等离子体制取羟自由基降解苯酚溶液及其历程的UV研究

研究了利用强电离放电产生等离子体方法制取羟基自由基氧化降解高浓度苯酚废水。当羟基自由基浓度达到1 037 mg·L-1时,初始浓度为1 215 mg·L-1的废水降解率达99.11%;初始浓度为8 853 mg·L-1的废水苯酚浓度下降到6 250 mg·L-1,1 mg羟基自由基可处理苯酚2.5 mg。在同样羟自由基浓度下,苯酚初始浓度越小,去除率越高;但初始浓度越高,处理的绝对量越大。阐述并解释了不同降解阶段废水pH值、电导率与羟基自由基浓度变化的关系。随着羟自由基浓度的增大,废水酸碱性由接近中性逐渐转为酸性,浓度越大,酸性越强;继续增大羟自由基浓度,变化渐趋平缓。随着羟自由基的通入,电导率有一个微小的降低阶段然后开始上升,说明苯酚不断的被氧化为有机酸。通过紫外图谱和色谱分析了降解中间产物,表明氧化初始阶段邻苯二酚、对苯二酚和苯醌是其中重要的化合物。     

褶合光谱法考察羟自由基清除剂对紫外照射致DNA变异的作用

采用褶合光谱法考察了紫外线UV A ,UV B ,UV C导致的DNA变异 ,并以褶合光谱差谱值的形式量化表达DNA细微突变的程度。DNA受UV A ,UV B ,UV C作用后 ,差谱值依次增大 ,表明变异程度增大 ;添加二甲亚砜、甘露醇等羟自由基清除剂以后 ,在UV A ,UV B ,UV C作用下 ,差谱值有不同程度的降低 ,呈现一定的抑制变异作用。尽管DNA的变异程度有所区别 ,但它们的差谱点分布区域相似 ,提示UV A ,UV B ,UV C导致的DNA变异类型可能相似 ,两种羟自由基清除剂抑制DNA变异的作用机制也可能相似     

Elementary reactions of formyl (HCO) radical studied by laser photolysis—transient absorption spectroscopy

Several elementary reactions of formyl radical of combustion importance were studied using pulsed laser photolysis coupled to transient UV–Vis absorption spectroscopy: HCO → H + CO (1), HCO + HCO → products (2), and HCO + CH₃ → products (3). One-pass UV absorption, multi-pass UV absorption as well as cavity ring-down spectroscopy in the red spectral region were used to monitor temporal profiles of HCO radical. Reaction (1) was studied over the buffer gas (He) pressure range 0.8–100 bar and the temperature range 498–769 K. Reactions (2a), (2b), (2c), (3a) and (3b) as well as the UV absorption spectrum of HCO, were studied at 298 and 588 K, and the buffer gas (He) pressure of 1 bar. Pulsed laser photolysis (308, 320, and 193 nm) of acetaldehyde, propionaldehyde, and acetone was used to prepare mixtures of free radicals. The second-order rate constant of reaction (1) obtained from the data at 1 bar is: k₁(He) = (0.8 ± 0.4) × 10⁻¹⁰exp(−(66.0 ± 3.4) kJ mol⁻¹/RT) cm³ molecule⁻¹ s⁻¹. The HCO dissociation rate constants measured in this work are lower than those reported in the previous direct work. The difference is a factor of 2.2 at the highest temperature of the experiments and a factor of 3.5 at the low end. The experimental data indicate pressure dependence of the rate constant of dissociation of formyl radical 1, which was attributed to the early pressure fall-off expected based on the theory of isolated resonances. The UV absorption spectrum of HCO was revised. The maximum absorption cross-section of HCO is (7.3 ± 1.2) × 10⁻¹⁸ cm² molecule⁻¹ at 230 nm (temperature independent within the experimental error). The measured rate constants for reactions (2a), (2b), (2c), (3a) and (3b) are: k₂ = (3.6 ± 0.8) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ (298 K); k₃ = (9.3 ± 2.3) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹(298 and 588 K).     

低强度超声场中羟自由基分光光度法检测研究

研究了不同pH(7～11)、不同乙醇体积分数(45%～85%)的孔雀石绿乙醇溶液的紫外-可见光吸收特性,通过最大吸收波长为620nm处的吸光度与浓度关系工作标准曲线,在低强度超声场中,分别检测超声条件和非超声条件下孔雀石绿溶液吸光度变化,两者的差值就是超声场产生的羟自由基导致的孔雀石绿吸光度变化,从而间接测定了超声场产生的羟自由基浓度。确定了4个超声条件产生的羟自由基浓度,最小检测限达到8.4×10-6 mmol.L-1,相对标准偏差为9.4×10-5～3.7×10-4 mmol.L-1,显示出较高精确度和较好重复性,特别适于中性、碱性乙醇溶液体系中羟自由基极低浓度情况下的快速检测。由于孔雀石绿对热敏感,因此该法可以比测量温度,更好地反映超声场热效应的作用。     

Numerical analysis of quantitative measurement of hydroxyl radical concentration using laser-induced fluorescence in flame

The aim of the present work is to quantitatively measure the hydroxyl radical concentration by using LIF(laserinduced fluorescence) in flame.The detailed physical models of spectral absorption lineshape broadening,collisional transition and quenching at elevated pressure are built.The fine energy level structure of the OH molecule is illustrated to understand the process with laser-induced fluorescence emission and others in the case without radiation,which include collisional quenching,rotational energy transfer(RET),and vibrational energy transfer(VET).Based on these,some numerical results are achieved by simulations in order to evaluate the fluorescence yield at elevated pressure.These results are useful for understanding the real physical processes in OH-LIF technique and finding a way to calibrate the signal for quantitative measurement of OH concentration in a practical combustor.     

Quantitative measurement of hydroxyl radical(OH) concentration in premixed flat flame by combining laser-induced fluorescence and direct absorption spectroscopy

An accurate and reasonable technique combining direct absorption spectroscopy and laser-induced fluorescence(LIF)methods is developed to quantitatively measure the concentrations of hydroxyl in CH_4/air flat laminar flame. In our approach, particular attention is paid to the linear laser-induced fluorescence and absorption processes, and experimental details as well. Through measuring the temperature, LIF signal distribution and integrated absorption, spatially absolute OH concentrations profiles are successfully resolved. These experimental results are then compared with the numerical simulation. It is proved that the good quality of the results implies that this method is suitable for calibrating the OH-PLIF measurement in a practical combustor.     

The reactivity of the 5‐formylcytosine with hydroxyl radical: A theoretical perspective

Hydroxyl radical (?OH) damages DNA/RNA by attacking pyrimidine nucleobases through the addition reaction and H‐atom abstraction. It may attack on the new cytosine derivative (5‐formylCytosine [5‐fCyt]) causing DNA oxidative damage, whereas the study of the related mechanism is still in its infancy. In the present work, 2 distinct mechanisms of ?OH‐mediated 5‐fCyt at the complete basis set methods (CBS‐QB3) and CBS‐QB3/polarized continuum model approaches have firstly been explored, the addition reaction (paths R1 ~ R3) and the abstraction reaction (paths R4 ~ R6), respectively, and it shows that the addition of ?OH to the C5═C6 double bond of 5‐fCyt is more favourable than other reactions, indicating that the ?OH addition to the C5 and C6 atoms have relatively high probability to happen. The proportion of the C5 and C6 adducts is large and may be detectable experimentally, which is in agreement with the conclusions of ?OH‐mediated cytosine reaction reported experimentally and theoretically. These hint that the new DNA base (5‐fCyt) is easily damaged when exposed the surrounding of ?OH environment. Therefore, the reducing free radical production or the addition of some antioxidants should be taken in embryonic stem cells to resistance DNA damage. Our results provide some evidences between 5‐fCyt and tumor development for the experimental scientists.     

Nitric oxide detection inside the cylinder of an SI engine by direct UV absorption spectroscopy

The present work is a first step for the implementation and the development of a rapid and quantitative measurement technique using the UV broadband-lamp absorption spectroscopy. This technique is applied to detect nitric oxide molecules inside the combustion chamber of a methane-fueled spark-ignition engine. The ability of this technique to detect NO in very harsh thermodynamic conditions is proved under certain engine operating conditions. In spite of the broadband absorption, mainly due to the hot CO₂ and H₂O, clear NO absorption γ-bands are observed when the engine is skip-fired or when NO is added at the intake port. It was however, not possible to detect any nitric oxide absorption during the combustion time when each cycle was ignited and no nitric oxide was added. Finally, using the skip-ignition mode, the acquired NO absorption spectra allowed to conclude that evacuation of the in-cylinder residual gases can be complete at the end of the sixth cycle.     

Measurement of the terrestrial ozone concentration by absorption UV spectroscopy

The conditions allowing one to measure the concentration of terrestrial ozone by the open-path DOAS method using a zero line are considered. A technique based on measuring signals at two wavelengths, at least one of which belongs to the ozone absorption UV band, is described. The error of measurements has been estimated. A block-diagram of the optical “open-path” meter for measuring the terrestrial ozone concentration, TrIO-2, is presented. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 832–836, November–December, 2005.     

强电场电离放电产生羟基等离子体反应过程的研究

从强电场等离子体反应室结构、电介质材料及加工工艺等方面出发．研究了在建立强电场并把O2、H2O电离后在分子层次上加工成OH^ 、eaq^-(水合电子)等自由基的等离子体反应过程。用这种方法产生的自由基的浓度、产成量均能满足工程上的需要．达到绿色化学12条原则要求,从源头上解决了环境污染问题。着重研究了羟基治理烟气SO2的绿色资源化的新方法．在无吸收剂、催化剂条件下,仅在0．8s内就能把烟气中SO2、H2O和O2电离后在分子层次上加工成H2SO4。     

Measurement of hydroxyl radical production in ultrasonic aqueous solutions by a novel chemiluminescence method

Measurement methods for ultrasonic fields are important for reasons of safety. The investigation of an ultrasonic field can be performed by detecting the yield of hydroxyl radicals resulting from ultrasonic cavitations. In this paper, a novel method is introduced for detecting hydroxyl radicals by a chemiluminescence (CL) reaction of luminol-hydrogen peroxide (H2O2)-K5[Cu(HIO6)2](DPC). The yield of hydroxyl radicals is calculated directly by the relative CL intensity according to the corresponding concentration of H2O2. This proposed CL method makes it possible to perform an in-line and real-time assay of hydroxyl radicals in an ultrasonic aqueous solution. With flow injection (FI) technology, this novel CL reaction is sensitive enough to detect ultra trace amounts of H2O2 with a limit of detection (3sigma) of 4.1 x 10(-11) mol L(-1). The influences of ultrasonic output power and ultrasonic treatment time on the yield of hydroxyl radicals by an ultrasound generator were also studied. The results indicate that the amount of hydroxyl radicals increases with the increase of ultrasonic output power (< or = 15 W mL(-1)). There is a linear relationship between the time of ultrasonic treatment and the yield of H2O2. The ultrasonic field of an ultrasonic cleaning baths has been measured by calculating the yield of hydroxyl radicals.     

Microwave spectrum of the OD-OH2 complex: A strong deuterium isotope effect on angular momentum quenching in the hydroxyl moiety

Microwave spectra of the hydrogen bonded complex ¹⁶OD-¹⁶OH₂ have been recorded using pulsed-nozzle Fourier transform microwave spectroscopy. The potential splitting, ρ, which describes the partial quenching of the OD orbital angular momentum upon complexation, is determined to be −142.703173(65) cm⁻¹. Within the spectroscopic model employed, this value implies an energy difference of 202.46 cm⁻¹ between the ground (²A′) and first excited (²A′′) states of the complex. The observed value of ρ represents a rather large change of 3.85710(11) cm⁻¹ relative to that in the parent complex and implies a 1.30 cm⁻¹ decrease in the ²A′-²A′′ energy spacing relative to the parent species. Comparison with previous results for the ¹⁸OH complex suggests that these changes likely arise from changes in vibrationally averaged geometry upon deuteration. Magnetic hyperfine structure from the deuterium and the water protons is analyzed, as is the nuclear electric quadrupole coupling of the deuterium nucleus. Assuming negligible changes in the axial component of the electric field gradient at the deuterium upon complexation, the deuterium quadrupole coupling constant implies an average angular excursion of the OD bond axis from the vibrationally averaged a-inertial axis of the complex of ∼24°.     

First report on the persist time of the free radical produced by shock wave pulses employed in clinical ESWL

The shock wave used in extracorporeal shock wave lithotripsy (ESWL) induces strong cavitation and generates a large amount of free radicals (FR). In order to evaluate the harmfulness of FR in the ESWL, information on the incidence and persist time of FR caused by shock waves is required. FR markers can estimate the amount of FR generated, but not how long the FRs will survive. The OH* FR generated by the ESWL shock wave reacts with luminol and emits blue light, which is called sonochemical luminescence (SCL) phenomenon. In this study, FR generation and persist time were measured by recording SCL phenomenon with a sensitive photomultiplier tube (PMT) that responds in nanoseconds. As a result of measurement with the PMT, when the electromagnetic shock wave used in clinical practice was irradiated to the luminol solution, the amount of light emitted per unit time reached its maximum value within a very short time (< ∼600us) and then exponentially decreased for a long time (∼several hundred ms). The measured FR persist time reaches a maximum of 1000 ms. As the output setting of the shock wave generator increases, the minimum or average FR persist time increases, but the maximum value does not show a high correlation with the output setting. The amount of generated FR shows a very high correlation with the shock wave setting, and when the setting is changed from low to high, it increases very sensitively, rapidly and non-linearly. In order to reduce the risk of FR in patient treatment using lithotripsy, the output setting of the shock wave should be minimized, and the interval between the shock wave pulses should be sufficiently larger than the FR persist time. Therefore, it is recommended to avoid increasing the output setting and setting the shock wave irradiation frequency below 1 Hz to shorten the treatment time in clinical practice. For the purpose of formulating these recommendations, additional studies on the generation and persist time of FR depending on the shock wave generation method and set conditions in living tissue or similar environment are required in the future.     

Exceptionally high decarboxylation rate of a primary aliphatic acyloxy radical determined by radical product yield analysis and quantitative 1H‐CIDNP spectroscopy

Symmetrical (RCO₂CO₂R; R = XCH₂CH₂) and asymmetrical (RCO₂CO₂R′; R = C₉H₁₉CH₂CH₂, R′ = CH₃ or m‐ClC₆H₄) primary diacyl peroxides were thermally decomposed under different conditions to analyze the decarboxylation rates of the thermally generated acyloxy radicals. Quantitative models of the geminate product yields, and qualitative and quantitative ¹H‐CIDNP spectroscopy were used to obtain the decarboxylation rate estimates. Results reported here suggest that, unlike short chain acyloxy radicals such as propanoyloxyl, long chain acyloxy radicals possess the highest decarboxylation rates of all known acyloxy radicals, estimated at (0.5–1.5) × 10¹² s^?1 between 80 and 140 °C. Given the nature of the dissociative state of acyloxy radicals, such rates appear to be the result of destabilization of the former by the steric bulk of the long chain substituents. Additionally, the rate of this order of magnitude suggests a nearly concerted decarboxylation of primary diacyl peroxides. Copyright © 2011 John Wiley & Sons, Ltd.     

水辅助下的OH自由基与CH_3OOH气相反应机理的理论研究

利用量子化学计算方法对单个水分子不存在与存在的情况下OH自由基与CH3OOH的气相氢抽取反应进行了理论研究.在BHand HLYP/6-311++G(2df,2pd)理论水平下优化了所有驻点的几何构型,在此基础上利用CCSD(T)/cc-p VTZ方法对所有驻点的单点能重新进行了计算.计算结果表明,OH自由基与CH3OOH反应的主要通道是OH自由基抽取CH3OOH中的-OH基团上的H原子.在单个水分子存在的情况下,反应的主要通道没有改变,但是水化过渡态的能量显著地降低,显然单个水分子对OH+CH3OOH反应具有催化效应.     

水辅助下的OH自由基与CH3OOH气相反应机理的理论研究

利用量子化学计算方法对单个水分子不存在与存在的情况下OH自由基与CH3OOH的气相氢抽取反应进行了理论研究。在BHandHLYP/6-311++G(2df,2pd)理论水平下优化了所有驻点的几何构型,在此基础上利用CCSD(T)/cc-pVTZ方法对所有驻点的单点能重新进行了计算。计算结果表明,OH自由基与CH3OOH反应的主要通道是OH自由基抽取CH3OOH中的-OH基团上的H原子。在单个水分子存在的情况下,反应的主要通道没有改变,但是水化过渡态的能量显著地降低,显然单个水分子对OH+CH3OOH反应具有催化效应。     

Penetration of hydroxyl radicals in the aqueous phase surrounding a cavitation bubble

In the sonochemical degradation of nonvolatile compounds, the free radicals must be delivered into the aqueous solution from the cavitation bubble to initiate reduction–oxidation reactions. The penetration depth in the liquid becomes an important parameter that influences the radical delivery efficiency and eventual treatment performance. However, the transport of radicals in the liquid phase is not well understood yet. In this paper, we focus on the most reactive OH radical and numerically simulate its penetration behavior. This is realized by solving the coupled equations of bubble dynamics, intracavity chemistry, and radical dispersion in the aqueous phase. The results present both the local and global penetration patterns for the OH radicals. By performing simulations over a wide range of acoustic parameters, we find an undesirable phenomenon that the penetration can be adversely suppressed when strengthening the radical production. A mechanistic analysis attributes this to the excessively vigorous recombination reactions associated with high radical concentrations near the bubble interface. In this circumstance, the radicals are massively consumed and converted into molecular species before they can appreciably diffuse away. Our study sheds light on the interplay between radical production inside the bubble and dispersion in the outside liquid. The derived conclusions provide guides for sonochemical applications from a new perspective.     

NaCCH自由基低能电子态的理论研究

采用CASSCF/CASPT2方法研究了NaCCH自由基的低能电子态,在C2v对称性下给出了NaCCH自由基9个低能激发态的几何、组态、CI系数、振子强度、垂直激发能和绝热激发能.研究结果表明,NaCCH自由基的基态X1Σ+几何和转动系数与实验值是一致的;谐振频率与其他理论方法得到的值也符合的很好;HOMO和LUMO轨道的能量间隔为3.80eV,对应着13Σ+的绝热激发能;除13Π外,其它低能激发态均是稳定状态;基态到三重态是自旋禁阻的.     

磺酸基对掺杂酞菁在溶胶-凝胶复合体系中UV/Vis吸收光谱的影响

选择、设计具有代表性无取代酞菁镍(NiPc)和周环带有4个磺酸基的四磺化酞菁镍(NiTSPc),采用溶胶-凝胶湿化学将其均匀掺入SiO₂凝胶基质,制备无机基质酞菁掺杂复合光功能材料并考察磺酸基的引入对掺杂酞菁在溶胶-凝胶复合体系中UV/Vis吸收光谱的影响。研究结果表明水溶性磺酸基的引入有助于改善酞菁的溶解性,进而实现其与溶胶-凝胶体系的稳定互溶,使酞菁均匀掺杂复合材料的制备成为可能。     

紫外光谱法检测COD中硝酸盐与温度影响的研究

以邻苯二甲酸氢钾配制的化学需氧量标准液为实验对象,采集1~800mg·L-1标准液的紫外吸收光谱,运用偏最小二乘法(PLS)建立了不同谱区的校正模型,结果表明,265~310nm谱区模型的相关性最高,误差最小;为了消除硝酸盐与温度对化学需氧量测量的影响,分别研究了不同浓度的硝酸钠与不同温度条件下标准液的紫外吸收光谱的变化情况,结果表明硝酸钠在208~238nm有明显的吸收,265~310nm谱区模型不受硝酸钠吸收的影响,温度的升高会导致标准液的紫外光谱吸光度的增大,通过预测分析建立了不同校正模型下的温度补偿函数。