2018 Vol. 31, No. 2

Content
Contents
2018, 31(2): 0-0.
Chinese abstract
Chinese Abstracts
2018, 31(2): I-Ⅱ.
Article
Complex-forming reactions widely exist in gas-phase chemical reactions.Various complexforming bimolecular reactions have been investigated and interesting phenomena have been discovered.The complex-forming reactions usually have small or no barrier in the entrance channel,which leads to obvious differences in kinetic and dynamic characteristics compared with direct reactions.Theoretically,quantum state-resolved reaction dynamics can provide the most detailed microscopic dynamic mechanisms and is now feasible for a direct reaction with only one potential barrier.However,it is of great challenge to construct accurate potential energy surfaces and perform accurate quantum dynamics calculations for a complex polyatomic reaction involving deep potential wells and multi-channels.This paper reviews the most recent progress in two prototypical oxyhydrogen complex-forming reaction systems,HO2 and HO3,which are significant in combustion,atmospheric,and interstellar chemistry.We will present a brief survey of both computational and experimental work and emphasize on some unsolved problems existing in these systems.
The determination of pesticide residue on agricultural products is increasingly important.Exposure to pesticides can cause severe acute reactions in humans,including aplastic anemia and leukemia.In this work,we developed a rapid and sensitive method to detect acetamiprid pesticide residue based on surface-enhanced Raman scattering.Silver nanorod (AgNR) arrays were fabricated by oblique angle deposition technology and were used as SERS substrates.Prior to detection,the AgNR arrays were cleaned with nitric acid solution or a mixture of methanol and acetone.Compared to the unwashed AgNR arrays,the AgNR arrays washed with methanol and acetone shows a signal enhancement 1000 times greater than the unwashed AgNR array due to the effective removal of the impurities on its surface.The limit of detection of acetamiprid was determined to be 0.05 mg/L.In addition,the molecular structure of acetamiprid was simulated and the corresponding vibration modes of the characteristic bands of acetamiprid were calculated by density function theory.To demonstrate its practical application,the AgNRs array substrates were applied successfully to the rapid identification of acetamiprid residue on a cucumber's surface.These results confirmed possibility of utilizing the AgNRs SERS substrates as a new method for highly sensitive pesticide residue detection.
The dynamic NMR (DNMR) method was used to detect kinetic parameters of the molecular exchange process between monomers in bulk solution and those in the micelle for Gemini surfactants,12-s-12 and 14-s-14(s=2,3 and 4).The escape rate constant,k-,was derived based on the simplified equations of DNMR theory,and the apparent activation energy of escape,Ea-,was obtained based on the Arrhenius equation through temperature variation experiments.Results show that the orders of magnitude of k- for 14-s-14 and 12-s-12 are respectively 10 and 103 s-1,Ea- of 14-s-14 and 12-s-12 are respectively 54.04-73.64 and 33.42-47.09 kJ/mol.Furthermore, increases and Ea- decreases with the spacer length growing.In combination with the micro-polarity measurements,it was revealed that molecules of 14-s-14 and 12-s-12 have to experience conformation changes when escaping from the micelles.The two-step molecular exchange mechanism for Gemini surfactants was therefore supported.
The fluorescence quenching of Rhodamine 6G (R6G) by graphene oxide (GO) was interrogated by R6G fluorescence measurements using a set of controlled GO samples with varied C/O ratios as the quencher.The carbonyl groups on the GO nanosheet turned to play a dominant role in quenching the R6G fluorescence.The quenching in the static regime can be described by the "sphere of action" model.The significant absorption of the R6G fluorescence by the ground-state complex formed between R6G and GO was identified to be responsible for the static quenching.This work offers helpful insights into the fluorescence quenching mechanisms in the R6G/GO system.
We perform density functional theory calculations to investigate the polaron pair (charge transfer state) photo-generation in donor-acceptor oligomer methyl-capped (4,7-benzo[2,1,3]thiadiazole-2,6-(4,4-bis (2-ethylhexyl)-4H-cyclopenta[1,2-b;3,4-b']dithiophene-4,7-benzo[2,1,3]thiadiazole)(CPDTBT).Results show that effective photo-generation of charge transfer state can happen in CPDTBT dimer when the group 4,7-benzo[2,1,3]thiadiazole (BT) in one monomer deviates against the conjugated plane (onset torsion angle is about 20°).The lower excitation energy (530 nm) can only generate the intramolecular excitonic state,while the higher excitation energy (370 nm) can generate the intermolecular charge transfer state,in good agreement with the experiment.Moreover,the mechanism of charge separation in CPDTBT oligomers is discussed.
The combination effect of cation vacancies and O2 adsorption on ferromagnetism of Na0.5Bi0.5TiO3(100) surface is studied by using density functional theory.An ideal Na0.5Bi0.5TiO3(100) surface is non-magnetic and the cation vacancy could induce the magnetism.By comparing the formation energies for Na,Bi and Ti vacancy,the Na vacancy is more stable than the others.Therefore,we focus on the configuration and electric structure for the system of O2 molecule adsorption on the Na0.5Bi0.5TiO3(100) surface with a Na vacancy.Among the five physisorption configurations we considered,the most likely adsorption position is Na vacancy.The O2 adsorption enhances the magnetism of the system.The contribution of spin polarization is mainly from the O 2p orbitals.The characteristics of exchange coupling are also calculated,which show that the ferromagnetic coupling is favorable.Compared with the previous calculation results,our calculations could explain the room-temperature ferromagnetism of Na0.5Bi0.5TiO3 nanocrytalline powders more reasonably,because of taking into account adsorbed oxygen and cation vacancies.Moreover,our results also show that adsorption of O2 molecule as well as introduction of cation vacancies may be a promising approach to improve multiferroic materials.
Thermal decomposition of a famous high oxidizer ammonium dinitramide (ADN) under high temperatures (2000 and 3000 K) was studied by using the ab initio molecular dynamics method.Two different temperature-dependent initial decomposition mechanisms were observed in the unimolecular decomposition of ADN,which were the intramolecular hydrogen transfer and N-NO2 cleavage in N (NO2)-.They were competitive at 2000 K,whereas the former one was predominant at 3000 K.As for the multimolecular decomposition of ADN,four different initial decomposition reactions that were also temperature-dependent were observed.Apart from the aforementioned mechanisms,another two new reactions were the intermolecular hydrogen transfer and direct N-H cleavage in NH4+.At the temperature of 2000 K,the N-NO2 cleavage competed with the rest three hydrogen-related decomposition reactions,while the direct N-H cleavage in NH4+ was predominant at 3000 K.After the initial decomposition,it was found that the temperature increase could facilitate the decomposition of ADN,and would not change the key decomposition events.ADN decomposed into small molecules by hydrogen-promoted simple,fast and direct chemical bonds cleavage without forming any large intermediates that may impede the decomposition.The main decomposition products at 2000 and 3000 K were the same,which were NH3,NO2,NO,N2O,N2,H2O,and HNO2.
Among the perovskite-type oxides with symmetrical structure applied in oxygen permeable membranes,cubic phase structure is the most favorable for oxygen permeation.In order to stabilize the cubic perovskite structure of BaFeO3-δ material at room temperature,iron was partially substituted by praseodymium.BaFe1-yPryO3-δ powders were synthesized by a solid state reaction method,and sintered samples were prepared from the synthesized BaFe1-yPryO3-δ powders.X-ray diffraction results reveal that the BaFe1-yPryO3-δ samples remain cubic structure at praseodymium substitution amount of y=0.05,0.075,0.1.Scanning electron microscope observation indicates that the sintered samples contain only a small amount of enclosed pores and the grain size of BaFe1-yPryO3-δ increase monotonically with the increase of the praseodymium doping amount,praseodymium doping promotes the grain size growth.Tests of electrical conductivity and oxygen permeation flux show that praseodymium doping improves the conduction properties of BaFe1-yPryO3-δ and BaFe0.9Pr0.1O3-δ composition has an electrical conductivity of 6.5 S/cm and an oxygen permeation of 1.112 mL/(cm2·min) at 900 ℃,respectively.High temperature XRD investigation shows that the crystal structure of BaFe0.975Pr0.025O3-δ membrane completely transform to cubic phase at 700 ℃.The present test results have shown that partially substitution of Fe by praseodymium in BaFeO3 can stabilize the cubic structure and improve the properties.
Cadmium-doped zinc oxide nanocrystals in the quantum confinement region have been firstly synthesized by a fast and facile sonochemical method.The alloyed structure of the nanocrystals is confirmed by X-ray diffraction,transmission electron microscopy,and infrared analysis.With the increase of cadmium to zinc molar ratio from 0 to 2.0,the crystallite sizes of the samples decrease from 5.1 nm to 2.6 nm,and the band gaps of the samples show a red shift then a blue shift,and a red shift again.The variations of band gaps of the samples can be interpreted by the crystallite size and the composition.It is found that both the non-thermal equilibrium environment established in the sonochemical reaction and the coordination ability of triethylene glycol solvent play crucial roles in the current preparation.
The MgO/NaY catalysts prepared by impregnation method were used for the conversion of glucose to fructose in water medium.The effects of MgO loading,reaction temperature,glucose concentration and reaction time on the catalytic performance for the reaction were studied.The activity testing results indicated that fructose could be generated effectively by controlling the components of the catalyst and reaction conditions.The maximal fructose yield of 33.8% with the selectivity of 67.3% was achieved over the 10% MgO/NaY catalyst at 100 ℃ for 2 h.Moreover,the catalysts were characterized by XRD,BET,and CO2-TPD techniques.The structural property of NaY with higher surface area facilitated glucose conversion,and the modulated basicity of the catalyst with MgO addition contributed to the formation of fructose in the tautomerization of aldose to ketose.
Poly (ether ether ketone)(PEEK) is a high-performance semi-crystalline thermoplastic polymer.Exposure of the polymeric surface to solvents can have a strong effect like softening/swelling of polymeric network or dissolution.In this study,nano-indentation analysis was performed to study the effect of acetone on the surface mechanical properties of PEEK using different exposure time.The experiments were performed with a constant loading rate (10 nm/s) to a maximum indentation displacement (1000 nm).A 30-second hold segment was included at the maximum load to account for any creep effects followed by an unloading segment to 80% unloading.The indentation hardness and the elastic modulus were computed as a continuous function of the penetration displacement in the continuous stiffness mode (CSM) indentation.The experimental data showed that the peak load decreased from ~5.2 mN to ~1.7 mN as exposure time in solvent environment increased from 0 to 18 days.The elastic modulus and the hardness of PEEK samples also displayed a decreasing trend as a function of exposure time in the solvent environment.Two empirical models were used to fit the experimental data of hardness as a function of exposure time which showed a good agreement with the experimental values.
Aluminum is widely used in transmission lines,and the accumulation of ice on aluminum conductor may inflict serious damage such as tower collapse and power failure.In this study,super-hydrophobic surface (SHS) on aluminum conductor with micro-nanostructure was fabricated using the preferential etching principle of crystal defects.The surface microstructure and wettability were investigated by scanning electron microscope and contact angle measurement,respectively.The icing progress was observed with a self-made icing experiment platform at different environment temperature.The results showed that,due to jumping and rolling down of coalesced droplets from SHS of aluminum conductor at low temperature,the formation of icing on SHS could be delayed.Dynamic icing experiment indicated that SHS on aluminum conductor could restrain the formation of icing in certain temperature range,but could not exert influence on the accumulation of icing.This study offers new insight into understanding the anti-icing performance of actual aluminum conductor.
Controllable syntheses of different-sized gold nanoclusters are of great significance for their fundamental science and practical applications.In this work,we achieve the controllable and selective syntheses of Au7 and Au13 clusters through adding HCl to the traditional Au11 synthetic route at different reaction time.Time-dependent mass spectra and UVVis spectra were employed to monitor these two HCl-directed processes,and revealed the distinct roles of HCl as an etchant or a growth promotor,respectively.Furthermore,parallel experiments on independent synthetic routes involving only non-chlorine H+(acetic acid) or Cl-(tetraethy lammonium chloride) instead of HCl were performed,which illustrated the main role of H+-etching and Cl--assisted growth in HCl-directed cluster synthetic routes.We propose the HCl-etching is mainly achieved via the H+ action to break the Au (I)-PPh3 part of clusters,while the HCl-promoted growth is realized via the attachment of Au-Cl species to the pre-formed clusters.
A novel and effective approach was developed to synthesize monodisperse hollow molecularly imprinted polymers (MHMIPs) with unfunctionalized SiO2 spheres in a mixture of toluene and CH3CN.The factors that affected the synthesis of MHMIPs were systematically investigated.It was determined that a suitable ratio of toluene to CH3CN and the use of a functional monomer that can generate double H-bonding interactions were the critical factors to obtain MHMIPs with high uniformity and monodispersion.The obtained MHMIPs exhibited a fast adsorption rate and high adsorption capacity (270 μmol/g) for bisphenol A.As the shell thickness increased from 90 nm to 130 nm,the binding capacity of the imprinted shells decreased gradually.The relative selectivity coefficients of MHMIPs for tetra-bromobisphenol A (TBBPA),phenol and p-tert-butylphenol (PTBP) were calculated as 1.53,1.83 and 1.90,respectively.These findings indicate that MHMIPs have good adsorption performances and suggest applications in the selective removal or sensitive analysis of bisphenol A.
Ulcerative colitis,an inflammatory bowel disease,is a chronic inflammatory disorder that results in ulcers of the colon and rectum without known etiology.Ulcerative colitis causes a huge public health care burden particularly in developed countries.Many studies suggest that ulcerative colitis results from an abnormal immune response against components of commensal microbiota in genetically susceptible individuals.However,understanding of the disease mechanisms at cellular and molecular levels remains largely elusive.In this paper,a network model is developed based on our previous study and computer simulations are performed using an agent-based network modeling to elucidate the dynamics of immune response in ulcerative colitis progression.Our modeling study identifies several important positive feedback loops as a driving force for ulcerative colitis initiation and progression.The results demonstrate that although immune response in ulcerative colitis patients is dominated by anti-inflammatory/regulatory cells such as alternatively activated macrophages and type Ⅱ natural killer T cells,proinflammatory cells including classically activated macrophages,T helper 1 and T helper 17 cells,and their secreted cytokines tumor necrosis factor-α,interleukin-12,interleukin-23,interleukin-17 and interferon-γ remain at certain levels (lower than those in Crohn's disease,another inflammatory bowel disease).Long-term exposure to these proinflammatory components,causes mucosal tissue damage persistently,leading to ulcerative colitis.Our simulation results are qualitatively in agreement with clinical and laboratory measurements,offering novel insight into the disease mechanisms.
Review
Two dimensional Fourier transform electronic spectroscopy (2DES) in the visible region enables direct observation of complex dynamics of molecules including quantum coherence in the condensed phase.This review aims to provide a bridge between the principles and intuitive physical description of 2DES for tutorial purpose.Special emphasis is laid upon how 2DES circumvents the restrictions from both uncertainty principle and the wave-packet collapse during the coherent detection,leading to the successful detection of the coherence in terms of energy difference between the eigenstates showing as the quantum beats;then upon the possible mixing among the pure electronic transition,single-mode and multi-mode coupled vibronic transition leading to the observed beating phenomena.Finally,recent advances in experimentally distinguishing between the electronic coherence and the vibrational coherence are briefly discussed.