Highly efficient ruthenium catalysts for the formation of tetrasubstituted olefins via ring-closing metathesis

[reaction: see text] A series of ruthenium-based metathesis catalysts with N-heterocyclic carbene (NHC) ligands have been prepared in which the N-aryl groups have been changed from mesityl to mono-ortho-substituted phenyl (e.g., tolyl). These new catalysts offer an exceptional increase in activity for the formation of tetrasubstituted olefins via ring-closing metathesis (RCM), while maintaining high levels of activity in ring-closing metathesis (RCM) reactions that generate di- and trisubstituted olefins.     

Optical Sensor for the Determination of Glucose Based on KIO4 Chemiluminescence Detection

A method to determine glucose using an optical sensor prepared by entrapping glucose oxidase into silica sol-gel column has been developed. The silica sol-gel film was coated on alumina substrate. The optical sensor is based on the chemiluminescence intensity from the reaction of periodate and hydrogen peroxide in K2CO3 medium. The effect of the ratio of water and alcohol for the preparation of TEOS sol on chemiluminescence intensity was investigated. The effects of pH of enzyme reactor, concentrations of potassium periodate and SDS, and flow rate on the chemiluminescence intensity were studied to find the optimum experimental conditions to determine glucose. The chemiluminescence intensity increased linearly with increasing glucose concentration from 5.0 x 10(-4) M to 1.0 x 10(-7) M and the detection limit was 4.0 x 10(-8) M. Interference effects from some metal ions on chemiluminescence intensity were also investigated.     

Tunable silver-shell dielectric core nano-beads array for thin-film solar cell application

The absorbance spectra of thin-film solar cells (TFSCs) can be enhanced by constructing the tunable periodic Ag-shell nano-bead (PASNB) arrays in the active material. In this paper, we investigated a plasmonic thin-film solar cell (TFSC) which composed of the arrays of PASNB deposited onto a crystalline silicon layer. By performing three-dimensional finite element method, we demonstrate that near field coupling among the PASNB arrays results in SPR modes with enhanced absorbance and field intensity. The proposed structure can significantly enhance the plasmonic activity in a wide range of incident light and enlarge working wavelength of absorbance in the range of near-UV, visible and near-infrared. We show that the sensitivity of the PASNB arrays reveals a linear relationship with the thickness of Ag-shell nano-bead (ASNB) for both the anti-bonding and bonding modes in the absorbance spectra. The broadband of absorbance spectra could be expanded as a wide range by varying the thickness of ASNB while the particle size is kept constant. Simulation results suggest this alternative scheme to the design and improvements on plasmonic enhanced TFSCs can be extended to other nanophotonic applications.     

Separation of isotropic chemical and second-order quadrupolar shifts by multiple-quantum double rotation NMR

Using a two-dimensional multiple-quantum (MQ) double rotation (DOR) experiment the contributions of the chemical shift and quadrupolar interaction to isotropic resonance shifts can be completely separated. Spectra were acquired using a three-pulse triple-quantum z-filtered pulse sequence and subsequently sheared along both the ν₁ and ν₂ dimensions. The application of this method is demonstrated for both crystalline (RbNO₃) and amorphous samples (vitreous B₂O₃). The existence of the two rubidium isotopes (⁸⁵Rb and ⁸⁷Rb) allows comparison of results for two nuclei with different spins (I = 3/2 and 5/2), as well as different dipole and quadrupole moments in a single chemical compound. Being only limited by homogeneous line broadening and sample crystallinity, linewidths of approximately 0.1 and 0.2 ppm can be measured for ⁸⁷Rb in the quadrupolar and chemical shift dimensions, enabling highly accurate determination of the isotropic chemical shift and the quadrupolar product, P_Q. For vitreous B₂O₃, the use of MQDOR allows the chemical shift and electric field gradient distributions to be directly determined—information that is difficult to obtain otherwise due to the presence of second-order quadrupolar broadening.     

Analysis of Vocal-fold Vibrations from High-Speed Laryngeal Images Using a Hilbert Transform-Based Methodology

This paper presents a Hilbert transform-based approach to analyze vocal fold vibrations in human subjects exhibiting normal and abnormal voice productions. This new approach is applied to the analysis of glottal area waveform (GAW) and is capable of providing useful information on the vocal fold vibration. The GAW is extracted from high-speed laryngeal images by delineating the glottal edge for each image frame. An analytic signal is generated through the Hilbert transform of the GAW, which yields a recognizable pattern of the vocal fold vibration in the analytic phase plane. The vibratory pattern is comprehensive and can be correlated with specific voice conditions. Quantitative measures of the glottal perturbation are introduced using the analytic amplitude and instantaneous frequency obtained from the analysis. Examples of clinical voice recordings are used to evaluate and test the effectiveness of this approach in providing qualitative representation and quantitative characteristics of vocal fold vibratory behavior. The results demonstrate the potential of using this new analytical tool incorporated with the high-speed laryngeal imaging modality for clinical voice assessment.     

Vowel intelligibility in clear and conversational speech for normal-hearing and hearing-impaired listeners

Several studies have demonstrated that when talkers are instructed to speak clearly, the resulting speech is significantly more intelligible than speech produced in ordinary conversation. These speech intelligibility improvements are accompanied by a wide variety of acoustic changes. The current study explored the relationship between acoustic properties of vowels and their identification in clear and conversational speech, for young normal-hearing (YNH) and elderly hearing-impaired (EHI) listeners. Monosyllabic words excised from sentences spoken either clearly or conversationally by a male talker were presented in 12-talker babble for vowel identification. While vowel intelligibility was significantly higher in clear speech than in conversational speech for the YNH listeners, no clear speech advantage was found for the EHI group. Regression analyses were used to assess the relative importance of spectral target, dynamic formant movement, and duration information for perception of individual vowels. For both listener groups, all three types of information emerged as primary cues to vowel identity. However, the relative importance of the three cues for individual vowels differed greatly for the YNH and EHI listeners. This suggests that hearing loss alters the way acoustic cues are used for identifying vowels.     

Contribution of consonant versus vowel information to sentence intelligibility for young normal-hearing and elderly hearing-impaired listeners

The purpose of this study was to examine the contribution of information provided by vowels versus consonants to sentence intelligibility in young normal-hearing (YNH) and typical elderly hearing-impaired (EHI) listeners. Sentences were presented in three conditions, unaltered or with either the vowels or the consonants replaced with speech shaped noise. Sentences from male and female talkers in the TIMIT database were selected. Baseline performance was established at a 70 dB SPL level using YNH listeners. Subsequently EHI and YNH participants listened at 95 dB SPL. Participants listened to each sentence twice and were asked to repeat the entire sentence after each presentation. Words were scored correct if identified exactly. Average performance for unaltered sentences was greater than 94%. Overall, EHI listeners performed more poorly than YNH listeners. However, vowel-only sentences were always significantly more intelligible than consonant-only sentences, usually by a ratio of 2:1 across groups. In contrast to written English or words spoken in isolation, these results demonstrated that for spoken sentences, vowels carry more information about sentence intelligibility than consonants for both young normal-hearing and elderly hearing-impaired listeners.     

Functional Analysis of Voice Using Simultaneous High-Speed Imaging and Acoustic Recordings

We present a comprehensive, functional analysis of clinical voice data derived from both high-speed digital imaging (HSDI) of the larynx and simultaneously acquired acoustic recordings. The goals of this study are to: (1) correlate dynamic characteristics of the vocal folds derived from direct laryngeal imaging with indirectly acquired acoustic measurements; (2) define the advantages of using a combined imaging/acoustic approach for the analysis of voice condition; and (3) identify new quantitative measures to evaluate the regularity of the vocal fold vibration and the complexity of the vocal output -- these measures will be key to successful diagnosis of vocal abnormalities. Image- and acoustic-based analyses are performed using an analytic phase plot approach previously introduced by our group (referred to as 'Nyquist' plot). Fast Fourier Transform (FFT) spectral analyses are performed on the same data for a comparison. Clinical HSDI and acoustic recordings from subjects having normal and specific voice pathologies, including muscular tension dysphonia (MTD) and recurrent respiratory papillomatosis (RRP) were analyzed using the Nyquist plot approach. The results of these analyses show that a combined imaging/acoustic analysis approach provides better characterization of the vibratory behavior of the vocal folds as it correlates with vocal output and pathology.     

Intramolecular exciplex and intermolecular excimer formation of 1,8-naphthalimide-linker-phenothiazine dyads

Steady-state fluorescence spectra were measured for 1,8-naphthahlimide-linker-phenothiazine dyads (NI-L-PTZ, where L = octamethylenyl ((CH2)8) and 3,6,9-trioxaundecyl ((CH2CH2O)3C2H4)), NI-C8-PTZ and NI-O-PTZ, as well as the NI derivatives substituted on the nitrogen atom with various linker groups without PTZ as the reference NI molecule in n-hexane. Normal fluorescence peaks were observed at 367-369 nm in all NI molecules together with a broader emission around 470 nm, which is assigned to the excimer emission between the NI in the singlet excited state (1NI*) and the NI moiety of another NI molecule (1[NI/NI]*). In addition, a broad peak around 600 nm was observed only for NI-L-PTZ, which is assigned to an intramolecular exciplex emission between donor (PTZ) and acceptor (NI) moieties in the excited singlet state, 1[NI-L-NI]*. The formation of an intramolecular exciplex corresponds to the existence of a conformer with a weak face-to-face interaction between the NI and PTZ moieties in the excited state because of the long and flexible linkers. The excited-state dynamics of the NI molecules in n-hexane were established by means of time-resolved fluorescence spectroscopy.     

Measurement of nitrogen dioxide in cigarette smoke using quantum cascade tunable infrared laser differential absorption spectroscopy (TILDAS)

Although nitrogen dioxide (NO(2)) has been previously reported to be present in cigarette smoke, the concentration estimates were derived from kinetic calculations or from measurements of aged smoke, where NO(2) was formed some time after the puff was taken. The objective of this work was to use tunable infrared laser differential absorption spectroscopy (TILDAS) equipped with a quantum cascade (QC) laser to determine if NO(2) could be detected and quantified in a fresh puff of cigarette smoke. A temporal resolution of approximately 0.16s allowed measurements to be taken directly as the NO(2) was formed during the puff. Sidestream cigarette smoke was sampled to determine if NO(2) could be detected using TILDAS. Experiments were conducted using 2R4F Kentucky Reference cigarettes with and without a Cambridge filter pad. NO(2) was detected only in the lighting puff of whole mainstream smoke (without a Cambridge filter pad), with no NO(2) detected in the subsequent puffs. The measurement precision was approximately 1.0 ppbVHz(-1/2), which allows a detection limit of approximately 0.2 ng in a 35 ml puff volume. More NO(2) was generated in the lighting puff using a match or blue flame lighter (29+/-21 ng) than when using an electric lighter (9+/-3 ng). In the presence of a Cambridge filter pad, NO(2) was observed in the gas phase mainstream smoke for every puff (total of 200+/-30 ng/cigarette) and is most likely due to smoke chemistry taking place on the Cambridge filter pad during the smoke collection process. Nitrogen dioxide was observed continuously in the sidestream smoke starting with the lighting puff.