The energy efficiency of formation of photons, radicals and ions during single-bubble cavitation

It is extremely difficult to perform a quantitative analysis of the chemistry associated with multibubble cavitation: unknown parameters include the number of active bubbles, the acoustic pressure acting on each bubble and the bubble size distribution. Single-bubble sonoluminescence (characterized by the emission of picosecond flashes of light) results from nonlinear pulsations of an isolated vapour-gas bubble in an acoustic field. Although the latter offers a much simpler environment in which to study the chemical activity of cavitation, quantitative measurements have been hindered by the tiny amount of reacting gas within a single bubble (typically <10(-13) mol). Here we demonstrate the existence of chemical reactions within a single cavitating bubble, and quantify the sources of energy dissipation during bubble collapse. We measure the yields of nitrite ions, hydroxyl radicals and photons. The energy efficiency of hydroxyl radical formation is comparable to that in multibubble cavitation, but the energy efficiency of light emission is much higher. The observed rate of nitrite formation is in good agreement with the calculated diffusion rate of nitrogen into the bubble. We note that the temperatures attained in single-bubble cavitation in liquids with significant vapour pressures will be substantially limited by the endothermic chemical reactions of the polyatomic species inside the collapsing bubble.     

Plasma formation and temperature measurement during single-bubble cavitation

Single-bubble sonoluminescence (SBSL) results from the extreme temperatures and pressures achieved during bubble compression; calculations have predicted the existence of a hot, optically opaque plasma core with consequent bremsstrahlung radiation. Recent controversial reports claim the observation of neutrons from deuterium-deuterium fusion during acoustic cavitation. However, there has been previously no strong experimental evidence for the existence of a plasma during single- or multi-bubble sonoluminescence. SBSL typically produces featureless emission spectra that reveal little about the intra-cavity physical conditions or chemical processes. Here we report observations of atomic (Ar) emission and extensive molecular (SO) and ionic (O2+) progressions in SBSL spectra from concentrated aqueous H2SO4 solutions. Both the Ar and SO emission permit spectroscopic temperature determinations, as accomplished for multi-bubble sonoluminescence with other emitters. The emissive excited states observed from both Ar and O2+ are inconsistent with any thermal process. The Ar excited states involved are extremely high in energy (>13 eV) and cannot be thermally populated at the measured Ar emission temperatures (4,000-15,000 K); the ionization energy of O2 is more than twice its bond dissociation energy, so O2+ likewise cannot be thermally produced. We therefore conclude that these emitting species must originate from collisions with high-energy electrons, ions or particles from a hot plasma core.     

A colorimetric sensor array for odour visualization

Array-based vapour-sensing devices are used to detect and differentiate between chemically diverse analytes. These systems--based on cross-responsive sensor elements--aim to mimic the mammalian olfactory system by producing composite responses unique to each odorant. Previous work has concentrated on a variety of non-specific chemical interactions to detect non-coordinating organic vapours. But the most odiferous, toxic compounds often bind readily to metal ions. Here we report a simple optical chemical sensing method that utilizes the colour change induced in an array of metalloporphyrin dyes upon ligand binding while minimizing the need for extensive signal transduction hardware. The chemoselective response of a library of immobilized vapour-sensing metalloporphyrin dyes permits the visual identification of a wide range of ligating (alcohols, amines, ethers, phosphines, phosphites, thioethers and thiols) and even weakly ligating (arenes, halocarbons and ketones) vapours. Water vapour does not affect the performance of the device, which shows a good linear response to single analytes, and interpretable responses to analyte mixtures. Unique colour fingerprints can be obtained at analyte concentrations below 2 parts per million, and responses to below 100 parts per billion have been observed. We expect that this type of sensing array will be of practical importance for general-purpose vapour dosimeters and analyte-specific detectors (for insecticides, drugs or neurotoxins, for example).     

Sonoluminescence from non-aqueous liquids

Our understanding of the chemical effects of high-intensity ultrasonic irradiation of liquids is still quite limited. It is generally accepted that sonochemistry results from acoustic cavitation: the creation, growth, and implosive collapse of bubbles in ultrasonically irradiated liquids. The mechanism of sonoluminescence in aqueous systems has been a matter of some dispute; recent discussions have suggested at least three possible origins: black-body emission, chemiluminescence from radical recombination, and electric discharge. Few studies of non-aqueous sonoluminescence, however, have been conducted. We present here the first spectrally resolved sonoluminescence spectra from hydrocarbon and halocarbon liquids. These spectra originate unambiguously from excited-state molecules created during acoustic cavitation. These high-energy species probably result from the recombination of radical and atomic species generated during the high temperatures and pressures of cavitation.     

利用光纤光栅实现压力和温度同时测量

结合光纤光栅弹簧管压力传感器的结构特点 ,在悬臂梁的上下两面分别粘贴两个应力和温度灵敏系数基本相同的光纤光栅 ,通过分别测量光纤光栅对的波长位移 ,实现了压力和温度的同时测量 ,压力和温度测量的分辨率分别为 0 .1 4 MPa和 0 .5℃ .     

Molecular emission from single-bubble sonoluminescence

Ultrasound can drive a single gas bubble in water into violent oscillation; as the bubble is compressed periodically, extremely short flashes of light (about 100 ps) are generated with clock-like regularity. This process, known as single-bubble sonoluminescence, gives rise to featureless continuum emission in water (from 200 to 800 nm, with increasing intensity into the ultraviolet). In contrast, the emission of light from clouds of cavitating bubbles at higher acoustic pressures (multi-bubble sonoluminescence) is dominated by atomic and molecular excited-state emission at much lower temperatures. These observations have spurred intense effort to uncover the origin of sonoluminescence and to generalize the conditions necessary for its creation. Here we report a series of polar aprotic liquids that generate very strong single-bubble sonoluminescence, during which emission from molecular excited states is observed. Previously, single-bubble sonoluminescence from liquids other than water has proved extremely elusive. Our results give direct proof of the existence of chemical reactions and the formation of molecular excited states during single-bubble cavitation, and provide a spectroscopic link between single- and multi-bubble sonoluminescence.     

Synthetic hosts by monomolecular imprinting inside dendrimers

Synthetic host systems capable of selectively binding guest molecules are of interest for applications ranging from separations and chemical or biological sensing to the development of biomedical materials. Such host systems can be efficiently prepared by 'imprinting' polymers or inorganic materials with template molecules, which, upon removal, leave behind spatially arranged functional groups that act as recognition sites. However, molecularly imprinted polymers have limitations, including incomplete template removal, broad guest affinities and selectivities, and slow mass transfer. An alternative strategy for moulding desired recognition sites uses combinatorial libraries of assemblies that are made of a relatively small number of molecules, interconverting in dynamic equilibrium; upon addition of a target molecule, the library equilibrium shifts towards the best hosts. Here we describe the dynamic imprinting of dendritic macromolecules with porphyrin templates to yield synthetic host molecules containing one binding site each. The process is based on our general strategy to prepare cored dendrimers, and involves covalent attachment of dendrons to a porphyrin core, cross-linking of the end-groups of the dendrons, and removal of the porphyrin template by hydrolysis. In contrast to more traditional polymer imprinting, our approach ensures nearly homogeneous binding sites and quantitative template removal. Moreover, the hosts are soluble in common organic solvents and amenable to the incorporation of other functional groups, which should facilitate further development of this system for novel applications.     

Mechanoluminescence: light from sonication of crystal slurries

Mechanoluminescence, also known as triboluminescence or fractoluminescence, is light emission induced as a result of mechanical action on a solid--for example, Francis Bacon noted as long ago as 1605 that lumps of sugar emitted light when scraped. Here we elicit mechanoluminescence by a new means, acoustic cavitation, and find intense luminescence and emission lines that are not generated by other mechanisms such as grinding, cleaving, rubbing, scratching, biting or thermal shock.