Detection of bio-constituents in complex biological tissue using Raman microscopy. Application to human nail clippings

Raman spectra of human nail clippings from various sources were collected and then deconvoluted to obtain the pure component spectra of the underlying constituents present. This blind-deconvolution was performed using a self-modeling curve resolution technique, namely band-target entropy minimization (BTEM). The aim was to simplify the complexity of the Raman spectra and hence to identify the underlying biological molecules in more detail. BTEM analysis could recover 13 pure component Raman spectral estimates from the collected 438 spectra measured from 113 nail samples. Six recovered pure component spectral estimates correspond to proteins or polypeptides that contain various amino acids such as phenylalanine, tyrosine, tryptophan, and cysteine. Two are associated with the secondary structures of proteins, and five are associated with two carotenoid species, lipid, ferulic acid, and calcium phosphate. Subsequently, the relative concentrations of these bio-constituents were calculated from the measured mixture spectra and the pure component BTEM estimates. These profiles indicated that the concentrations of some bio-constituents are correlated while others are not. A further analysis using target transformation factor analysis (TTFA) revealed the possible presence of curcumin in the human nails. Since the present approach and analysis is rather general, it might be extended to many other biological tissues in a rather straightforward and similar manner, thus revealing more detailed underlying biochemical information such as biomarkers that may be useful for diagnostic purposes.     

Electronic Excitation of [(μ4‐η2‐alkyne)Rh4(CO)8(μ‐CO)2]: An In Situ UV/Vis Spectroscopy,Spectral Reconstruction and DFT Study

Reactions of three alkynes, namely, 1‐heptyne, 3‐hexyne and 1‐phenyl‐1‐butyne, with [Rh₄(CO)₉(μ‐CO)₃] are performed in anhydrous hexane under argon atmosphere with multiple perturbations of alkynes and [Rh₄(CO)₉(μ‐CO)₃]. The reactions are monitored by in situ UV/Vis spectroscopy, and the collected electronic spectra are further analyzed with the band‐target entropy minimization (BTEM) family of algorithms to reconstruct the pure component spectra. Three BTEM estimates of [(μ₄‐η²‐alkyne)Rh₄(CO)₈(μ‐CO)₂], in addition to that of [Rh₄(CO)₉(μ‐CO)₃], are successfully reconstructed from the experimental spectra. Time‐dependent density functional theory (TD‐DFT) predicted spectra at the PBE0/DGDZVP level are consistent with the corresponding BTEM estimates. The present study demonstrates that: 1) the BTEM family of algorithms is successful in analyzing multi‐component UV/Vis spectra and results in good spectral estimates of the trace organometallics present; and 2) the subsequent DFT/TD‐DFT methods provide an interpretation of the nature of the electronic excitation and can be used to predict the electronic spectra of similar transition organometallic complexes.     

Analytical performances of FT-IR spectrometry and imaging for concentration measurements within biological fluids, cells, and tissues

FT-IR spectrometry has proved to be a useful tool for determining a series of plasma molecular concentrations. Dedicated experiments were first performed to test the analytical performance that could be obtained by FT-IR spectrometry using a synthesized N3-peptide exhibiting a -N3 absorption centered at 2110 cm(-1), a spectral region where no organic material of biological samples absorbs. Further, we investigated whether this technology was able to allow quantification of metabolic parameters (glucose and lactic acid) within plasma, cells, and tissues as an alternative method to the "classical" biochemical approaches, which require sophisticated biological material treatment and expensive reagents. For this purpose we used a series of plasma samples to determine glucose and lactic acid concentrations, which are common markers of cancer growth. We compared the results of the main spectral data treatments commonly achieved for FT-IR data analysis, such as univariate (Beer-Lambert) or multivariate (PLS) calibrations, as well as the deconvolution of the spectral interval of interest (1200-900 cm(-1)). No significant differences were found regarding the analytical performances of these methods. Spectral deconvolution was finally undertaken on cultured and on xenografted cells (U87 glial cells implied in human gliomas) to determine glucose and lactic acid concentrations. In this case, qualification was allowed by FT-IR imaging on the cellular models since biochemical approaches are not efficient to reach metabolic concentrations at the cellular level while keeping tissue organization.     

Experimental dipole moments for nonisolatable acetic acid structures in a nonpolar medium. A combined spectroscopic, dielectric, and DFT study for self-association in solution

Acetic acid can exist in many possible structural forms depending on its surrounding medium. A recently developed inverse problem methodology (J. Phys. Chem. B 2007, 111, 13064-13074) was utilized in order to elucidate acetic acid structures in a dilute nonpolar medium. In this regard, simultaneous and stopped-flow measurements of the bulk solution densities, refractive indices, relative permittivities, and IR spectra of acetic acid in toluene were performed at several different concentrations in a semibatch closed-loop experimental setup at 298.15 K and 0.1013 MPa. This combined IR spectroscopic and dielectric, density, and refractive index analysis was employed in order to distinguish acetic acid structures and to further determine the dipole moments of the monomer, cyclic dimer, and "lumped-sum" open dimers. The infrared spectra were first analyzed to provide qualitative understanding as well as quantitative estimates for each acetic acid species. Subsequently, the dipole moments of these species were calculated using a direct approach which was primarily based on response surface models. The present method allows the determination of individual dipole moments not only for the monomer but also for the cyclic dimer and the open dimer. The results obtained from this study experimentally show that the cyclic dimer with centrosymmetric structure has a dipole moment approximately 0 D. The results also suggest that the linear dimers are present as mixtures of linear dimers structures. The existence of the linear dimers mixture was also indicated by the experimental infrared analysis of the OH-stretching region (particularly for measurements in n-hexane as solvent) and comparison of these spectra with DFT predictions. Finally, the present methodology which incorporates simultaneous physicochemical and spectroscopic analysis is undoubtedly useful for physicochemical characterization for other nonisolatable solute species and self-associated structures in solution.     

A combination of spectral re-alignment and BTEM for the estimation of pure component NMR spectra from multi-component non-reactive and reactive systems

The deconvolution of multi-component mixtures in NMR spectroscopy is a challenging problem due to the spectral non-linearities. In the present contribution, two data sets were studied (A) 10 samples of a four-component non-reactive mixture measured with ¹H, ¹³C, ¹⁹F, ³¹P NMR and (B) a three-solute cyclo-addition reaction measured with ¹³C NMR. Both data sets were treated with a re-alignment procedure to correct for the non-stationary chemical shifts, followed by band-target entropy minimization (BTEM) analysis. For data set A, quite good spectral estimates of the two hydrogen-containing species, four carbon-containing species, two fluorine-containing species and two phosphorus-containing species were obtained from the multi-component data. For data set B quite good spectral estimates of all three carbon-containing reactants were obtained as well as their relative concentration profiles. The present contribution using model systems indicates the usefulness of re-alignment procedures for correcting non-stationary characteristics, prior to self-modeling curve resolution (SMCR), and the potential for investigating more complex problems.     

Application of band-target entropy minimization (BTEM) and residual spectral analysis to in situ reflection-absorption infrared spectroscopy (RAIRS) data from surface chemistry studies

The band-target entropy minimization (BTEM) curve resolution technique has been used to analyze in situ reflection-absorption infrared spectroscopy (RAIRS) data of CO chemisorption on Ni(1 1 1) single crystal surfaces. The bilinearity assumption for pRAIRS data, that is, negative logarithm to the base 10 of raw reflectance RAIRS data, was found to be sufficiently valid for the test data. A total of 11 real pure component pRAIRS spectra were elucidated via BTEM in tandem with an iterative residual spectral data analysis. Furthermore, 2 abstract pure component right singular vectors were found to account for all the pRAIRS non-linearities, baseline drifts and other spectral noise. In total, 100.2% of the pRAIRS signals were accounted for by these 13 spectral components. The 11 real pure component pRAIRS spectra and their corresponding relative concentration kinetic sequences correlate with 6 well-known adsorbed CO domain structures. Moreover, amongst the BTEM resolved spectra were five new bands that were not previously observed using conventional visual identification methods adopted by surface chemists. These new bands engendered new understanding to the mechanism of CO chemisorption on Ni(1 1 1). The combination of BTEM with residual spectral analysis was thus demonstrated to be efficacious for curve resolution of in situ RAIRS data obtained from surface chemistry studies.     

Spectral resolution of fluxional organometallics. The observation and FTIR characterization of all-terminal [Rh4(CO)12

In situ FTIR spectroscopy at 1 cm(-1) resolution was conducted on n-hexane solutions of the bridged [Rh4(CO)9(mu-CO)3] in the interval T= 268-288 K and P(T)= 0.1-7.0 MPa using either helium or carbon monoxide as dissolved gas. Analysis of the spectral data sets was conducted using band-target entropy minimization (BTEM), in order to recover the pure component spectra. A new spectral pattern was recovered with terminal vibrations at 2075, 2069.8, 2044.6 and 2042 cm(-1). The new spectrum is consistent with an all-terminal [Rh4(CO)12] species with a C(3v) anticubeoctahedron structure where 2 different [Rh(CO)3] moieties exist, although the presence of some Td structure can not be entirely excluded. The equilibrium between all-terminal [Rh4(CO)12] and the bridged [Rh(4)(CO)9(mu-CO)3] was determined in the presence of both helium and CO. The equilibrium constant K(eq)=[Rh4(CO)12]/[Rh4(CO)9(mu-CO)3] at 275 K was ca. 0.011 and the determined equilibrium parameters were Delta(r)G= 12.63 +/- 4.8 kJ mol(-1), Delta(r)H=-21.45 +/- 2.3 kJ mol(-1) and Delta(r)S=-114.3 +/- 8.35 J mol(-1) K(-1). The free energy indicates a very small difference between the bridged and terminal geometry, and the lower entropy is consistent with a higher symmetry. This finding helps to address a long-standing issue concerning the existence of various [M4(CO)12] symmetries. In a more general context, the present study illustrates the considerable utility of quantitative infrared spectroscopy (occurring on a fast vibrational timescale) combined with sophisticated deconvolution techniques in order to resolve systems which have been demonstrated to be fluxional on the NMR timescale.     

Synthesis of 2-amino-5-chloro-3-(trifluoromethyl)benzenethiol and conversion into 4H-1,4-benzothiazines and their sulfones

The synthesis of 2-amino-5-chloro-3-(trifluoromethyl)benzenethiol was achieved by hydrolytic cleavage of 2-amino-6-chloro-4-(trifluoromethyl)benzothiazole which was prepared by cyclization of 4-chloro-2-(trifluoromethyl)phenylthiourea by bromine in chloroform, the phenylthiourea was prepared by the reaction of 4-chloro-2-(trifluoromethyl)aniline with ammonium thiocyanate in hydrochloric acid. Condensation and oxidative cyclization of 2-amino-5-chloro-3-(trifluoromethyl)benzenethiol with β-diketones/β-ketoesters provided 4H-1,4-benzothiazines. Fluorinated sulfones were obtained by oxidation of the corresponding benzothiazines with 30% hydrogen peroxide in glacial acetic acid. The structures of the newly synthesized compounds were confirmed by spectral studies.     

Experimental and theoretical studies of the kinetics of the reactions of OH radicals with acetic acid, acetic acid-d3 and acetic acid-d4 at low pressure

The kinetics of the reactions of OH with acetic acid, acetic acid-d3 and acetic acid-d4 were studied from 2 to 5 Torr and 263-373 K using a discharge flow system with resonance fluorescence detection of the OH radical. The measured rate constants at 300 K for the reaction of OH with acetic acid and acetic acid-d4 (CD3C(O)OD) were (7.42+/-0.12)x10(-13) and (1.09+/-0.18)x10(-13) cm3 molecule-1 s-1 respectively, and the rate constant for the reaction of OH with acetic acid-d3 (CD3C(O)OH) was (7.79+/-0.16)x10(-13) cm3 molecule-1 s-1. These results suggest that the primary mechanism for this reaction involves abstraction of the acidic hydrogen. Theoretical calculations of the kinetic isotope effect as a function of temperature are in good agreement with the experimental measurements using a mechanism involving the abstraction of the acidic hydrogen through a hydrogen-bonded complex. The rate constants for the OH+acetic acid and OH+acetic acid-d4 reactions display a negative temperature dependence described by the Arrhenius equations kH(T)=(2.52+/-1.22)x10(-14) exp((1010+/-150)/T) and kD(T)=(4.62+/-1.33)x10(-16) exp((1640+/-160)/T) cm3 molecule-1 s-1 for acetic acid and acetic acid-d4, respectively, consistent with recent measurements that suggest that the lifetime of acetic acid at the low temperatures of the upper troposphere is shorter than previously believed.     

Synthesis,characterization and biological activities of homo-binuclear Cu(II) and Zn(II) complexes derived from 2-hydroxy-5-methyl-1,3-benzenedicarboxaldehyde derivatives

Few novel binuclear Schiff base metal complexes [M₂LCl₃], where M = Cu(II) and Zn(II); L= 2,6-bis-({2-[(3-hydroxy-4-nitrobenzylidene)amino]ethylimino}methyl)-4-methylphenol (BHEM), 2,6-bis-({2-[(3,4-dimethoxybenzylidene)amino]ethylimino} methyl)-4-methylphenol (BDEM) and 2,6-bis-({2-[(2,3,5-trichlorobenzylidene)amino]ethylimino}methyl)-4-methylphenol (BTEM), have been synthesized and characterized by analytical and spectral data. The data suggest that BHEM/BDEM/BTEM ligands afford square-pyramidal/distorted square-pyramidal geometry on metalation with Zn(II)/Cu(II). The binding behaviour of these complexes with DNA has been investigated using electronic absorption spectroscopy as well as viscosity and voltammetric measurements; the results show that they interact with DNA through intercalating way. From the DNA cleavage study of these complexes, investigated by gel electrophoresis, we found that they efficiently cleave supercoiled pUC19 DNA in the presence of a reducing agent (3-mercaptopropionic acid) and on irradiation with UV light of 360 nm wavelength. The mechanism reveals that singlet oxygen (¹O₂) plays a significant role in the photo cleavage. The superoxide dismutase (SOD) mimetic activity of the synthesized complexes demonstrates that most of the complexes have promising SOD-mimetic activity. The antimicrobial study indicates that the complexes inhibit the growth of bacteria and fungi more than the free ligands.     

The reactions of Rh2(CO)4Cl2 with 1,5-cyclooctadiene and tetramethylallene. A combined in-situ vibrational spectroscopies, spectral reconstruction and DFT study

Reactions of Rh₂(CO)₄Cl₂ with 1,5-cyclooctadiene (COD) and tetramethylallene (TMA) were performed separately in anhydrous hexane under argon atmosphere. Multiple perturbations of Rh₂(CO)₄Cl₂, COD and TMA were also performed during the reactions. These two reactions were monitored by in-situ FTIR (FIR and MIR) and/or Raman spectroscopies and the collected spectra were further analyzed with BTEM family of algorithms. DFT calculations were performed to identify the organometallic species present. The known diene complex Rh₂(CO)₂Cl₂(η⁴-C₈H₁₂) and a new allene complex Rh₂(CO)₃Cl₂(η²-C₇H₁₂) were formed as the two primary organo-rhodium products. Their pure component spectra were reconstructed in the three characteristic regions of 200-680, 800-1360, and 1500-2200 cm⁻¹. Their relative concentrations were also obtained by the least square fitting of the carbonyl region 1500-2200 cm⁻¹. The present contribution shows the usefulness of combining in-situ spectroscopic measurements, BTEM analysis and DFT spectral prediction in order to analyze organometallic reactions at high dilution and identify the reaction products.     

Pure component spectral analysis of surface adsorbed species measured under real conditions. BTEM-DRIFTS study of CO and NO reaction over a Pd/gamma-Al2O3 catalyst

The adsorption of NO and CO was studied on an alumina-supported palladium catalyst by in situ diffuse reflectance infrared spectroscopy (DRIFTS). The temperature range was 50-160 degrees C and a wide variety of partial pressures was used. The band-target entropy minimization (BTEM) algorithm was applied to the DRIFTS data sets resulting in the pure component spectra of numerous species adsorbed on both the Pd (primarily a variety of Pd-CO and Pd-NO species, in various oxidation states and coordinations) and alumina surface species (i.e. nitrates, nitrites, carbonates, bicarbonates, formates, and isocyanates) as well as gas phase species. Twenty seven previously known species were identified as well as three new and previously unreported or previously unassigned spectra. The present study indicates that BTEM can be meaningfully applied to Pd/Al2O3 DRIFTS in order to provide enhanced spectroscopic analysis. Moreover, the present results are compared in detail with the recent BTEM analysis of CO and NO adsorption on Pt/Al2O3 using DRIFTS (Phys. Chem. Chem. Phys. 2008, 10, 3535).     

Determination of acetic acid in aqueous samples, by water-phase derivatisation, solid-phase microextraction and gas chromatography

The direct derivatisation of acetic acid with n-hexyl chloroformate and with benzyl bromide in water was evaluated. With n-hexyl chloroformate, acetic acid did not give the n-hexyl acetate derivative, but the reaction of acetic acid with benzyl bromide in aqueous solution resulted in the formation of benzyl acetate. The derivatisation of acetic acid with benzyl bromide and the headspace solid-phase microextraction (SPME) of benzyl acetate were optimised. Under optimum conditions, the limit of detection for acetic acid was 260 nM, and the relative standard deviation of the overall procedure at 1.10(-4) M acetic acid was 15.6% (n = 10). A linear response was obtained in the 1 x 10(-4) to 5 x 10(-6) M concentration range (R2 = 0.993, n = 6). Although Carbowax-divinylbenzene (CW-DVB)-coated fibres exhibited a higher extraction capacity for benzyl acetate, polyacrylate (PA) was selected, because its mechanical stability was better than that of CW-DVB fibres. Moreover, the relative standard deviation of the SPME was better with PA (1.5%, n = 10 at 1 x 10(-5) M) than with CW-DVB-coated fibres (8.0%, n = 10 at 1 x 10(-5) M). Thus, a new analytical method for the quantitative determination of micromolar concentrations of acetic acid in the aqueous phase was developed. This method is based on water-phase derivatisation with benzyl bromide, headspace SPME with PA fibres and GC-FID. It was observed experimentally that benzyl alcohol formed by hydrolysis of the reagent affected the fibre-gas phase partitioning of benzyl acetate.     

Pb(II) and Zn(II) adsorption onto Na- and Ca-montmorillonites in acetic acid/acetate medium: experimental approach and geochemical modeling

Smectites are usually used as a clay barrier at the bottom of subsurface waste landfills due to their low permeability and their capacity to retain pollutants. The Na- and Ca-saturated SWy2 montmorillonites were interacted with initial Zn(NO(3))(2) or Pb(NO(3))(2) concentrations ranging from 10(-6) to 10(-2)M with a solid/liquid ratio of 10 g L(-1) and using acetic acid/acetate as buffer at pH 5 in order to reproduce a biodegradable leachate of a young landfill. These experiments revealed that Zn and Pb sorption onto Na-SWy2 is higher than that onto Ca-SWy2 in the whole range of concentrations. Metal retention into both montmorillonites increases with the decrease in acetic acid/acetate concentration. The two-site protolysis model with no electrostatic term (2SPNE model) was used to model these experiments. As the experimental data of Zn sorption were well fitted, this model was validated and has been improved by taking into account the metal-acetate complexation in solution. In order to validate the model for Pb sorption, new selectivity coefficients have been determined, namely logK(c)(PbNa)=0.5 for Na-montmorillonite and logK(c)(PbCa)=0.3 for Ca-montmorillonite.     

A Comparison of the Properties of Contactless Conductivity and Diode‐Array Photometric Detectors in Analyses of Low‐Molecular,Biologically Active Substances by Capillary Electrophoresis in Acetic Acid Solutions

The performance of the contactless conductivity (C⁴D) and diode array photometric (DAD) detectors has been compared for CE separations of creatinine, arginine and 3‐methylhistidine in acetic acid background electrolytes. The contactless conductivity detector response has also been modeled. It has been found that the two detectors provide similar responses and can readily be used for dual CE detection. Changes in the acetic acid concentration affect the C⁴D noise less than the DAD noise, but their effect on the C⁴D response to the analytes is greater than with DAD. In general, C⁴D provides better detection results at higher acetic acid concentrations, while DAD is more sensitive and reliable at very low ones. Capillaries with greater internal diameters are preferable for both detectors, provided that the separation efficiency is not adversely affected. Acetic acid is a suitable background electrolyte for CE separations of small, basic organic molecules.     

Uptake measurements of acetic acid on ice and nitric acid-doped thin ice films over upper troposphere/lower stratosphere temperatures

The adsorption of gaseous acetic acid (CH(3)C(O)OH) on thin ice films and on ice doped with nitric acid (1.96 and 7.69 wt %) was investigated over upper troposphere and lower stratosphere (UT/LS) temperatures (198-208 K), and at low gas concentrations. Experiments were performed in a Knudsen flow reactor coupled to a quadrupole mass spectrometer. The initial uptake coefficients, γ(0), on thin ice films or HNO(3)-doped ice films were measured at low surface coverage. In all cases, γ(0) showed an inverse temperature dependence, and for pure thin ice films, it was given by the expression γ(0)(T) = (4.73 ± 1.13) × 10(-17) exp[(6496 ± 1798)/T]; the quoted errors are the 2σ precision of the linear fit, and the estimated systematic uncertainties are included in the pre-exponential factor. The inverse temperature dependence suggests that the adsorption process occurs via the formation of an intermediate precursor state. Uptakes were well represented by the Langmuir adsorption model, and the saturation surface coverage, N(max), on pure thin ice films was (2.11 ± 0.16) × 10(14) molecules cm(-2), independent of temperature in the range 198-206 K. Light nitration (1.96 and 7.69 wt %) of ice films resulted in more efficient CH(3)C(O)OH uptakes and larger N(max) values that may be attributed to in-bulk diffusion or change in nature of the gas-ice surface interaction. Finally, it was estimated that the rate of adsorption of acetic acid on high-density cirrus clouds in the UT/LS is fast, and this is reflected in the short atmospheric lifetimes (2-8 min) of acetic acid; however, the extent of this uptake is minor resulting in at most a 5% removal of acetic acid in UT/LS cirrus clouds.     

Acidic herbicides in surface waters of Lower Fraser Valley, British Columbia, Canada

In the period 2003-2005 a study was conducted to determine the occurrence, spatial and temporal distribution of five acidic herbicides in the Lower Fraser Valley (LFV) region of British Columbia, Canada. A high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) method capable of detecting analytes at the sub ng/L level was developed for this study. Samples were collected and analyzed from two references, five agricultural, two urban and five agricultural and urban mixed sites. Only (4-chloro-2-methylphenoxy)acetic acid and triclopyr were detected at the reference sites. The highest concentration of herbicide detected at the reference sites was 0.109ng/L for (4-chloro-2-methylphenoxy)acetic acid. Varying levels of all of the herbicides monitored were detected at the urban, agricultural and the mixed sites. For the urban sites the highest concentration of herbicide detected was 66.6ng/L for 2-(4-chloro-2-methylphenoxy)propanoic acid. For the agricultural sites the highest concentration of herbicide detected was 345ng/L for (2,4-dichlorophenoxy)acetic acid (2,4-D). For the mixed sites the highest concentration of herbicide detected was 1230ng/L for 2,4-D. Overall the mixed sites showed highest concentrations and detection frequencies followed by the agricultural and urban sites. With few exceptions higher concentrations of herbicides were observed for samples collected during spring than for samples collected during fall. The detected concentrations of herbicides were evaluated against established water quality criteria. Herbicide data presented in this study provide reference levels for future pesticide monitoring programs in the region.     

3-巯基香豆素和二苯胺的α-氨甲基化反应(Mannich反应)的动力学研究

通过实验及动力学研究, 证明-3巯基香豆素(6)和二苯胺发生α-氨甲基化反应时, 是(6)首先和甲醛反应, 生成S-半缩醛——3-羟甲硫基香豆素(7), 然后再与二苯胺反应形成3-二苯胺甲硫基香豆素(8), 3-羟甲硫基香豆素与二苯胺在冰醋酸的催化作用下进行反应时, 随着酸浓度的改变, 反应机理发生了改变, 本文对这一反应机理进行了讨论和解释。     

Monitoring of substrate and product concentrations in acetic fermentation processes for onion vinegar production by NIR spectroscopy: value addition to worthless onions

Wastes and by-products of the onion-processing industry pose an increasing disposal and environmental problem and represent a loss of valuable sources of nutrients. The present study focused on the production of vinegar from worthless onions as a potential valorisation route which could provide a viable solution to multiple disposal and environmental problems, simultaneously offering the possibility of converting waste materials into a useful food-grade product and of exploiting the unique properties and health benefits of onions. This study deals specifically with the second and definitive step of the onion vinegar production process: the efficient production of vinegar from onion waste by transforming onion ethanol, previously produced by alcoholic fermentation, into acetic acid via acetic fermentation. Near-infrared spectroscopy (NIRS), coupled with multivariate calibration methods, has been used to monitor the concentrations of both substrates and products in acetic fermentation. Separate partial least squares (PLS) regression models, correlating NIR spectral data of fermentation samples with each kinetic parameter studied, were developed. Wavelength selection was also performed applying the iterative predictor weighting–PLS (IPW-PLS) method in order to only consider significant spectral features in each model development to improve the quality of the final models constructed. Biomass, substrate (ethanol) and product (acetic acid) concentration were predicted in the acetic fermentation of onion alcohol with high accuracy using IPW-PLS models with a root-mean-square error of the residuals in external prediction (RMSEP) lower than 2.5% for both ethanol and acetic acid, and an RMSEP of 6.1% for total biomass concentration (a very satisfactory result considering the relatively low precision and accuracy associated with the reference method used for determining the latter). Thus, the simple and reliable calibration models proposed in this study suggest that they could be implemented in routine applications to monitor and predict the key species involved in the acetic fermentation of onion alcohol, allowing the onion vinegar production process to be controlled in real time.     

The detection of laser-induced structural change of MnO2 using in situ Raman spectroscopy combined with self-modeling curve resolution technique

In this paper, we present the use of one of the self-modeling curve resolution techniques, band-target entropy minimization (BTEM), which is independent of any spectral library, to elucidate Raman pure component spectra of two different manganese oxides arising from laser-induced structural changes. It is often extremely difficult to obtain the pure Raman spectrum of MnO₂ without changing it to another structural form. However, using BTEM to analyze the collected in situ Raman spectra measured as a function of laser exposure time, has enabled us to obtain both the pure component spectra of the original sample and the product due to laser irradiation. This technique proves to be an efficient Raman spectral interpretation method for thermal sensitive solid samples.