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291.
The time-dependent changes which are observed in the infrared and Raman spectra of samples of the two Hofmann aniline clathrates M(NH3)2Ni(CN)4.an2 {M = Cd(II), Ni(II), an = C6H5NH2} indicate the occurrence of a solid state ligand replacement reaction in which the aniline guest molecule replaces the coordinated ammonia to give Man2Ni(CN)4 as the final product. The rate of replacement is greater for the cadmium than for the nickel clathrate, and for both clathrates evacuation of the sample greatly increases the rate of replacement. The Man2Ni(CN)4 complexes can themselves act as host lattices forming clathrates containing guest molecules such as aniline.  相似文献   
292.
Summary The solid phase synthesis of libraries containing a 1,3,4,6-tetrasubstituted-2,5-diketo-1,4-piperazine scaffold (DKP) or a 3,4,6-trisubstituted-2,5-diketo-1,4-morpholme scaffold (DKM) from -bromocarboxylic acids and amines is described. Using a design strategy which we refer to as divergent library design, both templates were prepared from a common intermediate. The general utility of this synthetic route in creating novel, non-peptidyl chemical libraries is discussed.  相似文献   
293.
We present experimental evidence of the optical spring effect in a silica microtoroid resonator. The variation of the measured mechanical resonant frequency as a function of optical power, optical coupling, and optical detuning is in very good agreement with a model for radiation-pressure-induced rigidity in a silica microtoroid.  相似文献   
294.
Quantitative analysis of genetically modified (GM) foods requires estimation of the amount of the transgenic event relative to an endogenous gene. Regulatory authorities in the European Union (EU) have defined the labelling threshold for GM food on the copy number ratio between the transgenic event and an endogenous gene. Real-time polymerase chain reaction (PCR) is currently being used for quantification of GM organisms (GMOs). Limitations in real-time PCR applications to detect very low number of DNA targets has led to new developments such as the digital PCR (dPCR) which allows accurate measurement of DNA copies without the need for a reference calibrator. In this paper, the amount of maize MON810 and hmg copies present in a DNA extract from seed powders certified for their mass content and for their copy number ratio was measured by dPCR. The ratio of these absolute copy numbers determined by dPCR was found to be identical to the ratios measured by real-time quantitative PCR (qPCR) using a plasmid DNA calibrator. These results indicate that both methods could be applied to determine the copy number ratio in MON810. The reported values were in agreement with estimations from a model elaborated to convert mass fractions into copy number fractions in MON810 varieties. This model was challenged on two MON810 varieties used for the production of MON810 certified reference materials (CRMs) which differ in the parental origin of the introduced GM trait. We conclude that dPCR has a high metrological quality and can be used for certifying GM CRMs in terms of DNA copy number ratio.  相似文献   
295.
Recent studies have demonstrated the ability to detect images based on intermolecular multiple-quantum coherences (iMQCs) that correspond to flipping of two or more separated spins simultaneously, as opposed to conventional magnetic resonance where only one spin is flipped at a time. Until now, iMQC imaging has only acquired one coherence signal per pulse sequence. Here we report a new sequence that successfully detects five orders of coherence (2, 1, 0, −1, and −2-quantum coherence images) in one pulse sequence, with each signal having its full intensity. The simultaneous acquisition highlights substantial contrast differences between conventional and iMQC images, and between the different types of iMQC images.  相似文献   
296.
Heavy water detection using ultra-high-Q microcavities   总被引:1,自引:0,他引:1  
Armani AM  Vahala KJ 《Optics letters》2006,31(12):1896-1898
Ultra-high-Q optical microcavities (Q>10(7)) provide one method for distinguishing chemically similar species. Resonators immersed in H(2)O have lower quality factors than those immersed in D(2)O due to the difference in optical absorption. This difference can be used to create a D(2)O detector. This effect is most noticeable at 1,300 nm, where the Q(H(2)O) is 106 and the Q(D(2)O) is 107. By monitoring Q, concentrations of 0.0001% [1 part in 106 per volume] of D(2)O in H(2)O have been detected. This sensitivity represents an order of magnitude improvement over previous techniques. Reversible detection was also demonstrated by cyclic introduction and flushing of D(2)O.  相似文献   
297.
We analyze experimentally and theoretically mechanical oscillation within an optical cavity stimulated by the pressure of circulating optical radiation. The resulting radio frequency cavity vibrations (phonon mode) cause modulation of the incident, continuous-wave (cw) input pump beam. Furthermore, with increasing cw pump power, an evolution from sinusoidal modulation to random oscillations is observed in the pump power coupled from the resonator. The temporal evolution with pump power is studied, and agreement was found with theory. In addition to applications in quantum optomechanics, the present work suggests that radiation-pressure-induced effects can establish a practical limit for the miniaturization of optical silica microcavities.  相似文献   
298.
Effects of imposing a sinusoidal acoustic and visual forcing function at various frequencies onto an EEG process are examined in terms of various indices of the nonlinear dynamics. Conjoint use of four methods of data analysis; Lyapunov exponents, the entropic analogue of the Schwarzian derivative, surrogate distributions, and higher-order kernel analyses in the time domain, is illustrated. Local epochs with unstable dynamics are identifed on very short series.  相似文献   
299.
    
When bushfires occur near wine regions, grapevine exposure to smoke can taint grapes due to the uptake of smoke-derived volatile compounds that can subsequently impart unpleasant smoky, medicinal, burnt rubber and ashy characters to wine. Whereas early research sought to understand the effects of smoke on grapevine physiology, and grape and wine chemistry, research efforts have shifted towards the strategic imperative for effective mitigation strategies. This study evaluated the extent to which excised grape bunches could be reproducibly tainted during smoke exposure in a purpose-built ‘smoke box’. The volatile phenol composition of grapes exposed to smoke for 30 min was similar to that of smoke-affected grapes from field trials involving grapevine exposure to smoke. Some variation was observed between replicate smoke treatments, but implementing appropriate controls and experimental replication enabled the smoke box to be used to successfully evaluate the efficacy of several agrochemical sprays and protective coverings as methods for mitigating the smoke exposure of grapes. Whereas the agrochemical sprays did not provide effective protection from smoke, enclosing grape bunches in activated carbon fabric prevented the uptake of up to 98% of the smoke-derived volatile phenols observed in smoke-affected grapes. As such, the study demonstrated not only a convenient, efficient approach to smoke taint research that overcomes the constraints associated with vineyard-based field trials, but also a promising new strategy for preventing smoke taint.  相似文献   
300.
    
The stereoselective formation of 1,2‐cis‐glycosidic bonds is challenging. However, 1,2‐cis‐selectivity can be induced by remote participation of C4 or C6 ester groups. Reactions involving remote participation are believed to proceed via a key ionic intermediate, the glycosyl cation. Although mechanistic pathways were postulated many years ago, the structure of the reaction intermediates remained elusive owing to their short‐lived nature. Herein, we unravel the structure of glycosyl cations involved in remote participation reactions via cryogenic vibrational spectroscopy and first principles theory. Acetyl groups at C4 ensure α‐selective galactosylations by forming a covalent bond to the anomeric carbon in dioxolenium‐type ions. Unexpectedly, also benzyl ether protecting groups can engage in remote participation and promote the stereoselective formation of 1,2‐cis‐glycosidic bonds.  相似文献   
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