The Criegee intermediates are carbonyl oxides postulated to play key roles in the reactions of ozone with unsaturated hydrocarbons; these reactions constitute an important mechanism for the removal of unsaturated hydrocarbons and for the production of OH in the atmosphere. Here, we report the transient infrared (IR) absorption spectrum of the simplest Criegee intermediate CH2OO, produced from CH2I + O2 in a flow reactor, using a step-scan Fourier-transform spectrometer. The five observed bands provide definitive identification of this intermediate. The observed vibrational frequencies are more consistent with a zwitterion rather than a diradical structure of CH2OO. The direct IR detection of CH2OO should prove useful for kinetic and mechanistic investigations of the Criegee mechanism.

Abstract:The rapid and non-destructive monitoring of the canopy leaf nitrogen concentration (LNC) in crops is important for precise nitrogen (N) management. Nowadays, there is an urgent need to identify next-generation bio-physical variable retrieval algorithms that can be incorporated into an operational processing chain for hyperspectral satellite missions. We assessed six retrieval algorithms for estimating LNC from canopy reflectance of winter wheat in eight field experiments. These experiments represented variations in the N application rates, planting densities, ecological sites and cultivars and yielded a total of 821 samples from various places in Jiangsu, China over nine consecutive years. Based on the reflectance spectra and their first derivatives, six methods using different numbers of wavelengths were applied to construct predictive models for estimating wheat LNC, including continuum removal (CR), vegetation indices (VIs), stepwise multiple linear regression (SMLR), partial least squares regression (PLSR), artificial neural networks (ANNs), and support vector machines (SVMs). To assess the performance of these six methods, we provided a systematic evaluation of the estimation OPEN ACCESS Remote Sens. 2015, 7 14940 accuracies using the six metrics that were the coefficients of determination for the calibration (R 2 C) and validation (R 2 V) sets, the root mean square errors of prediction (RMSEP) for the calibration and validation sets, the ratio of prediction to deviation (RPD), the computational efficiency (CE) and the complexity level (CL). The following results were obtained: (1) For the VIs method, SAVI(R1200, R705) produced a more accurate estimation of the LNC than other indices, with R² C, R² V, RMSEP, RPD and CE values of 0.844, 0.795, 0.384, 2.005 and 0.10 min, respectively; (2) For the SMLR, PLSR, ANNs and SVMs methods, the SVMs using the first derivative canopy spectra (SVM-FDS) offered the best accuracy in terms of R² C, R² V, RMSEP, RPD, and CE, at 0.96, 0.78, 0.37, 2.02, and 21.17, respectively; (3) The PLSR-FDS, ANN-OS and SVM-FDS methods yield similar accuracies if the CE and CL are not considered, however, ANNs and SVMs performed better on calibration set than the validation set which indicate that we should take more caution with the two methods for over-fitting. Except PLS method, the performance for most methods did not enhance when the spectrum were operated by the first derivative. Moreover, the evaluation of the robustness demonstrates that SVM method may be better suited than the other methods to cope with potential confounding factors for most varieties, ecological site and growth stage; (4) The prediction accuracy was found to be higher when more wavelengths were used, though at the cost of a lower CE. The findings are of interest to the remote sensing community for the development of improved inversion schemes for hyperspectral applications concerning other types of vegetation. The examples provided in this paper may also serve to illustrate the advantages and shortcomings...

The staphylococcal chromosome cassette (SCC)mec types of 382 hospital-acquired methicillin-resistant Staphylococcus aureus (HA-MRSA) isolates in Taiwan were analysed over a 7-year period (1999-2005). There was an abrupt increase in SCCmec type IV in HA-MRSA during 2005. The molecular epidemiology of a subset (n = 69) of HA-MRSA isolates with SCCmec types III, IV or V was characterised and compared with that of community-acquired MRSA (CA-MRSA) (n = 26, collected during 2005). Pulsed-field gel electrophoresis revealed three major pulsotypes (A, B and C) and 15 minor clones. Pulsotypes B and C, which contained isolates carrying SCCmec types IV and V, respectively, included both CA-MRSA and HA-MRSA isolates. Among 24 toxin genes analysed, five genes had significant differential distribution between CA-MRSA and SCCmec type III HA-MRSA. Furthermore, among SCCmec type IV isolates, the seb gene was detected more commonly in HA-MRSA. Analysis of representative members of the three major pulsotypes by multilocus sequence typing revealed two sequence types (STs), namely ST239 (SCCmecIII) and ST59 (SCCmecIV or SCCmecV). This suggests that ST59:SCCmecIV, which is usually community-acquired, has become an important nosocomial pathogen in the hospital studied.

The simplest Criegee intermediate CH2OO is important in atmospheric chemistry. It has been detected in the reaction of CH2I + O2 with various spectral methods, including infrared spectroscopy; infrared absorption of CH2OO was recorded at resolution 1.0 cm(-1) in our laboratory. We have improved our system and recorded the infrared spectrum of CH2OO at resolution 0.25 cm(-1) with rotational structures partially resolved. Observed vibrational wavenumbers and relative intensities are improved from those of the previous report and agree well with those predicted with quantum-mechanical calculations using the MULTIMODE method on an accurate potential energy surface. Observed rotational structures also agree with the simulated spectra according to theoretical predictions. In addition to derivation of critical vibrational and rotational parameters of the vibrationally excited states to confirm the assignments, the spectrum with improved resolution provides new assignments for bands 2ν9 at 1234.2 cm(-1) and ν5 at 1213.3 cm(-1); some hot bands and combination bands are also tentatively assigned.

The Criegee intermediates are carbonyl oxides that play critical roles in ozonolysis of alkenes in the atmosphere. So far, the mid-infrared spectrum of only the simplest Criegee intermediate CH2OO has been reported. Methyl substitution of CH2OO produces two conformers of CH3CHOO and consequently complicates the infrared spectrum. Here we report the transient infrared spectrum of syn- and anti-CH3CHOO, produced from CH3CHI + O2 in a flow reactor, using a step-scan Fourier-transform spectrometer. Guided and supported by high-level full-dimensional quantum calculations, rotational contours of the four observed bands are simulated successfully and provide definitive identification of both conformers. Furthermore, anti-CH3CHOO shows a reactivity greater than syn-CH3CHOO towards NO/NO2; at the later period of reaction, the spectrum can be simulated with only syn-CH3CHOO. Without NO/NO2, anti-CH3CHOO also decays much faster than syn-CH3CHOO. The direct infrared detection of syn- and anti-CH3CHOO should prove useful for field measurements and laboratory investigations of the Criegee mechanism.