常温和100~800 MPa压力下石膏的Raman光谱研究

 利用金刚石压腔装置测量了高压下石膏中S—O键的4种振动模式和结晶水中羟基伸缩振动Raman位移，研究结果表明：在常温（25 ℃）和100~800 MPa压力范围内，石膏中S—O键的Raman谱峰的位移随压力的增加而向高波数方向移动，结晶水中羟基的两个伸缩谱峰随着压力的增加而向低波数方向移动，同时得到了各个谱峰与压力之间的关系式，其中结晶水中羟基的两个伸缩谱峰的dν/dp值有较大不同，是由于结晶水中含有两个强度不同的氢键所致。     

激光诱导多孔硅晶格畸变的Raman光谱和光致发光谱研究

研究了掺钛水热法制备多孔硅的Raman光谱和光致发光谱.实验发现,当激光功率较低时,多孔硅的Raman光谱在略低于520cm^-1附近表现为一锐的单峰,和晶体硅的Raman光谱类似.随激光功率增大,该单峰向低波数移动,Raman和光致发光峰的强度与激光强度的一次方成正比.当激光功率增大到一定值时,该单峰分裂成两个Raman峰,光致发光谱的强度突然增大,与激光强度之间不再满足一次方的关系,位于低波数一侧的Raman峰随激光功率增大进一步向低波数移动.多孔硅Raman光谱随激光功率的变化是 关键词： 多孔硅 Raman光谱 光致发光     

温度对鱼鳞胶原蛋白二级结构的影响

从草鱼鱼鳞中提取酶溶性胶原蛋白(PSC),通过SDS-PAGE电泳分析为典型Ⅰ型胶原蛋白且达到电泳纯。在此基础上利用傅里叶变换红外光谱(FTIR)、拉曼光谱(Raman)和圆二色谱(CD)研究了温度对鱼鳞胶原蛋白二级结构的影响。FTIR分析表明：鱼鳞胶原蛋白具有典型的胶原蛋白特征吸收带,酰胺Ⅰ、酰胺Ⅱ和酰胺Ⅲ带的特征吸收频率分别出现在1658,1552和1238cm-1处。随温度升高,酰胺A和酰胺B峰位向低波数移动,1658cm-1处吸收峰裂解成多个吸收峰;1552cm-1处的吸收峰在35℃微略红移,随后发生明显蓝移;1238cm-1处吸收峰随温度升高向低波数移动。在拉曼光谱中,胶原蛋白的酰胺Ⅰ、酰胺Ⅱ和酰胺Ⅲ带的特征吸收频率分别出现在1669,1557和1245cm-1处,都较红外光谱的波数高;此外,921和855cm-1处脯氨酸的特征谱峰在拉曼光谱中体现出来。圆二色谱分析表明,胶原蛋白溶液在221.6和204.4nm分别有一正、负峰,具有典型胶原蛋白三螺旋结构的特征圆二色谱峰型。胶原蛋白冻干品的FTIR光谱和Raman谱线大都在35～60℃时发生波数和强度改变,而胶原蛋白乙酸溶液的CD谱线在20～35℃之间发生剧烈改变。由此可以判断胶原蛋白在固态和溶液状态下,变性温度存在一定差异,胶原蛋白冻干品比其乙酸溶液更稳定。     

常温和0.1～1 400 MPa条件下黄铜矿的拉曼光谱研究

实验利用金刚石压腔装置研究了常温和0.1～1 400 MPa范围内黄铜矿A₁振动模式的原位拉曼光谱特征。结果显示在实验条件范围内,该拉曼振动峰的强度和形态保持稳定,表明晶格内Cu-S和Fe-S间的相互作用没有发生质变。实验发现黄铜矿该拉曼振动的波数随着压力升高连续向高频方向移动,两者的线性关系为：ν₂₉₀＝0.031 2p+290.60(0.1≤p<58.8 MPa)和ν₂₉₀＝0.005 72p+292.10(58.8≤p<1 400 MPa)dν/dp。常温下58.8 MPa是黄铜矿该拉曼波数随压力变化率的一个突变点,低于和高于该压力时分别为31.2和5.72 cm-1·GPa-1,显著的差异表明黄铜矿的结构可能发生了某种改变。     

290K下0.1～600MPa水的Raman光谱原位研究

在 2 90K和 0 0 1～ 6 0 0MPa条件下 ,就压力对液态水对称伸缩振动的影响进行了原位Raman散射光谱研究。表明 :( 1)在 0 1～ 2 0 0MPa范围内 ,(ν1) max随着压力升高而减小 ;( 2 )在 2 0 0～ 4 0 0MPa范围内 ,压力升高导致 (ν1) max增大 ,并在 4 0 0MPa时达到最大值 ;( 3) (ν1) max随着压力的进一步升高 ( >4 0 0MPa)而降低。这表明在 2 0 0和 4 0 0MPa时 ,液态水结构的变化是不连续的 ,这也与在该压力范围内rOO 的变化特征是一致的。可认为与冰Ⅰh→冰Ⅲ→冰Ⅴ的相变相类似 ,也许存在液态水Ⅰh→水Ⅲ→水Ⅴ的相变     

爆轰合成纳米超微金刚石的Raman光谱表征

 用炸药爆轰的方法制备了纳米超微金刚石,对纳米超微金刚石进行了激光Raman光谱分析。研究发现,在1 321 cm^-1和1 600 cm^-1附近观察到了对应于sp³金刚石和sp²石墨的特征峰,金刚石的Raman峰向低波数方向移动了约10 cm^-1,其半高宽约30 cm^-1,同时在低波数方向出现尾巴,呈现非对称的Raman波谱。Raman光谱分析的结果与X射线衍射分析的结果符合。     

纳米磷化镓粉体还原氦过程的Raman光谱分析

利用Raman光谱对还原氮后的纳米磷化镓(GaP)粉体进行了表征。结果表明：纳米GaP粉体表面含有Ga-O，P-O和H-O化学键。此外，进行氮还原过程后，在Raman位移约为1700～3300cm^-1范围内(相当于709～800nm或1．55～1．75eV)，纳米GaP的Raman光谱出现了一个宽、强荧光发射峰；而在未进行通氮处理的纳米GaP Raman光谱中，没有观察到该荧光峰的存在。本文对该荧光发射峰的起因作了初步分析。     

高压下正戊醇的拉曼光谱原位研究

在室温(23℃)高压条件下,利用立方氧化锆压腔研究了正戊醇在波数800~3 000 cm-1范围内的拉曼光谱。拉曼谱峰随着压力的增大变得越来越尖锐,C—H伸缩振动峰在高压下不易被分离。在0.1 MPa~1.75 GPa,其C—H伸缩振动峰均随着压力的增大向高波数方向线性移动,拉曼频移与压力的线性拟合方程分别为:P(MPa)=69.652 65.(Δνp)single,T=23℃+105.806 93,0(Δpν)single(cm-1)≤23;P(MPa)=77.974 04.(Δpν)2 960,T=23℃+95.390 5,0(Δνp)2 960(cm-1)≤21;P(MPa)=126.956 39.(Δpν)2 863,T=23℃-110.648 09,0(Δpν)2 863(cm-1)≤13。正戊醇的C—H伸缩振动单峰拟合的波数随压力的变化关系为(sνingle/P)T=(14±1)cm-1,适合用来标定体系压力。在压力为1.75 GPa时,正戊醇的拉曼谱峰有明显跳跃,同时镜下观察到其液-固相转变。液-固相转变过程中的摩尔体积变化为ΔVm=1.84×10-6m3.mol-1。     

离子注入法制备GaN∶Er薄膜的Raman光谱分析

对离子注入法制备的u-,n-和p-GaN∶Er三种类型的薄膜样品进行了Raman光谱分析。Er+注入GaN样品后新出现了293,362和670 cm-1等波数的Raman峰,其中293 cm-1处的Raman峰被指认为无序激活的Raman散射(DARS),362 cm-1和670 cm-1处的Raman峰可能与离子注入后形成的GaN晶格缺陷有关。上述GaN∶Er样品在800℃退火前后的E₂(high)特征峰均向高频方向移动,表明薄膜晶格中均存在着压应力。采用洛伦兹拟合分析了Raman光谱中组成A₁(LO)模式峰的未耦合LO模与等离子体激元耦合模LPP+在不同样品中的出现情况,定性指出了GaN∶Er系列样品中载流子浓度的变化规律。     

铝硅酸盐Raman活性分子振动解析

分别测定了蓝晶石、红柱石和硅线石三种铝硅酸盐天然矿物晶体以及K₂O-Al₂O₃-SiO₂三元铝硅酸盐玻璃的Raman光谱。构建了一组硅铝四面体聚集体结构模型,采用量子化学自洽场分子轨道从头计算的方法计算了其Raman振动频率。分析研究了上述Raman光谱振动特征,确定了特征谱峰的归属,解析了铝对铝硅酸盐Raman活性分子振动特征的影响。结果表明,随四配位铝的增加,导致800～1 200 cm-1波数区间内谱峰频率降低,该区间的谱峰是Si—O_nb间非桥氧对称伸缩振动引起的,其中不含Al—O振动;700～800 cm-1区间内出现的谱峰归属于Al—O_nb间非桥氧的对称伸缩振动。     

Wastes Treatment: Hydrothermal electrolytic oxidation of wastewater

Abstract

Electrochemical evolution of hydrogen gas, oxygen gas and chlorine at the electrodes is the usual reaction in conventional electrolysis of aqueous salt solution. However, here we demonstrate that the electrolysis governing reaction in hydrothermal solutions is different from the electrolysis performed at atmospheric pressure and temperatures up to 100°C. Experimental electrolytic reaction of aqueous salt solution carried out inside a sealed 300-mL batch autoclave showed that; accumulation of hydrogen gas, oxygen gas and chlorine is highly suppressed under hydrothermal (250°C and 7 MPa) conditions. We have also observed that, when organics are present in the aqueous salt solution being hydrothermally electrolyzed, an effective oxidation of organics is accomplished. Furthermore, for hydrothermal electrolytic oxidation (HEO) with oxygen gas added, experimentally observed TOC removal profile demonstrates apparent anodic oxidation electrical current efficiency of almost 200% for highconcentrated acetic acid solutions.     

ICP光源中载气压力对等离子体辐射强度的影响

为了提高ICP光源等离子体的辐射强度,利用常规同心气动雾化器,增大载气压力,提高样品溶液的雾化效率,并且通过释放掉部分气溶胶的方法,以合适的流速将样品送入等离子体焰。经过测量水样品中元素Ca,Si,Sr和Zn的谱线强度表明,在常规条件下载气压力为0.05 MPa时有谱线峰值强度;当释放掉部分气溶胶以后,在0.07 MPa的载气压力下测得的峰值强度分别提高了38%,79%,45%和70%。另外,使用较高的载气压力并不影响等离子体辐射的稳定性。     

24 ℃和0.1～900 MPa压力下乙醇的拉曼光谱研究

在24 ℃和0.1～900 MPa压力下测量了含50%水的乙醇溶液和纯乙醇的激光拉曼光谱。研究结果表明,纯乙醇和50%乙醇溶液中的C—H基团振动波数均随压力的增大而增大,它们的各振动峰与压力的关系分别为： 纯乙醇： ν₁=2 881.890+0.001 27 P+6.213×10-6 P2;ν₂=2 928.707+0.004 38 P+4.772×10-6 P2;ν₃=2 973.457+0.008 89 P+3.245×10-6 P2;50%乙醇溶液： ν₁ =2 885.616+0.010 8 P-2.699×10-6 P2;ν₂ =2 932.734+0.013 7 P-3.346×10-6 P2;ν₃ =2 978.115+0.016 5 P-4.914×10-6 P2。另外,还观察到在低于550 MPa压力范围,50%乙醇溶液中的氢键强度随压力的增大而明显增加,550 MPa以上压力时不再随压力而发生变化。     

The variability of times to detect growth from individual Clostridium botulinum type E endospores is differentially affected by high pressure treatments

High pressure thermal (HPT) processing is a candidate technology for the production of safe and stable food. However, little is known about the effect of HPT or high hydrostatic pressure (HHP) treatments at ambient temperature on the variability of times to detect growth from individual spores. We investigated this effect by treating Clostridium botulinum type E spores with HHP (200–600?MPa, 20°C) and HPT (600?MPa, 80°C and 800?MPa, 60°C). Our results indicate that the mean detection times increase and the frequency distribution shifts toward longer times when HHP treatment intensity is increased. HPT treatments result in a highly scattered distribution. In contrast, pressure levels ≤300?MPa decrease detection times and heterogeneity of their distribution, which could lead to an increase in the potential risk originating from C. botulinum type E spores. Data provided here could help to refine risk assessment regarding this important food intoxicator.     

水性质的不连续证据:高温高压下水的红外光谱研究

在温度 35～ 35 0℃、压力 1 7～ 2 7GPa下用水热金刚石压腔进行了水的红外光谱测量和研究。研究结果表明 :在低于 2 1GPa时水的伸缩振动吸收峰的频率及半高宽分别随着压力增大而增高和减小 ,且在2 1GPa的压力存在着不连续 ,即随着压力的增大和在 2 1GPa压力下水的吸收峰具有明显和不连续的变化。这表明水在高压下的性质是不连续的 ,并与高压下纯水和NaCl溶液的电导率存在不连续的现象一致 ,也与含水矿物叶蜡石和蛇纹石在 2 0GPa处的脱水温度与压力的关系发生逆转现象一致。水的这种不连续性将对岩石圈中的矿物或岩石起重要作用 ,需要进行进一步的研究。     

Hydrostatic pressure effects on the fluorescence of tyrosine solution with different concentrations of copper ion

The effects of hydrostatic pressure on the fluorescence of tyrosine (Tyr) solution with different concentrations of copper ion (Cu²⁺) were investigated. The fluorescent intensity of pure Tyr aqueous solution enhanced with the increase of hydrostatic pressure, the fluorescent intensity increased by 8.8% when the pressure was up to 60 MPa. The fluorescence of Tyr aqueous solution was quenched obviously due to complex formation with Cu²⁺ and the quenching became stronger when the concentration of Cu²⁺ was higher. When the concentration ratio of Cu²⁺ and Tyr ([Cu²⁺]/[Tyr]) increased from 0 to 40, the fluorescent intensity decreased to 19.0% at 0.1 MPa and 24.2% at 60 MPa. It was also found that the effects of pressure on the fluorescent intensity of Tyr aqueous solution were different at various [Cu²⁺]/[Tyr]. The fluorescent intensity increased by 14.4% and 38.4% for 1 and 40 ratio respectively when the pressure was changed from 0.1 MPa to 60 MPa.     

Effect of high pressure on cod (Gadus morhua) desalting

The effect of high pressure on salt and water diffusion in the desalting process of cod was studied. Under pressure, up to 300 MPa, the osmotic equilibrium is reached much faster, compared to desalting at atmospheric pressure. Water (D _ew) and salt (D _es) effective diffusion coefficients reached a maximum at 200 MPa, increasing 500- and 160-fold, respectively, compared with desalting at atmospheric pressure. Increasing pressure up to 300 MPa causes a reduction in both effective diffusion coefficients, although they were still about 70-fold higher than at atmospheric pressure. Up to 200 MPa, a linear correlation was found between D _ew and D _es and pressure. However, the total diffused amounts of water and salt, when the osmotic equilibrium was reached, were lower under pressure. At atmospheric pressure cod water content increased 1.65-fold, but under pressure the increment was on average 1.25-fold, while salt content decreased to 0.51-fold the initial value at atmospheric pressure and to around 0.75-fold under pressure.     

Poly(o-anisidine) coatings on brass: Synthesis,characterization and corrosion protection

Poly(o-anisidine) (POA) coatings were synthesized on brass by electrochemical polymerization of o-anisidine in aqueous salicylate solution by using cyclic voltammetry. These coatings were characterized by cyclic voltammetry, UV–visible absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The corrosion protection aspects of POA coatings on brass in aqueous 3% NaCl solution were investigated by potentiodynamic polarization technique and electrochemical impedance spectroscopy (EIS). The potentiodynamic polarization measurements show that the POA coating has ability to protect the brass against corrosion. The corrosion potential was about 0.204 V versus SCE more positive for the POA coated brass than that of uncoated brass and reduces the corrosion rate of brass almost by a factor of 800. The corrosion behavior of the POA coatings was also investigated by EIS through immersion tests performed in aqueous 3% NaCl solution. The evolution of the impedance parameters with the immersion time was studied and the results show that the POA acts as a protective coating on brass against corrosion in 3% NaCl solution. The water uptake and delamination area were also determined to further support the corrosion protection performance of the POA coating.     

一种高压光学样品池系统的设计与实验研究

设计和研制了一种用于溶液样品光学特性原位检测的高压光学样品池成套系统,组件包括手动泵、增压器和高压样品池。其中样品池开有3处光学窗口,以水为传压介质,设计的最高使用压力为600MPa。当用JGS1石英作窗口时,密封和保压效果良好;由于受到石英材质强度的限制,使用压力应控制在300MPa以下。为检验该系统在高压原位检测方面应用的可行性,进行了色氨酸高压荧光光谱的采集。