Varietal discrimination of Chilean wines by direct injection mass spectrometry analysis combined with multivariate statistics

A simple, direct injection, electrospray ionization Fourier transform mass spectrometry (ESI FT-MS) method, in combination with multivariate statistics, was used for the characterization and sorting of Chilean wines. 47 commercial red wines labelled as Cabernet Sauvignon, Carménère, Syrah, and Pinot noir, and 25 white wines of the varieties Chardonnay and Sauvignon blanc were diluted, directly infused into the mass spectrometer, and analyzed in negative ion mode. The signature ions used for statistical analyses were manually filtered out from the signals with m/z ratios over 10%. The results of principal component analysis allowed a good sorting of white wines, but not so in the case of reds. The main three principal components explained 96.82% and 85.65% of the variance for white and red wines, respectively. Instead, linear discriminant analysis, allowed the correct discrimination of 100.00% of white and 95.74% of red samples. The validation of these results using the leave-one-out cross-validation method gave lower percentages of correct classification (76.00% and 61.70% of white and red samples respectively), suggesting that some of the wine samples analyzed might have been blends of more than one variety. Consequently, ESI FT-MS direct injection analysis of wines can be used for sample discrimination, but requires a stronger mathematical model built with spectral information of pure and blended samples before improving the percentages of classification.     

Single-particle detection efficiencies of aerosol time-of-flight mass spectrometry during the North Atlantic marine boundary layer experiment

During the North Atlantic marine boundary layer experiment (NAMBLEX) sampling campaign at Mace Head, Ireland, both continental and maritime air masses were sampled. Aerosol was characterized both with a TSI 3800 time-of-flight mass spectrometer (ATOFMS) and a MOUDI microorifice impactor, and particle number counts were measured independently with an aerodynamic particle sizer. The data have been analyzed in order to elucidate factors determining the particle detection efficiencies of the ATOFMS. These are broken down according to the efficiency of the inlet system, the hit efficiency on particles which enter the sensing zone of the instrument and the sensitivity of the measured ion signal to the chemical species. A substantial matrix effect depending on the chemical composition of the aerosol sampled at the time was found, which is reflected in variations in the hit efficiency of particles entering the sensing zone of the instrument with the main desorption-ionization laser. This is in addition to the strong inverse power-law dependence of inlet transmission efficiency on particle diameter. The variation in hit efficiency with particle type is likely attributable to differences in the energetics of laser energy absorption, ablation, and ion formation. However, once variations in both inlet transmission and hit efficiencies are taken into account, no additional matrix dependence of ATOFMS response is required to obtain a linear relationship between the ion signal and the concentration of a particular chemical species. The observations show that a constant mass of material is ionized from each particle, irrespective of size. Consequently the integrated ion signal for a given chemical component and particle size class needs to be increased by a factor related to the cube of particle diameter in order to correlate with the airborne mass of that component.     

Introduction of sulfhydryl groups and disulfide linkage to mungbean 8Sα globulin and effects on physicochemical and functional properties

Sulfhydryl groups and disulfide bond were introduced in mungbean's major storage protein, 8Sα globulin, by protein engineering to improve structural stability and functional properties. Five modified proteins or mutants (F59C, I99C, A213C, one free sulfhydryl group; I99C/A213, one disulfide bridge; F59C/I99C/A213C, one free sulfhydryl group and one disulfide linkage) were expressed in Escherichia coli at a yield similar to that of the unmodified protein or wild type (WT) in soluble form (38%). The number of introduced groups in the mutants was confirmed by Ellman analysis. Mutant and WT proteins exhibited similar elution patterns on gel filtration indicating their trimeric native conformation. Mutants had 2 to 3.8 °C higher T_m values than WT and were digested by chymotrypsin at 52–58% in 60 min but exhibited different digestion patterns. All mutants showed greater hardness of heat-induced gels than WT, especially I99C/A213C and F59C/I99C/A213C. Results indicate the improved structural stability of the modified 8Sα globulin.     

Electrospray ionization mass spectrometry fingerprinting of Brazilian cacha?as produced in copper alembic and in stainless-steel column stills

Brazilian cacha?a can be produced in two different ways: distilled in stainless steel column or in copper alembic stills. We evaluated 36 samples of commercial non-aged cacha?as: 18 samples of sweetened cacha?as distilled in stainless steel column, and 18 samples distilled in copper alembic stills. Fingerprints were obtained through electrospray ionization mass spectrometry by recording the intensity of the 15 most abundant ions. Principal component analysis was applied to the data and separated the samples in two groups. However, after sample standardization with sugar (20?g?L^?1), it was not possible to group them by type of distillation. The results showed that the technique applied did not allow differentiation of cacha?as based on the distillation system, but for the presence or absence of sugar in them.     

抑制家用纺织品异味的方法

描述了异味的产生,对人体的负作用以及能分析异味的测试方法.列举了消除异味的化学方法和市场上已有的纺织产品实例.叙述了异味吸收剂在实施和使用过程中的局限和可能产生的问题.     

The Di- and triesters of the lipids of steer and human meibomian glands

Three groups of diesters have been isolated and identified in the lipids of steer meibomian glands. The first group, designated as α Type I, with the abbreviated formula FA-αOHFA-FA1c, consisted of α-hydroxy fatty acids esterified to fatty acids and fatty alcohols in the approximate molar ratio 1∶1∶1. The second group, designated as ω Type I-St, with the abbreviated formula FA-ωOHF A-St, consisted of ω-hydroxy fatty acids esterified to fatty acids and sterols in the approximate molar ratio 1∶1∶1. The third group, designated as α,ω Type II, with the abbreviated formula FA-α,ωdiol-FA, consisted of α,ω-diols esterified to 2 moles of fatty acids. The sum of the different diesters comprised about 9% of total steer meibomian lipids. Capillary GLC of the fatty acids of αType I diesters showed the fatty acids to be a family with a two-cluster profile, one at C₁₂ to C₂₀ and the other at C₂₁ to C₃₁, with anteiso chains predominating. Fatty acids from ωType I-St and α,ωType II diesters gave mainly a one-cluster profile in the short long chain, C₂₃ to C₃₀, with anteiso chains predominating, while the α-hydroxy fatty acids were short chain C₁₃ to C₁₈ acids with C₁₆ predominating. The sterols in diesters ωType I-St were cholesterol (∼60%), Δ7 cholestenol (∼35%) and an unidentified compound (∼5%) with a GLC retention time slightly longer than Δ7 cholestenol on SE-30 phase. The ω-hydroxy fatty acids and α,ω-diols both were of exceedingly long chain lengths, C₂₉−C₃₈, and showed similar GLC profiles. Two types of triesters comprising approximately 1% of total steer meibomian lipids have been isolated but incompletely characterized. In terms of molar ratios, one group of triesters gave fatty acids:ω-hydroxy fatty acids:α-hydroxy fatty acids:sterols + fatty alcohols as approximately 1∶1∶1∶1. The other contained fatty acids, α-hydroxy fatty acids and α,ω-diols in what appears to be a complex mixture of several triesters. Diesters ωType I and α,ωType II also were found in human meibum. Hitherto these two diesters have not been found in any animal tissue.     

Comparison of methanol/hydrochloric,ferric chloride acid versus tribochemical silica coating for adhesion of resin cement to zirconium dioxide

This study compared air-abrasion and etching regimens on adhesion of resin luting agent to zirconium dioxide. Ceramic specimens (LAVA, 3 M ESPE) (N = 16) were embedded in acrylic resin and exposed surfaces were polished. The specimens were randomly assigned into four groups (n = 12, 3 specimens for each disc): SC: Air-borne particle abrasion (30 μm aluminum oxide particles coated with silica, CoJet, 3 M ESPE); MH: Heated chemical solution (Methanol-800 mL; 37% Hydrochloric Acid-200 mL; Ferric Chloride-2 g) at 100 °C for 30 min, MHP: Primer (Metal/Zirconia Primer, Ivoclar Vivadent) + MH, P: Primer only (Metal/Zirconia Primer). Cylindrical molds (internal diameter: 0.7 mm; height: 1.5 mm) were placed on each conditioned specimen, filled with resin cement (Multilink Automix) and photo-polymerized for 60 s. After 24 h, the molds were removed and the specimens were stored in distilled water at 37 °C for six months). Microshear test was performed in a Universal Testing Machine (1 mm/min). Failures types were classified as adhesive, mixed, or cohesive. In another set of specimens (n = 2 per group) contact angle measurements were recorded. Data were analyzed statistically using Kruskal–Wallis and Dunn’s tests (α = 0.05). The surface conditioning method significantly affected the mean bond strength (MPa) (p < 0.0001): SC(18.3 ± 0.3)^a < P(5.00 ± 0.07)^b < MHP(4.7 ± 0.08)^c < MH(0.84 ± 0.01)^c. While Group SC showed mainly adhesive (58%) and mixed (41.7%) failure types, groups MH, MHP, and P presented exclusively adhesive failures. SC, MHP, and P (29–32°) showed lower contact angle than MH (78.9°). Volume loss was the highest with MHP (9.92 μl) followed by SC (9.67 μl).     

Changes in structure of triglycerides from maturing kernels of corn

Kernels of corn inbred H51 were collected at five intervals after hand pollination. The triglyceride content of the total lipids increased from 8.6% at 10 days after pollination to 78.3% at 60 days. The most active period of triglyceride synthesis occurred from 20 to 45 days after pollination, when the weight of triglycerides per kernel increased from 1.1 to 7.5 mg. Over all the collection periods the percentages of palmitic, linoleic and linolenic acids decreased while oleic acid increased, but from 30 to 60 days after pollination the fatty acid composition of the triglycerides was nearly constant. Stereospecific analysis revealed a general fatty acid pattern for the triglycerides, in which the concentration of the saturated acids was highest in position 1, linoleic acid in 2 and oleic acid in 3. From 20 to 60 days after pollination there was little change in the fatty acid composition at the 1 position, but the largest changes occurred at the 3 position where palmitic and oleic acids decreased 5.1% and 7.3%, respectively, and linoleic acid increased 13.4%. The variations in the molecular species of the triglycerides were determined by silver nitrate thin layer chromatography and were found to be small from 20 to 60 days after pollination, except for an increase in trilinolein from 5.2 to 11.9%. Stereospecific analyses of four major triglycerides species, SMD, M₂D, SD₂, and MD₂, revealed larger changes in fatty acid distribution at individual positions during maturation than were apparent from analyses of the total triglycerides. Presented in part at the AOCS Meeting, Ottawa, September 1972.     

Effects of fatty acid concentration and positional specificity on maize triglyceride structure

The effects of fatty acid concentration and positional specificity on maize triglyceride structure were evaluated from the stereospecific analyses of triglycerides from 12 genotypes. The fatty acids at each position were influenced by the fatty acid concentration in the total triglyceride except for the saturates in the 2 position. The fatty acid concentration had the greatest effect on the fatty acid composition of position 3. The existence of positional specificity was evident from the nonrandom distribution of the fatty acids among the three positions of the triglycerides. The concentration and positional specificity effects could be separated in selected genotypes and their crosses. This indicated different genetic controls for each effect.     

The selective utilization of diglyceride species into maize triglycerides

The maize triglycerides were resolved into species by silver nitrate thin layer chromatography. The distribution of the fatty acids among the 1, 2 and 3 positions of each triglyceride species was determined by stereospecific analysis. From these data the relative amounts of each positional isomer were calculated. The results indicate that esterification of the fatty acids at each position proceeds with a specificity that is correlated with the composition of the other positions of the triglyceride.