavior

The ability to control material properties in space and time for functionally graded viscoelastic materials makes them an asset where they can be adapted to different design requirements. The continuous microstructure makes them advantageous over conventional composite materials. Functionally graded porous structures have the added advantage over conventional functionally graded materials of offering a significant weight reduction compared to a minor drop in strength. Functionally graded porous structures of acrylonitrile butadiene styrene (ABS) had been fabricated with a solid‐state constrained foaming process. Correlating the microstructure to material properties requires a deterministic analysis of the cellular structure. This is accomplished by analyzing the scanning electron microscopy images with a locally adaptive image threshold technique based on variational energy minimization. This characterization technique of the cellular morphology is analyst independent and works very well for porous structures. Inferences are drawn from the effect of processing on microstructure and then correlated to creep strain and creep compliance. Creep is strongly correlated to porosity and pore sizes but more associated to the size than to porosity. The results show the potential of controlling the cellular morphology and hence tailoring creep strain/compliance of ABS to some desired values. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 795–803     

Synthesis of diblock copolymers by combination of organocatalyzed ring‐opening polymerization and atom transfer radical polymerization using trichloroethanol as a bifunctional initiator

This study reports an application of trichloroethanol (TCE) as a bifunctional initiator for the synthesis of block copolymers (BCPs) by organocatalyzed ring‐opening polymerization (OROP) and atom transfer radical polymerization (ATRP). TCE was employed to synthesize a low dispersity poly (valerolactone) macroinitiator, which was subsequently used for the ATRP of tert‐butyl methacrylate. While it is known that TCE can serve as an initiator in ATRP, the ability to induce polymerization under OROP is reported for the first time. The formation of well‐defined BCPs was confirmed by gel permeation chromatography and ¹H NMR. Computational studies were performed to obtain a molecular‐level understanding of the ring‐opening polymerization mechanism involving TCE as initiator. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 563–569     

Synthesis of polymer with defined fluorescent end groups via reversible addition fragmentation transfer polymerization for characterizing the conformations of polymer chains in solutions

A new type of chain transfer agent used in reversible addition fragmentation chain transfer (RAFT) polymerization named 9‐anthracenylmethyl (4‐cyano‐4‐(N‐carbazylcarbodithioate) pentanoate) (ACCP) was synthesized with a total yield over 75% by the incorporation of both fluorescent donor and acceptor chromophores. Polymerization of heterotelechelic α,ω end‐labeled dye‐functionalized polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(n‐butyl methacrylate) (PBMA) with adjustable molecular weights and narrow polydispersity could be conducted by a one‐pot procedure through RAFT polymerization with this bischromophore chain transfer agent. The polymerizations demonstrated “living” controlled characteristics. By taking advantage of the characteristic fluorescence resonance energy transfer (FRET) response between the polymer chain terminals, the variation of chain dimensions in solution from the dilute region to the semidilute region can be monitored by changes in the ratio of the fluorescence intensities of the carbazolyl group to the anthryl group, which lends itself to potential applications in characterizing chain dimensions in solutions for thermodynamic or dynamic studies. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2413–2420