Excited‐state hydrogen bond strengthening of coumarin 153 in ethanol solvent: a TDDFT study

So far, coumarin dyes have been extensively studied with various means to understand their photophysical behaviors and photochemical properties. Here, our performing time‐dependent density functional theory calculation is aimed at exploring the excited‐state hydrogen bonding dynamics of coumarin 153 (C153) in protic ethanol (EtOH) solvent. The calculated results suggest that the excited‐state hydrogen bond C?O?H?O between C?O group and O?H group in the C153‐EtOH complex is strengthened, and the S₀ → S₁ transition of the complex corresponds to the highest occupied molecular orbital (HOMO) hopping to the lowest unoccupied molecular orbital (LUMO). The excited‐state hydrogen bond strengthening has been further confirmed by its larger binding energy in the S₁ state than in the S₀ state. In addition, because of the formation of the hydrogen bond C?O?H?O, a red shift of about 7 nm occurs in the electronic spectra of the C153‐EtOH complex, which is in good accordance with the experiment result. Copyright © 2016 John Wiley & Sons, Ltd.     

利用光栅光谱仪研究乙醇汽油溶液的吸收特性

利用WGD-8A型多功能光栅光谱仪测量了不同汽油体积含量的乙醇汽油溶液对波长为300.0～430.0 nm光的吸收光谱,分析了乙醇汽油吸光度和汽油浓度的关系,在稀溶液吸光度的朗伯-比尔定律基础上,进一步研究了2种高浓度混合溶液吸光度的计算方法,并得出了入射光波长为377.0,382.0,391.5,410.9 nm时乙醇汽油的吸光度与汽油体积浓度的关系式.     

Adsorption and reactions of ethanol on Mo2C/Mo(1 0 0)

The adsorption, desorption and dissociation of ethanol have been investigated by work function, thermal desorption (TPD) and high resolution electron energy loss (HREELS) spectroscopic measurements on Mo₂C/Mo(1 0 0). Adsorption of ethanol on this sample at 100 K led to a work function decrease suggesting that the adsorbed layer has a positive outward dipole moment By means of TPD we distinguished three adsorption states, condensed layer with a Tp = 162 K, chemisorbed ethanol with Tp = 346 K and irreversibly bonded species which decomposes to different compounds. These are hydrogen, acetaldehyde, methane, ethylene and CO. From the comparison of the Tp values with those obtained following their adsorption on Mo₂C it was inferred that the desorption of methane and ethylene is reaction limited, while that of hydrogen is desorption limited process. HREEL spectra obtained at 100 K indicated that at lower exposure ethanol undergoes dissociation to give ethoxy species, whereas at high exposure molecularly adsorbed ethanol also exists on the surface. Analysis of the spectral changes in HREELS observed for annealed surface assisted to ascertain the reaction pathways of the decomposition of adsorbed ethanol.     

罗丹明6G在醇溶液中的荧光频移特性分析

罗丹明6G在甲醇、乙醇、乙二醇溶液中均发出较强的荧光。当醇溶液浓度为33.3%时,基本不存在频移现象。当醇溶液浓度为99.7%时,荧光峰发生蓝移或红移,分析认为该频移是由罗丹明6G和醇类物质分子相互作用(如氢键、静电吸引)导致激发态能量升高、荧光峰蓝移,与醇类物质分子中羟基OH的孤对电子跃迁导致荧光能量降低、荧光峰红移,这两种因素相互竞争的结果,且在高浓度醇溶液中,羟基OH数量越多,红移越明显。     

Investigation on Three-Dimensional Solubility Parameters for Explanation and Prediction of Swelling Degree of Polydimethylsiloxane Pervaporation Membranes

Using polydimethylsiloxane (PDMS) as a basic matrix to prepare ethanol and butanol permselective pervaporation membranes is a vibrant field. Many studies have verified that the three-dimensional Hansen solubility parameters (HSP) theory offers a valid explanation for the swelling performance of ethanol and butanol in PDMS. Five parameters (δ_D, δ_P, δ_H, δ_t, and R_a) are defined in HSP theory which can be individually used to explain the interaction strength between a solvent and a polymer. However, for the above five parameters, which one is the most effective parameter for deciding the swelling degree still needs to be determined. In this study, a commonly used hydroxy-terminated PDMS precursor was adopted to prepare the PDMS network. The HSP of the chosen PDMS precursor was measured by an advanced “solubility-rating” method. The special software package HSPiP (4.1.03), purchased from the HSPiP team, was used to process the “solubility-rating” results. The equilibrium swelling degree (Q value) of the PDMS network in water, ethanol, butanol, and toluene was measured and the relationships between the five HSP parameters of the solvents and the logarithmic equilibrium swelling degree, log(Q), were discussed. It was found that the measured polar parameter, δ_P, of PDMS was 0.12 MPa^0.5. The measured hydrogen bonding parameter, δ_H, was larger than δ_P, attaining a value of 8.6 MPa^0.5, because the hydroxy groups directly contributed to the hydrogen bonding solubility parameter, δ_H. With respect to the relationships between log(Q) and δ_D, δ_P, δ_H, δ_t, and R_a, linear relationships existed after plotting log(Q) vs. δ_P and log(Q) vs. δ_H. The linear relation degree of the fitted lines was 0.995 and 0.989, respectively. Their standard deviations were 0.149 and 0.232, respectively. Therefore, a better linear relationship existed between log(Q) and δ_P than the other solubility parameters. This indicated that the polar interaction was the main effect for deciding the swelling degree of the PDMS network in water and alcohol systems.     

Enhanced renal image contrast by ethanol fixation in phase‐contrast X‐ray computed tomography

Phase‐contrast X‐ray imaging using a crystal X‐ray interferometer can depict the fine structures of biological objects without the use of a contrast agent. To obtain higher image contrast, fixation techniques have been examined with 100% ethanol and the commonly used 10% formalin, since ethanol causes increased density differences against background due to its physical properties and greater dehydration of soft tissue. Histological comparison was also performed. A phase‐contrast X‐ray system was used, fitted with a two‐crystal X‐ray interferometer at 35 keV X‐ray energy. Fine structures, including cortex, tubules in the medulla, and the vessels of ethanol‐fixed kidney could be visualized more clearly than that of formalin‐fixed tissues. In the optical microscopic images, shrinkage of soft tissue and decreased luminal space were observed in ethanol‐fixed kidney; and this change was significantly shown in the cortex and outer stripe of the outer medulla. The ethanol fixation technique enhances image contrast by approximately 2.7–3.2 times in the cortex and the outer stripe of the outer medulla; the effect of shrinkage and the physical effect of ethanol cause an increment of approximately 78% and 22%, respectively. Thus, the ethanol‐fixation technique enables the image contrast to be enhanced in phase‐contrast X‐ray imaging.     

Cu/ZrO2催化剂上乙醇水蒸气重整反应的研究Ⅱ反应条件的影响

采用沉淀法或醇凝胶法、浸渍法制备Cu/ZrO2催化剂,在常压微型固定床石英管反应器上进行乙醇水蒸气重整反应,采用程序升温还原（TPR）技术表征催化剂的还原特性。考察了催化剂还原温度、反应温度、水醇比、空速等对反应的影响以及催化剂的稳定性。结果表明,在300℃～500℃,随反应温度升高,乙醇转化率增大,H2选择性下降。不同还原温度对转化率的影响不是很大,对于H2选择性,300℃、400℃还原的催化剂优于500℃还原的催化剂。高水醇比有利于提高转化率和H2选择性。随空速增大,转化率和H2选择性呈现下降的趋势。8%Cu/ZrO2催化剂在400℃或450℃反应22h显示出良好的稳定性。     

Pt-SnO2 / C催化剂对乙醇和吸附态CO的电催化氧化

由于乙醇最有可能成为直接甲醇燃料电池（DMFC）的替代燃料，因此近年来。对乙醇的电化学氧化及直接乙醇燃料电池的研究已引起人们的很大兴趣。甲醇毒性较大并且易透过Nafion膜进入阴极造成阴极的混合电位而影响DMFC的阴极性能．这是制约DMFC走向实用化的主要问题之一。因此人们在致力于研究直接甲醇燃料电池的同时．也寻求其它的小分子醇作为甲醇的替代燃料。乙醇是除甲醇以外最简单的醇．它来源广泛．无毒，是可再生和环保型能源．并且也有较高的能量密度和反应活性。但是乙醇在电极上的完全氧化因涉及到C-C键的断裂要比甲醇困难．阳极反应动力学过程也比较缓慢。到目前为止铂基催化剂仍然是乙醇氧化最好的催化剂．虽然也有使用非铂催化剂研究乙醇的电氧化，但催化活性远不如铂基催化剂高。     

乙醇重整制氢对马来酸酐原位加氢制备四氢呋喃的研究

制备了两种聚乙烯吡咯烷酮(PVP)稳定的γ-Al_2O_3负载型稀土金属催化剂(PVP-La/Al_2O_3,PVP-Ce/Al_2O_3),并首次将乙醇催化重整制氢运用于马来酸酐(MA)液相加氢制备四氢呋喃(THF)的过程中。同时,对比研究了一种PVP稳定的钯催化剂(PVP-Pd/Al_2O_3)催化马来酸酐加氢的活性。结果表明,两种稀土金属催化剂显示出比PVP-Pd/Al_2O_3更优的催化性能。进而,系统考察了反应条件对PVPLa/Al_2O_3催化马来酸酐加氢反应的影响。在优化的条件下,MA实现了100%的转化,THF的选择性超过95.0%,最高达到98.2%的THF选择性。     

Dispersed Structure of Ethanol‐Gasoline Fuel According to Dynamic Light Scattering Method

The dispersed structures of mixtures of five different gasolines with anhydrous ethanol were investigated by the dynamic light scattering (DLS) method. The aim of the work was to find whether these blends are colloid systems. Influence of different parameters was investigated to verify the results of this research. Ethanol‐gasoline blends were found to be colloid systems with the drop size of 20–150 nm.