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291.
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   
292.
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   
293.
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   
294.
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   
295.
    
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   
296.
    
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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299.
    
Predicting the stereochemical outcome of chemical reactions is challenging in mechanistically ambiguous transformations. The stereoselectivity of glycosylation reactions is influenced by at least eleven factors across four chemical participants and temperature. A random forest algorithm was trained using a highly reproducible, concise dataset to accurately predict the stereoselective outcome of glycosylations. The steric and electronic contributions of all chemical reagents and solvents were quantified by quantum mechanical calculations. The trained model accurately predicts stereoselectivities for unseen nucleophiles, electrophiles, acid catalyst, and solvents across a wide temperature range (overall root mean square error 6.8%). All predictions were validated experimentally on a standardized microreactor platform. The model helped to identify novel ways to control glycosylation stereoselectivity and accurately predicts previously unknown means of stereocontrol. By quantifying the degree of influence of each variable, we begin to gain a better general understanding of the transformation, for example that environmental factors influence the stereoselectivity of glycosylations more than the coupling partners in this area of chemical space.

A random forest algorithm, trained on a concise dataset and validated experimentally, accurately predicts the stereoselectivity of a complex organic coupling varying all reaction parameters as well as previously unknown mechanistic influences.  相似文献   
300.
    
Smoke taint has become a prominent issue for the global wine industry as climate change continues to impact the length and extremity of fire seasons around the world. Although the issue has prompted a surge in research on the subject in recent years, no singular solution has yet been identified that is capable of maintaining the quality of wine made from smoke-affected grapes. In this review, we summarize the main research on smoke taint, the key discoveries, as well as the prevailing uncertainties. We also examine methods for mitigating smoke taint in the vineyard, in the winery, and post production. We assess the effectiveness of remediation methods (proposed and actual) based on available research. Our findings are in agreement with previous studies, suggesting that the most viable remedies for smoke taint are still the commercially available activated carbon fining and reverse osmosis treatments, but that the quality of the final treated wines is fundamentally dependent on the initial severity of the taint. In this review, suggestions for future studies are introduced for improving our understanding of methods that have thus far only been preliminarily investigated. We select regions that have already been subjected to severe wildfires, and therefore subjected to smoke taint (particularly Australia and California) as a case study to inform other wine-producing countries that will likely be impacted in the future and suggest specific data collection and policy implementation actions that should be taken, even in countries that have not yet been impacted by smoke taint. Ultimately, we streamline the available information on the topic of smoke taint, apply it to a global perspective that considers the various stakeholders involved, and provide a launching point for further research on the topic.  相似文献   
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