Quantitative Spectral Analysis Research Articles

Molecular Orientation Analysis of Alkyl Methylene Groups from Quantitative Coherent Anti-Stokes Raman Scattering Spectroscopy.

Quantitative data analysis in coherent anti-Stokes Raman scattering (CARS) spectroscopy is important for extracting molecular structural information. We developed a method to derive molecular tilt angle with respect to the surface normal based on quantitative CARS spectral analysis. We showed that the tilt angle of methylene alkyl chains on a surface can be directly obtained from the CH2 symmetric/asymmetric peak ratio in a CARS spectrum. The lipid alkyl chain tilt angle from a lipid monolayer was measured to be ∼0° and was verified by sum frequency generation spectroscopy, which probes the orientations of the lipid methyl end groups. The tilt angle of a silane monolayer alkyl chain was derived to be ∼35°, which agrees with the theoretical prediction. This method is submonolayer sensitive and can also be used to interpret polarization-dependent signals in CARS microscopy. It can be applied to elucidate detailed molecular structure from CARS spectroscopic and microscopic measurements.

Mechanisms of azole resistance in Candida albicans clinical isolates from Shanghai, China

This study was undertaken to characterize the mechanism(s) of azole resistance in clinical isolates of Candida albicans collected in Shanghai, China, focusing on the role of efflux pumps, target enzymes of fluconazole (Erg11), respiratory status and the ergosterol biosynthetic pathway. Clinical isolates of C. albicans (n = 30) were collected from 30 different non-HIV-infected patients in four hospitals in Shanghai. All 30 C. albicans isolates were susceptible to amphotericin B and 5-fluorocytosine. Twelve C. albicans isolates showed resistance to at least one type of triazole antifungal. Flow cytometry analysis of rhodamine 6G efflux showed that azole-resistant isolates had greater efflux pump activity, which was consistent with elevated levels of CDR1 and CDR2 genes that code for ABC efflux pumps. However, we did not observe increased expression of ERG11 and MDR1 or respiratory deficiency. Several mutations of ERG11 and TAC1 genes were detected. The F964Y mutation in the TAC1 gene was identified for the first time. Two main sterols, ergosterol and lanosterol, were identified by GC–MS chromatogram, and no missense mutations were found in ERG3. Furthermore, seven amino acid substitutions in ERG11, A114S, Y132H, Y132F, K143Q, K143R, Y257H and G448E were found, by Type II spectral quantitative analysis, to contribute to low affinity binding between Erg11 and fluconazole.

Quality assessment of ZiYuan-3 multispectral and panchromatic images fusion: applied in Jiangsu coastal wetland area, China

The new launched ZiYuan-3 (ZY-3) satellite with multispectral (MS) bands and a panchromatic (PAN) band has presented a new opportunity to assess image fusion methods for coastal wetland mapping. This study focuses on image fusion quality assessment through both quantitative spectral and spatial quality analysis and object-oriented classification comparison. Various methods for pan-sharpening ZY-3 MS and PAN bands are tested, including generalized intensity-hue-saturation transform (GIHS), a trous wavelet transform (AWT), nonsubsampled contourlet transform (NSCT), and a combination of NSCT with GIHS (NSCT_GIHS). Spectral fidelity and spatial preservation of fused bands are compared with the original MS bands as reference, and spatial information injections of fused bands are compared with the resampled PAN band as reference. The fusion results demonstrate that, on average, the NSCT_GIHS method has the best performance on spectral fidelity and spatial preservation as well as spatial information injection. The near-infrared (NIR) band has the best spatial information injection in terms of entropy and cross-entropy indices, whereas the NIR band has the best spatial preservation in terms of entropy and structure similarity indices. The classification results show that NSCT_GIHS method also obtains the highest overall accuracy (96%) and Kappa coefficient (0.9425); this is in agreement with the quantitative analysis.

An ancient F-type subdwarf from the halo crossing the Galactic plane

AIMS: We selected the bluest object, WISE~J0725$-$2351, from Luhman's new high proper motion (HPM) survey based on observations with the Wide-field Infrared Survey Explorer (WISE) for spectroscopic follow-up observations. Our aim was to unravel the nature of this relatively bright ($V$$\sim$12, $J$$\sim$11) HPM star ($\mu$$=$267\,mas/yr). METHODS: We obtained low- and medium-resolution spectra with the European Southern Observatory (ESO) New Technology Telescope (NTT)/EFOSC2 and Very Large Telescope (VLT)/XSHOOTER instruments, investigated the radial velocity and performed a quantitative spectral analysis that allowed us to determine physical parameters. The fit of the spectral energy distribution based on the available photometry to low-metallicity model spectra and the similarity of our target to a metal-poor benchmark star (HD~84937) allowed us to estimate the distance and space velocity. RESULTS: As in the case of HD~84937, we classified WISE~J0725$-$2351 as sdF5: or a metal-poor turnoff star with $[Fe/H]$$=$$-$2.0$\pm$0.2, $T_{eff}$$=$6250$\pm$100\,K, $\log{g}$$=$4.0$\pm$0.2, and a possible age of about 12\,Gyr. At an estimated distance of more than 400\,pc, its proper motion translates to a tangential velocity of more than 500\,km/s. Together with its constant (on timescales of hours, days, and months) and large radial velocity (about $+$240\,km/s), the resulting Galactic restframe velocity is about 460\,km/s, implying a bound retrograde orbit for this extreme halo object that currently crosses the Galactic plane at high speed.

Quantitative EEG and medial temporal lobe atrophy in Alzheimer's dementia: Preliminary study.

Backgrounds:The electroencephalogram (EEG) abnormalities in Alzheimer's disease (AD) have been widely reported, and medial temporal lobe atrophy (MTLA) is one of the hallmarks in early stage of AD. We aimed to assess the relationship between EEG abnormalities and MTLA and its clinical validity.Materials and Methods:A total of 18 patients with AD were recruited (the mean age: 77.83 years). Baseline EEGs were analyzed with quantitative spectral analysis. MTLA was assessed by a T1-axial visual rating scale (VRS).Results:In relative power spectrum analysis according to the right MTLA severity, the power of theta waves in C4, T4, F4, F8, and T5 increased significantly and the power of beta waves in T6, C4, T4, F8, T5, P3, T3, and F7 decreased significantly in severe atrophy group. In relative power spectrum analysis according to the left MTLA severity, the power of theta waves in T3 increased significantly and that of beta waves in P4, T6, C4, F4, F8, T5, P3, C3, T3, F3, and F7 decreased significantly in severe atrophy group.Conclusion:The severe MTLA group, regardless of laterality, showed more severe quantitative EEG alterations. These results suggest that quantitative EEG abnormalities are correlated with the MTLA, which may play an important role in AD process.

Dynamic orientation of azopyridine units within the shell of vesicles PNIPAM-b-PAzPyn copolymers

Vesicles with hydrophobic shells have been self-assembled through three kinds of amphiphilic block copolymers containing pendent azopyridine groups with different spacers, namely PNIPAM-b-PAzPyn (n = 0, 2, 6), respectively. By polarization laser-trapping Raman spectroscopy, the photoinduced orientation behaviors of azopyridine groups within the vesicle shells have been investigated and it is found that spacer lengths affect the orientation of the azopyridine groups and the morphologic structure of the vesicle shells. The exact experimental results show that the orientation is dynamic for the pendent azopyridine groups with connecting spacers of 2 or 6 methylene units rather than those without spacers, so the vesicles of PNIPAM-b-PAzPy6 can be changed to show a typical “soft” character compared with its solid films when irradiated with a relatively weak polarized UV light of 190 µW/cm2. However, the vesicles of PNIPAM-b-PAzPy0 without spacers do not change even though the azopyridine units can be oriented. By quantitative Raman spectral analysis, it is found that the isomerization degree of azopyridine units is 70% for PNIPAM-b-PAzPy6 yet it is 10% for PNIPAM-b-PAzPy0, which shows a close relationship between aggregation and isomerization of azopyridine units under a weak UV light. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 415–421

Non-thermal atmospheric plasma brush induces HEMA grafting onto dentin collagen

ObjectiveNon-thermal atmospheric plasma (NTAP) brush has been regarded as a promising technique to enhance dental interfacial bonding. However, the principal enhancement mechanisms have not been well identified. In this study, the effect of non-thermal plasmas on grafting of HEMA, a typical dental monomer, onto dentin collagen thin films was investigated. MethodsHuman dentin was sectioned into 10-μm-thick films. After total demineralization in 0.5M EDTA solution for 30min, the dentin collagen films were water-rinsed, air-dried, treated with 35wt% HEMA aqueous solution. The films were then subject to plasma-exposure under a NTAP brush with different time (1–8min)/input power (5–15W). For comparison, the dentin collagen films were also treated with the above HEMA solution containing photo-initiators, then subject to light-curing. After plasma-exposure or light-curing, the HEMA-collagen films were rinsed in deionized water, and then examined by FTIR spectroscopy and TEM. ResultsThe FITR results indicated that plasma-exposure could induce significant HEMA grafting onto dentin collagen thin films. In contrast, light-curing led to no detectable interaction of HEMA with dentin collagen. Quantitative IR spectral analysis (i.e., 1720/3075 or 749/3075, HEMA/collagen ratios) further suggested that the grafting efficacy of HEMA onto the plasma-exposed collagen thin films strongly depended on the treatment time and input power of plasmas. TEM results indicated that plasma treatment did not alter collagen's banding structure. SignificanceThe current study provides deeper insight into the mechanism of dental adhesion enhancement induced by non-thermal plasmas treatment. The NTAP brush could be a promising method to create chemical bond between resin monomers and dentin collagen.

Plant leaf chlorophyll content retrieval based on a field imaging spectroscopy system.

A field imaging spectrometer system (FISS; 380–870 nm and 344 bands) was designed for agriculture applications. In this study, FISS was used to gather spectral information from soybean leaves. The chlorophyll content was retrieved using a multiple linear regression (MLR), partial least squares (PLS) regression and support vector machine (SVM) regression. Our objective was to verify the performance of FISS in a quantitative spectral analysis through the estimation of chlorophyll content and to determine a proper quantitative spectral analysis method for processing FISS data. The results revealed that the derivative reflectance was a more sensitive indicator of chlorophyll content and could extract content information more efficiently than the spectral reflectance, which is more significant for FISS data compared to ASD (analytical spectral devices) data, reducing the corresponding RMSE (root mean squared error) by 3.3%–35.6%. Compared with the spectral features, the regression methods had smaller effects on the retrieval accuracy. A multivariate linear model could be the ideal model to retrieve chlorophyll information with a small number of significant wavelengths used. The smallest RMSE of the chlorophyll content retrieved using FISS data was 0.201 mg/g, a relative reduction of more than 30% compared with the RMSE based on a non-imaging ASD spectrometer, which represents a high estimation accuracy compared with the mean chlorophyll content of the sampled leaves (4.05 mg/g). Our study indicates that FISS could obtain both spectral and spatial detailed information of high quality. Its image-spectrum-in-one merit promotes the good performance of FISS in quantitative spectral analyses, and it can potentially be widely used in the agricultural sector.

Quantitative analysis of neutron captured γ spectra using a sequential quadratic programming method

Abstract High-precision, quantitative analysis is a key element in ensuring that neutron captured γ spectral logging can be used to accurately distinguish rock minerals and rock types from complex reservoirs. We solve a nonlinear optimization problem by implementing a sequential quadratic programming method into a quantitative spectral analysis. To quantitatively test our method, we build three kinds of formation models with different porosities: a sandstone model, a mixed model of sandstone and limestone, and mixed model of sandstone, limestone, and ferric oxide. Combining results from Monte Carlo simulations, we analyze quantitatively the mixed spectra of the models using a sequential quadratic programming method and compare the results to those obtained with the weighted least-squares method. The results indicate that the sequential quadratic programming method can ensure high-precision, quantitative spectral analysis and that its spectral analysis precision is slightly higher than that of the weighted least-squares method. The sequential quadratic programming method has higher ability of adapting to complex lithology formation and can be used to analyze quantitatively the neutron γ spectrum in complex lithology formations.

Quantitative Spectral Analysis of Coherent Anti-Stokes Raman Scattering Signals: C-H Stretching Modes of the Methyl Group.

Coherent anti-Stokes Raman scattering (CARS) vibrational spectroscopy has been extensively developed into a powerful analytical technique to study various molecules. Quantitative interpretation of CARS spectra can help to improve CARS for chemical analysis and extend its analytical applications. In this work, we quantitatively analyzed CARS signals originating from the methyl groups in poly(dimethylsiloxane) (PDMS), with the help of the bond additivity method. Experimentally, a home-built CARS spectrometer modified from a commercial sum frequency generation spectrometer was used to collect CARS spectra from a PDMS film. Theoretically, we successfully reproduced the peak intensity ratio of C-H symmetric and asymmetric stretching modes of the PDMS methyl group in different polarization combinations based on bond additivity method and Raman depolarization ratio. This research shows that bond additivity theory can help to obtain the third-order nonlinear susceptibility tensor properties probed by different polarization combinations used in CARS spectroscopy. The method developed in this work could also be applied to CARS vibrational stretching analysis of other functional groups, providing quantitative understanding of CARS spectrum for applications in spectroscopy.

LP4: Spectral quantitative EEG analysis on patients with vascular dementia and Alzheimer disease

LP4: Spectral quantitative EEG analysis on patients with vascular dementia and Alzheimer disease

A new method for an objective,χ2-based spectroscopic analysis of early-type stars

A precise quantitative spectral analysis - encompassing atmospheric parameter and chemical elemental abundance determination - is time consuming due to its iterative nature and the multi-parameter space to be explored, especially when done "by eye". A robust automated fitting technique that is as trustworthy as traditional methods would allow for large samples of stars to be analyzed in a consistent manner in reasonable time. We present a semi-automated quantitative spectral analysis technique for early-type stars based on the concept of $\chi^2$ minimization. The method's main features are: far less subjective than typical "by eye" methods, correction for inaccurate continuum normalization, consideration of the whole useful spectral range, simultaneous sampling of the entire multi-parameter space (effective temperature, surface gravity, microturbulence, macroturbulence, projected rotational velocity, radial velocity, elemental abundances) to find the global best solution, applicable also to composite spectra. The method is fast, robust and reliable as seen from formal tests and from a comparison with previous analyses. Consistent quantitative spectral analyses of large samples of early-type stars can be performed quickly with very high accuracy.

Shining a spotlight on intact proteins

Cells react to cues from their environment using various mechanisms that include changes in metabolites, gene expression, protein binding partners, protein localization, and protein posttranslational modifications (PTMs), all of which contribute to altered cellular signatures that enable appropriate cellular responses. Given the seemingly infinite number of mechanisms available to affect protein function and modulate biological processes, the question arises as to how cells manage to interpret protein readouts to accomplish the appropriate cell-type specific response to a particular stimulus.

Quantitative Quantum Mechanical Spectral Analysis (qQMSA) of 1H NMR spectra of complex mixtures and biofluids

The quantitative interpretation of 1H NMR spectra of mixtures like the biofluids is a demanding task due to spectral complexity and overlap. Complications may arise also from water suppression, T2-editing, protein interactions, relaxation differences of the species, experimental artifacts and, furthermore, the spectra may contain unknown components and macromolecular background which cannot be easily separated from baseline. In this work, tools and strategies for quantitative Quantum Mechanical Spectral Analysis (qQMSA) of 1H NMR spectra from complex mixtures were developed and systematically assessed. In the present approach, the signals of well-defined, stoichiometric components are described by a QM model, while the background is described by a multiterm baseline function and the unknown signals using optimizable and adjustable lines, regular multiplets or any spectral structures which can be composed from spectral lines. Any prior knowledge available from the spectrum can also be added to the model. Fitting strategies for weak and strongly overlapping spectral systems were developed and assessed using two basic model systems, the metabolite mixtures without and with macromolecular (serum) background. The analyses show that if the spectra are measured in high-throughput manner, the consistent absolute quantification demands some calibration to compensate the different response factors of the protons and compounds. On the other hand, the results show that also the T2-edited spectra can be measured so that they obey well the QM rules. In general, qQMSA exploits and interprets the spectral information in maximal way taking full advantage from the QM properties of the spectra and, at the same time, offers chemical confidence which means that individual components can be identified with high confidence on the basis of their accurate spectral parameters.

Theta frequency activity during rapid eye movement (REM) sleep is greater in people with resilience versus PTSD

Emotional memory consolidation has been associated with rapid eye movement (REM) sleep, and recent evidence suggests that increased electroencephalogram spectral power in the theta (4-8Hz) frequency range indexes this activity. REM sleep has been implicated in posttraumatic stress disorder (PTSD) as well as in emotional adaption. In this cross-sectional study, thirty young healthy African American adults with trauma exposure were assessed for PTSD status using the Clinician Administered PTSD Scale. Two consecutive night polysomnographic (PSG) recordings were performed and data scored for sleep stages. Quantitative electroencephalographic spectral analysis was used to measure theta frequency components sampled from REM sleep periods of the second-night PSG recordings. Our objective was to compare relative theta power between trauma-exposed participants who were either resilient or haddeveloped PTSD. Results indicated higher right prefrontal theta power during the first and last REM periods in resilient participants compared with participants with PTSD. Right hemisphere prefrontal theta power during REM sleep may serve as a biomarker of the capacity for adaptive emotional memory processing among trauma-exposed individuals.

Simplified versus standard EEG to measure the depth of sedation in mechanically ventilated ICU patients

The accurate measure of sedation depth among mechanically ventilated ICU patients remains challenging. The Patient State Index (PSI) is a quantitative measure calculated using an algorithm derived from a simplified four-channel EEG. The aim of this study was to examine the value of the PSI to assess the level of sedation, and to verify its accuracy in comparison with the quantitative spectral analysis derived from a standard 19-channel EEG.

QEEG Spectral and Coherence Assessment of Autistic Children in Three Different Experimental Conditions

We studied autistics by quantitative EEG spectral and coherence analysis during three experimental conditions: basal, watching a cartoon with audio (V–A), and with muted audio band (VwA). Significant reductions were found for the absolute power spectral density (PSD) in the central region for delta and theta, and in the posterior region for sigma and beta bands, lateralized to the right hemisphere. When comparing VwA versus the V–A in the midline regions, we found significant decrements of absolute PSD for delta, theta and alpha, and increments for the beta and gamma bands. In autistics, VwA versus V–A tended to show lower coherence values in the right hemisphere. An impairment of visual and auditory sensory integration in autistics might explain our results.

In Situ Attenuated Total Reflectance Fourier Transform Infrared (ATR FT-IR) Spectroscopy Monitoring of 1,2-Butylene Oxide Polymerization Reaction by Using Iterative Concentration-Guided Classical Least Squares

There has been rapid growth in the application of in situ optical spectroscopy techniques for reaction and process monitoring recently in both academia and industry. Vibrational spectroscopies such as mid-infrared, near-infrared spectroscopy, and Raman spectroscopy have proven to be versatile and informative. Accurate determination of concentrations, based on highly overlapped spectra, remains a challenge. As an example, 1,2-butylene oxide (BO) polymerization, an important industrial reaction, initiated by propylene glycol (PG) and catalyzed by KOH, is studied in this work in a semi-batch fashion by using in situ attenuated total reflectance Fourier transform infrared spectroscopy (ATR FT-IR) monitoring. The weak BO absorbance, the constantly changing interference from the product oligomers throughout the course of the reaction, and the change in BO spectral features with system polarity posed challenges for quantitative spectral analysis based on conventional methods. An iterative concentration-guided classical least-squares (ICG-CLS) method was developed to overcome these challenges. Taking advantage of the concentration-domain information, ICG-CLS enabled the estimation of the pure oligomer product spectra at different stages of the semi-batch process, which in turn was used to construct valid CLS models. The ICG-CLS algorithm provides an in situ calibration method that can be broadly applied to reactions of known order. Caveats in its applications are also discussed.

Time‐lens based hyperspectral stimulated Raman scattering imaging and quantitative spectral analysis

We demonstrate a hyperspectral stimulated Raman scattering (SRS) microscope through spectral-transformed excitation. The 1064 nm Stokes pulse was from a synchronized time-lens source, generated through time-domain phase modulation of a continuous wave (CW) laser. The tunable pump pulse was from linear spectral filtering of a femtosecond laser output with an intra-pulse spectral scanning pulse shaper. By electronically modulating the time-lens source at 2.29 MHz, hyperspectral stimulated Raman loss (SRL) images were obtained on a laser-scanning microscope. Using this microscope, DMSO in aqueous solution with a concentration down to 28 mM could be detected at 2 μs time constant. Hyperspectral SRL images of prostate cancer cells were obtained. Multivariate curve resolution analysis was further applied to decompose the SRL images into concentration maps of CH₂ and CH₃ bonds. This method offers exciting potential in label-free imaging of live cells using fingerprint Raman bands.

Dissociative Mental States Are Canonically Associated with Decreased Temporal Theta Activity on Spectral Analysis of EEG

Quantitative electroencephalographic (QEEG) changes relating to dissociative experiences have only rarely been demonstrated, and dissociative states were not quantified in those studies. The aim of this study was to explore concurrent associations between quantified dissociative states and QEEG spectral parameters, in particular theta activity, in psychiatric patients. Fifty psychiatric patients completed the State Scale of Dissociation (SSD) immediately after a 15-min EEG recording. The EEG was assessed by conventional clinical visual analysis as well as by quantitative (QEEG) spectral analysis. Canonical analysis was performed between the set of SSD subscale scores and the following QEEG parameters: alpha–theta magnitude ratios, and relative as well as absolute theta magnitude obtained from right and left mid- to posterior-temporal and parieto-occipital derivations. The SSD transferred well to the present data in terms of reliability and internal criterion-related validity. The SSD and Dissociative Experiences Scale (DES) correlated significantly (r = .73, p < .001). Conventional EEG analysis identified 29 EEGs (58%) as abnormal. The main abnormality in 23 EEGs was slowing, maximal temporally in half of these cases. Canonical analyses confirmed a statistically significant relationship between the dissociation variables (especially conversion and depersonalization symptoms) and the QEEG variables (especially relative theta magnitude in the temporal regions; R = .72, p = .03, for SSD–QEEG; and R = .66, p = .04, for DES–QEEG). Quantified dissociative mental states are positively canonically associated with decreased temporal theta activity and increased alpha–theta ratios on QEEG in psychiatric patients with a high tendency to dissociate. The potential implications of the dissociation–theta–alpha relationship for understanding normal attentional processes need to be studied further.