不同方法制备的CO2-3替换磷灰石固溶体晶体化学的FTIR研究

采用不同方法制备了CO2-3替换的磷灰石固溶体,利用FTIR结合XRD对其进行了晶体化学研究,结果表明均相沉淀法制备的碳羟磷灰石(CHAP)属B型替换且替换方式是[CO3·OH]四面体替换[PO4]四面体;固相离子交换法制备的CHAP属A型替换且替换方式是[CO3]三角形配位体替换通道位置的OH-;固相反应法制备的碳氟磷灰石(CFAP)属B型替换,其替换方式是[CO3·F]四面体替换[PO4]四面体;sol-gel法制备的CHAP属AB混合型替换,其Ψ3分裂为Ψ3-1,Ψ3F,Ψ3-4.高斯函数法拟合表明Ψ3F峰是A型替换的Ψ3-2与B型替换的Ψ3-3的叠合.当WCO2-3＜3.34%时,随CO2-3含量增加,A型替换量增大,且当WCO2-3=3.34%时达最大值,当3.34%＜WCO2-3＜7.52%时,随CO2-3含量增加,B型替换量增大,且当WCO2-3= 7.52%时亦到饱和.     

Low temperature and low pressure CO oxidation on gold clusters supported on MgO(100)

CO oxidation has been investigated on Au/MgO(100) model catalysts at RT and low pressure. The gold particles prepared by UHV evaporation on clean MgO surfaces are characterized by HRTEM. The gold particles are FCC single crystals or multiple twins with five-fold symmetry. Infrared spectroscopy indicates that two types of adsorption sites are present which correspond to loosely and strongly bound CO. The equilibrium CO coverage for the strongly bound CO is smaller than 0.1 ML. CO titration experiments show that oxygen does not dissociate on the gold nanoparticles. The CO oxidation reaction is studied at RT by molecular beam methods. A steady state CO reaction probability up to 0.50 is measured, for the first time at low pressure, for gold particles with a mean size of 1.5 nm. A reaction mechanism is proposed in which CO adsorbed on low coordinated gold atoms reacts with oxygen adsorbed molecularly, possibly at the Au/MgO interface.     

Synthesis of Pt modified ZSM-5 and beta zeolite catalysts: influence of ultrasonic irradiation and preparation methods on physico-chemical and catalytic properties in pentane isomerization

Influence of preparation methods and ultrasound irradiation on physico-chemical and catalytic properties was investigated by synthesizing Pt-ZSM-5 and Pt-Beta catalysts by in-situ and impregnation methods and applying ultrasound irradiation to synthesis gel mixture of ZSM-5 and Beta zeolites. It was concluded from the X-ray powder diffraction patterns of Pt-ZSM-5 and Pt-Beta zeolite catalysts that introduction of Pt by in-situ method and ultrasound irradiation did not influence the structures of ZSM-5 and Beta zeolites. Morphology of ZSM-5 and Beta zeolites were investigated by scanning electron microscopy. SEM micrographs showed that the Pt-ZSM-5-IS-US catalyst synthesized by in-situ method with ultrasound irradiation resulted in smaller crystals of ZSM-5 than Pt-ZSM-5-IS catalyst prepared without ultrasound irradiation. Furthermore SEM micrographs of Pt-Beta-11-IS-US zeolite synthesized using ultrasound irradiation showed much smaller crystals than Pt-Beta-11-IM indicating that ultrasound irradiation had a significant effect on the morphology of Beta zeolite. Conversion of n-pentane and selectivity to iso-pentane over the Pt-ZSM-5-IS-US zeolite catalysts prepared by ultrasound irradiation during in-situ introduction of platinum was higher than the catalysts prepared without the ultrasound irradiation. Furthermore ultrasound irradiated and in-situ synthesized Pt-Beta-11-IS-US catalyst also showed higher selectivity to iso-pentane than Pt-H-Beta-11-IM prepared by impregnation method.     

Ultrasound responsive carbon monoxide releasing micelle

Carbon monoxide (CO), an endogenously produced gasotransmitter, has shown various therapeutic effects in previous studies. In this work, we developed an ultrasound responsive micelle for localized CO delivery. The micelle is composed of a pluronic shell and a core of a CO releasing molecule, CORM-2. The mechanism is based on the ultrasound response of pluronics, and the reaction between CORM-2 and certain biomolecules, e.g. cysteine. The latter allows CO release without significantly breaking the micelles. In a 3.5 mM cysteine solution, the micelles released low level of CO, indicating effective encapsulation of CORM-2. Treatment with a low intensity, non-focused ultrasound led to four times as much CO as the sample without ultrasonication, which is close to that of unencapsulated CORM-2. Significantly reduced proliferation of prostate cancer cells (PC-3) was observed 24 h after the PC-3 cells were treated with the CORM-2 micelles followed by ultrasound activation.     

Synthesis of 1,5-dinitroaryl-1,4-pentadien-3-ones under ultrasound irradiation

1,5-Dinitroaryl-1,4-pentadien-3-ones were synthesized with ultrasound irradiation in the presence of K(2)CO(3) as catalyst. The reaction mechanism and the factors influencing the product were also discussed. The present procedure is more convenient with shorter reaction time and higher yields compared with conventional methods.     

Selective hydrogenation of furfural to furfuryl alcohol over catalysts prepared via sonochemistry

Copper-chromite oxide and TiO2-supported copper-chromite oxide catalysts are prepared by various methods. They are characterized with ICP, BET, XRD, XPS, SEM, and TEM, etc. Their catalytic performance for liquid phase hydrogenation of furfural to furfuryl alcohol is also valuated. The catalysts prepared by ultrasound exhibit good performance. Catalytic activity of TiO2-supported catalysts is higher than that of catalyst without TiO2, notwithstanding they are all prepared by ultrasound. It is worth stressing that after reduced the TiO2-supported catalysts, which are X-ray amorphous, display good performance at 140 degrees C, while the catalysts without TiO2 show no activity under the same condition. Obtained results indicate that the catalytic performance of catalysts depends upon the amount of reducible copper ions and the activity decay is related to the loss of metal elements on the surface of catalyst.     

Dose-dependent inhibition of ultrasound-induced cell killing and free radical production by carbon dioxide

Previous studies have shown that if a solution for cell suspension is saturated with CO(2), ultrasound-induced in vitro cell killing and free-radical production are inhibited. However, the dose dependency of this observation has not been explored. Here, we used NaHCO(3) and HCl to produce a predictable concentration of CO(2) within the culture medium. Using 1 MHz continuous wave 4 W/cm(2) ultrasound, we sonicated U937 cells suspension for 1 min at 37 degrees C with CO(2) at different concentrations. At 2 mM, reduced cell killing was observed that further decreased with increasing CO(2) concentration until 100% protection was attained at 20 mM. Ultrasound-induced free-radical production was significantly decreased at 1 mM and became undetectable at 2 mM CO(2). This finding shows that CO(2)-mediated inhibition is concentration dependent and that the threshold for free-radical production is one order of magnitude higher than the threshold for cell killing induced by ultrasound. In addition, it also cautions researchers when adding acids and acid-based agents to a culture medium, which almost always contains NaHCO(3), in experiments related to the bioeffects of ultrasound.     

纳米薄膜合金电极上二氧化碳电催化还原的红外光谱研究

运用电化学循环伏安和原位ＦＴＩＲ反射光谱，研究ＣＯ２的电催化还原过程。结果表明，纳米薄膜合金材料Ｓｂ－Ｐｂ－Ｐｔ／ＧＣ对ＣＯ２还原具有较高的活性。还原产物以小分子羧酸和伯醇为主。     

Effects of ultrasound on apoptosis induced by anti-CD20 antibody in CD20-positive B lymphoma cells

AIM: The present study was conducted to examine the thermal and non-thermal effects of ultrasound on apoptosis induced by anti-CD20 monoclonal antibody (rituximab). MATERIALS AND METHODS: SU-DHL-4 cells, a CD20-positive cell line derived from B cell lymphomas with a BCL2 gene rearrangement, were exposed to continuous 1 MHz ultrasound for therapeutic use under an air- or CO(2)-saturated condition to control cavitation. Early apoptosis (EA) and secondary necrosis (SN) were examined by flow cytometry. Cavitation was determined by detecting the hydroxyl radicals derived from pyrolysis of water molecules using electron paramagnetic resonance-spin trapping. To assess thermal effects, cells were treated in a temperature-controlled water bath. RESULTS: There was a significant additive increase in EA and EA+SN observed in cells treated with rituximab combined with heat at 42 degrees C or non-thermal ultrasound at 0.5 W/cm(2) under an air-saturated condition, where heat or ultrasound induced some cell death. A significant synergistic increase in EA and EA+SN was observed in cells treated with rituximab and ultrasound at 2.5 W/cm(2) under CO(2)-saturated conditions, where inertial cavitations were completely suppressed. No enhancement was observed at a temperature less than 40 degrees C or ultrasound at 0.5 W/cm(2) under CO(2)-saturated conditions. CONCLUSION: These results suggest that the immuno-therapeutic application of ultrasound at relatively high-intensities combined with rituximab thus produces synergistic effects under conditions where the non-thermal and non-cavitational effects are predominant.     

Sono-synthesis and characterization of bimetallic Ni–Co/Al2O3–MgO nanocatalyst: Effects of metal content on catalytic properties and activity for hydrogen production via CO2 reforming of CH4

Sono-dispersion of Ni, Co and Ni–Co over Al₂O₃–MgO with Al/Mg ratio of 1.5 was prepared and tested for dry reforming of methane. The samples were characterized by XRD, FESEM, PSD, EDX, TEM, BET and FTIR analyses. In order to assess the effect of ultrasound irradiation, Ni–Co/Al₂O₃–MgO with Co content of 8% prepared via sonochemistry and impregnation methods. The sono-synthesized sample showed better textural properties and higher activity than that of impregnated one. Comparison of XRD patterns indicated that the NiO peaks became broader by increasing Co content over the support. The FESEM images displayed the particles are small and well-dispersed as a result of sonochemistry method. Also, EDX analysis demonstrated better dispersion of Ni and Co as a result of sonochemistry method in confirmation of XRD analysis. The sono-synthesized Ni–Co/Al₂O₃–MgO as a superior nanocatalyst with Co content of 3% illustrates much higher conversions (97.5% and 99% for CH₄ and CO₂ at 850 °C), yields (94% and 96% for H₂ and CO at 850 °C) and 0.97 of H₂/CO molar ratio in all samples using an equimolar feed ratio at 850 °C. During the 1200 min stability test, H₂/CO molar ratio remained constant for the superior nanocatalyst.     

Gas jets as ultrasonic waveguides

The study of the propagation of ultrasound within a gas jet is extended to obtain waveguide effects, where the jet collimates the ultrasonic beam from a transducer within the flow. Two methods have been investigated to achieve this--cooling the gas within the air jet, and using a different gas whose acoustic velocity is lower than air. Cooling an air jet to a temperature less than that of the surrounding air produced a noticeable waveguide effect. In addition, studies have been carried out using other selected gases, such as carbon dioxide (CO2) with a lower acoustic velocity than air, and helium (He) with a higher value. The former gas enhanced confinement of the ultrasonic beam, whereas the latter caused divergence. An ideal solution was found to be a CO2/air mixture, which produced a well-collimated sound field along the axis, while limiting the excess attenuation of pure CO2 gas jets. The effectiveness of the waveguide using mixed gas jets in producing images in air-coupled testing of solids is demonstrated.     

Cu/HMOR催化二甲醚羰基化合成乙酸甲酯: 催化剂制备方法的影响 (cited: 2)

采用氨蒸发法、尿素水解法、离子交换法及浸渍法制备HMOR负载的Cu催化剂, 考察其催化二甲醚(DME)羰基化合成乙酸甲酯(MA)性能. 结果表明离子交换法制得Cu/HMOR催化剂在Cu的金属中心和酸性分子筛载体的共同作用下具有较好催化反应活性. 在210 oC、1.5 MPa、空速4883 h^-1,DME转化率为95.3%,MA选择性为94.9%. 对催化剂进行N2物理吸附、X射线衍射、NH₃程序升温脱附和CO程序升温脱附等表征发现,离子交换法制得Cu/HMOR催化剂具有较高比表面、大量弱酸及一定中强酸、适中的CO吸附强度,提高了CO插入DME羰基化反应活性.     

Ultrasound assisted co-precipitation synthesis and catalytic performance of mesoporous nanocrystalline NiO-Al2O3 powders

Mesoporous nanocrystalline NiO-Al₂O₃ powders with high surface area were synthesized via ultrasound assisted co-precipitation method and the potential of the selected samples as catalyst was investigated in dry reforming reaction for preparation of synthesis gas. The prepared samples were characterized by N₂ adsorption (BET), X-ray diffraction (XRD), Temperature programmed reduction and oxidation (TPR, TPO) and scanning electron microscopy (SEM) techniques. The effects of pH, power of ultrasound irradiation, aging time and calcination temperature on the textural properties of the catalysts were studied. The sample prepared under specified conditions (pH10, 70 W, without aging time and calcined at 600 °C) exhibited the highest surface area (249.7 m² g⁻¹). This catalyst was calcined at different temperature and employed in dry reforming of methane and the catalytic results were compared with those obtained over the catalysts prepared by impregnation and co-precipitation methods. The results showed that the catalyst prepared by ultrasound assisted co-precipitation method exhibited higher activity and stability with lower degree of carbon formation compared to catalysts prepared by co-precipitation and impregnation methods.     

Insight into the synthesis procedure of Fe3+/TiO2-based photocatalyst applied in the selective photo-oxidation of benzyl alcohol under sun-imitating lamp

Fe³⁺/TiO₂/zeolite Y photocatalyst synthesized by using sonophotodeposition method was compared with photocatalysts prepared by simple photodeposition and sonodeposition methods in order to clarify the role of light irradiation and ultrasounds while they are used simultaneously. To gain an insight into the mechanism of this method a detailed characterization of the photocatalysts was carried out by means of the following techniques: UV–vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, Mössbauer measurements and photocatalytic test reaction. Basing on the results from these techniques the chemical role of light and mainly mechanical role of ultrasound were observed. The selective photocatalytic oxidation of benzyl alcohol into benzaldehyde in liquid phase was a test reaction verifying the utility of the prepared materials. The best photocatalytic efficiency in this reaction was performed by photocatalyst synthesized using compilation of ultrasound energy with photoexcitation.     

Ultrasound assisted supercritical fluid extraction of oil and coixenolide from adlay seed

Oil and coixenolide are important components of adlay seed (Coix lachrymal-jobi L. var. Adlay) with many beneficial functions to human health. In this work, a novel extraction technique--ultrasound assisted supercritical fluid extraction (USFE)--was studied. Effects of operating conditions on the extraction, including extraction temperature (T), pressure (P), time (t), CO(2) flow rate (F) and ultrasonic power (I) were investigated. There are optimum temperatures which gives the maximum extraction yields (EYs) for the supercritical fluid extractions with and without ultrasound. The effect of pressure on EYs for is similar to that of pressure on CO(2) density. Based on the yield of extraction, the favorable conditions for supercritical fluid extraction (SFE) were: T at 45 degrees C, P at 25 MPa, t at 4.0 h and F at 3.5L/h. While ultrasound was applied as in USFE, the following parameters were preferred: T at 40 degrees C, P at 20 MPa, t at 3.5h and F at 3.0 L/h, respectively. The results show that supercritical fluid extraction with the assistance of ultrasound could reduce the temperature, pressure, CO(2) flow rate, as well as time used in the process. Compared with SFE, USFE could give a 14% increase in the yield for extracting oil and coixenolide from adlay seed with less severe operating conditions.     

Interaction of oxygen and CO with thin Ag films at AgTi2 substrates

Clean Ag overlayers with a thickness of about three atomic layers are prepared at polycrystalline AgTi₂ surfaces. Adsorption of oxygen and CO at these overlayers is studied with AES, UPS, and TDS methods. UP spectra reveal that oxygen adsorbs dissociatively on the surface of the Ag overlayers at 120 K, similar as at the surfaces of bulk Ag crystals. At higher temperatures, O atoms diffuse into the overlayer and get trapped at Ti at the interface underneath the Ag layer. Unlike at bulk Ag, oxygen adsorption proceeds with high sticking probability, which is attributed to a reduced activation barrier. CO adsorbs at the Ag overlayers in a weakly chemisorbed state with an adsorption energy of ca. 9 kcal/mol, whereas at bulk Ag true physisorption has been observed. Accordingly, UP spectra of CO adsorbed at 120 K exhibit well separated 4σ, 1π and 5σ emission peaks at energetic positions which are essentially different from the CO/Ag physisorption system. This observation is interpreted as a demonstration of the ligand effect, i.e., the activation of weak CO bonding at Ag by strong bonding Ti.     

超声动态向量血流成像的产品化实现

传统超声彩色多普勒成像测量的是血流沿超声传播方向上的速度分量,故无法得到垂直于超声传播方向的血流。向量血流成像是一种更加先进的超声血流成像技术。它不受角度限制,可以直接计算出血流速度的大小和方向。本文总结了现有多种超声向量血流成像技术的特点和发展情况,并从产品化实现的角度分析了各项技术的优缺点。从超声系统发射接收、血流成像、向量速度方向合成、显示等几个方面详述了迈瑞超声向量血流成像技术产品化实现过程中遇到的主要问题及解决方案。实验采用了中科院声学所研制的超声多普勒仿血流体模,通过向量血流成像和脉冲多普勒成像分别测量体模的仿血流速度。将向量血流成像直接计算出来的速度值与脉冲多普勒经过角度校正得到的速度进行对比。在不同条件下,经过多次测量,二者的平均相对误差均在10%以内。     

Preparation of polyacrylamide and gamma-zirconium phosphate nanocomposites by intercalative polymerization

A new inorganic-organic nanocomposite of polyacrylamide (PAM) and gamma-zirconium phosphate (gamma-ZrP) was prepared by intercalative polymerization. Intercalation of acrylamide (AM) monomer in gamma-ZrP was investigated by sonochemical and refluxing methods. High-intensity ultrasound does not induce the polymerization of AM but enhances greatly the intercalation rate. On the other hand, ultrasound also enhanced hydrolyzation of -CONH2 and shrinkage of PAM gel. The interlayer distance of AM-intercalated gamma-ZrP is 16.4 A. The polymerization and intercalation of AM occurred nearly at the same time by refluxing method. The same gamma-ZrP/PAM nanocomposites were obtained with (NH4)2S2O8 treatment.     

Use of ultrasound for the determination of flour quality

Within the baking industry, the control of dough properties is required to achieve final product quality and consistency. Traditional methods for dough testing are slow and off-line and do not provide fundamental rheological information. There is therefore a need for the development of fast and on-line instruments capable of providing relevant data for baking. Ultrasonics provide a non-destructive, rapid and low cost technique for the measurement of physical food characteristics.In this work, the water content of dough is investigated using ultrasonic techniques. The capability of ultrasound measurements for discriminating flours for different purposes is also studied. Doughs from more than 30 flours were characterised rheologically using a Chopin Alveograph and a Brabender Extensograph. Ultrasound measurements on the doughs prepared from these flours were also performed. The measurements were correlated, showing that ultrasound was an alternative measurement method to discriminate types of flours for different purposes.     

Ultrasound-assisted dextranase entrapment onto Ca-alginate gel beads

In this research work, dextranase has immobilized onto calcium alginate beads using a novel ultrasound method. The process of immobilization of the enzyme was carried out in a one-step ultrasound process. Effects of ultrasound conditions on loading efficiency and immobilization yield of the enzyme onto calcium alginate beads were investigated. Furthermore, the activity of the free and immobilized enzymes prepared with and without ultrasound treatment, as a function of pH, temperature, recyclability and enzyme kinetic parameters, was compared. The maximum loading efficiency and the immobilization yield were observed when the immobilized dextranase was prepared with an ultrasonic irradiation at 25 kHz, 40 W for 15 min, under which the loading efficiency and the immobilization yield increased by 27.21% and 18.77%, respectively, compared with the immobilized enzymes prepared without ultrasonic irradiation. On the other hand, immobilized enzyme prepared with ultrasonic irradiation showed V_max and K_M value higher than that for the immobilized enzyme prepared without ultrasonic irradiation, likewise, both the catalytic and specificity constants of immobilized enzyme prepared with ultrasonic irradiation were higher than that for immobilized enzyme prepared without ultrasound, indicating that, this new ultrasonic method improved the catalytic kinetics activity of immobilized dextranase at all the reaction conditions studied. Compared with immobilized enzyme prepared without ultrasound treatment, the immobilized enzymes prepared with ultrasound irradiation exhibited: a higher pH optimum, optimal reaction temperature, activation energy, and thermal stability, as well as, a higher recyclability, which, illustrating the effectiveness of the sonochemical method. To the best of our knowledge, this is the first report on the effect of ultrasound treatments on the immobilization of dextranase.