Mass Peak Intensities Research Articles

Post column infusion of an internal standard into LC-FT-ICR MS enables semi-quantitative comparison of dissolved organic matter in original samples.

Ultrahigh resolution mass spectrometry hyphenated with liquid chromatography (LC) is an emerging tool to explore the isomeric composition of dissolved organic matter (DOM). However, matrix effects limit the potential for semi-quantitative comparison of DOM molecule abundances across samples. We introduce a post-column infused internal standard (PCI-IS) for reversed-phase LC-FT-ICR MS measurements of DOM and systematically evaluate matrix effects, detector linearity and the precision of mass peak intensities. Matrix effects for model compounds spiked into freshwater DOM samples ranging from a headwater stream to a major river were reduced by 5-10% for PCI-IS corrected mass peak intensities as compared to raw (i.e., untransformed) intensities. A linear regression of PCI-IS corrected DOM mass peak intensities across a typical DOM concentration range (2-15 mg dissolved organic carbon L-1) in original, non-extracted freshwater samples demonstrates excellent linearity of the detector response (r2 > 0.9 for 98% of detected molecular formulas across retention times). Importantly, PCI-IS could compensate for 80% of matrix effects across an environmental gradient of DOM composition from groundwater to surface water. This enabled studying the ionization efficiency of DOM isomers and linking the observed differences to the biogeochemical sources. With PCI-IS original, non-extracted DOM samples can be analysed by LC-FT-ICR MS without carbon load adjustment, and mass peak intensities can be reliably used to semi-quantitatively compare isomer abundances between compositionally similar DOM samples.

Intensity-dependent mass search for improving metabolite database matches in chemical isotope labeling LC-QTOF-MS-based metabolomics

Liquid chromatography mass spectrometry (LC-MS) has been increasingly used for metabolome analysis. One of the critical steps in the LC-MS metabolome analysis workflow is related to metabolite identification. Among the measured parameters, peak mass is commonly used to search against a database for potential metabolite matches. Higher accuracy mass measurement allows the use of a narrower mass tolerance window for mass search. While various types of mass analyzers can routinely measure a peak mass with an error of less than a few ppm, mass measurement accuracy is not uniform for peaks with different intensities, particularly for quadrupole time-of-flight (QTOF) MS. Herein we present a simple and convenient method to determine the relation between peak intensity and mass error in LC-QTOF-MS-based metabolome analysis, followed by intensity-dependent mass search (IDMS) of a database for metabolite matches. This method is based on running a series of sodium formate mass calibrants, as part of the standard operating procedure (SOP) in LC-MS data acquisition, and then curve-fitting the measured mass errors and peak intensities. We show that, in two different quadrupole time-of-flight (QTOF) mass analyzers, mass accuracy is generally reduced as peak intensity decreases, which is independent of m/z values in the range commonly used for metabolite detection (e.g., m/z < 1000). We demonstrate the improvement in metabolite matches using IDMS in the analyses of dansyl labeled standards and human urine samples. We have implemented the IDMS method in the freely available MCID database at www.mycompoundid.org, which is composed of 8021 known human endogenous metabolites and their predicted metabolic products (375,809 compounds from one metabolic reaction and 10,583,901 compounds from two reactions).

A Temporal Graph Model to Predict Chemical Transformations in Complex Dissolved Organic Matter.

Dissolved organic matter (DOM) is a complex mixture of thousands of natural molecules that undergo constant transformation in the environment, such as sunlight induced photochemical reactions. Despite molecular level resolution from ultrahigh resolution mass spectrometry (UHRMS), trends of mass peak intensities are currently the only way to follow photochemically induced molecular changes in DOM. Many real-world relationships and temporal processes can be intuitively modeled using graph data structures (networks). Graphs enhance the potential and value of AI applications by adding context and interconnections allowing the uncovering of hidden or unknown relationships in data sets. We use a temporal graph model and link prediction to identify transformations of DOM molecules in a photo-oxidation experiment. Our link prediction algorithm simultaneously considers educt removal and product formation for molecules linked by predefined transformation units (oxidation, decarboxylation, etc.). The transformations are further weighted by the extent of intensity change and clustered on the graph structure to identify groups of similar reactivity. The temporal graph is capable of identifying relevant molecules subject to similar reactions and enabling to study their time course. Our approach overcomes previous data evaluation limitations for mechanistic studies of DOM and leverages the potential of temporal graphs to study DOM reactivity by UHRMS.

Proteomic fingerprinting enables quantitative biodiversity assessments of species and ontogenetic stages in Calanus congeners (Copepoda, Crustacea) from the Arctic Ocean.

Species identification is pivotal in biodiversity assessments and proteomic fingerprinting by MALDI-TOF mass spectrometry has already been shown to reliably identify calanoid copepods to species level. However, MALDI-TOF data may contain more information beyond mere species identification. In this study, we investigated different ontogenetic stages (copepodids C1-C6 females) of three co-occurring Calanus species from the Arctic Fram Strait, which cannot be identified to species level based on morphological characters alone. Differentiation of the three species based on mass spectrometry data was without any error. In addition, a clear stage-specific signal was detected in all species, supported by clustering approaches as well as machine learning using Random Forest. More complex mass spectra in later ontogenetic stages as well as relative intensities of certain mass peaks were found as the main drivers of stage distinction in these species. Through a dilution series, we were able to show that this did not result from the higher amount of biomass that was used in tissue processing of the larger stages. Finally, the data were tested in a simulation for application in a real biodiversity assessment by using Random Forest for stage classification of specimens absent from the training data. This resulted in a successful stage-identification rate of almost 90%, making proteomic fingerprinting a promising tool to investigate polewards shifts of Atlantic Calanus species and, in general, to assess stage compositions in biodiversity assessments of Calanoida, which can be notoriously difficult using conventional identification methods.

Microbial metabolism changes molecular compositions of riverine dissolved organic matter as regulated by temperature

This study investigated the control of dissolved organic matter (DOM) molecular compositions by microbial community shifts under temperature regulation (range from 5 to 35 °C), using riverine DOM and in situ microorganisms as examples. The functioning of different microbial metabolisms, including the utilization and generation processes, was comprehensively analyzed. Though the overall quantity of DOM was less temperature-affected, more molecules were identified at moderate temperatures (e.g., 15 and 25 °C) and their accumulated mass peak intensities increased with the temperature. The results were ascribed to 1) the microbial production of macromolecular (m/z > 600) CHO, CHON, and CHONS species was stimulated at higher temperatures; 2) the microorganisms consumed more DOM molecules at both higher and lower temperatures; and 3) the simultaneously decreased utilization and increased generation of recalcitrant CHO and CHON molecules with m/z < 600 at higher temperatures. The strong correlations among the temperature, community structures, and DOM chemodiversity suggested that temperature promoted the community evenness to increase the DOM generation. In addition, the higher temperature decreased the abundance of microorganisms that utilized more recalcitrant molecules and produced fewer new molecules (e.g., Proteobacteria, Acinetobacter, and Erythrobacter) while increased others that functioned the opposite (e.g., Verrucomicrobia, Bacteroidetes, and Flavobacterium) to increase the DOM production. The constructed temperature-community-DOM chemistry relationship deepened the molecular-level understanding of DOM variations and provided implications for the warming future.

Evaluation of the Isotopic Abundance Ratio of Consciousness Energy Healing Treated L-Tryptophan Using LC-MS Spectrometry

L-tryptophan is an essential α-amino acid, necessary for the normal growth in newborns, nitrogen balance in adults, protein synthesis, precursor of serotonin, melatonin, niacin, and albeit inefficiently in human, also the precursor of indole alkaloids and auxins in plants. This current study was designed to investigate the impact of the Trivedi Effect®-Biofield Energy Healing Treatment (Blessing) on the structural properties and the isotopic abundance ratio of L-tryptophan using LC-MS analytical technique. L-tryptophan sample was divided into two parts, one part of L-tryptophan was considered as the control sample (no Biofield Energy Treatment was provided), while the second part was treated with the Trivedi Effect®-Consciousness Energy Healing Treatment/Blessing remotely by a renowned Biofield Energy Healer, Dahryn Trivedi and termed as the treated sample. The mass spectra of both the control and treated samples with respect to the chromatographic peak at retention time (Rt) 2.1 minutes exhibited the mass of the molecular ion peak adduct with hydrogen ion at m/z 205.08 (calcd for C11H13N2O2+, 205.1), along with low molecular fragmented mass peaks at m/z 188, 159, and 102 for C11H12N2O2+, C10H11N2+, and C8H6+, respectively were also observed. The isotopic abundance ratio of PM+1/PM (2H/1H or 13C/12C or 15N/14Nor17O/16O) in the treated L-tryptophan was significantly increased by 35.93% compared with the control sample. Hence,the 13C, 2H, 15N, and 17O contributions from C11H13N2O2+ to m/z 206.08 in the treated L-tryptophan was significantly increased compared to the control sample. It could be hypothesized that the changes in the isotopic abundance and mass peak intensities due to the modification in nuclei possibly through the interference of neutrino particles using the Trivedi Effect®-Consciousness Energy Healing Treatment. The Biofield Energy Treated/Blessed L-tryptophan with increased stable isotopic abundance ratio might have changed the physicochemical properties with higher force constant in the molecule. The new form of treated L-tryptophan would be a better and more stable in the supplements, nutraceutical, and pharmaceutical formulations, which would be advantageous for the prevention and treatment of pellagra, depression, kynurenine. It could also maintain the normal label of tryptophan and avoid increase of its metabolite, lower the neurotoxin and a metabotoxin behavior, glutaric aciduria type I (glutaric acidemia type I) disorder, eosinophilia-myalgia syndrome (EMS), incurable and sometimes fatal flu-like neurological condition, etc. As tryptophan is the precursor for the plant hormones like indole alkaloids and auxins, hence, this treated L-tryptophan would be advantageous for the improvement of yield, productivity, and quality of crops and other plants.

Superatomic Signature and Reactivity of Silver Clusters with Oxygen: Double Magic Ag 17 – with Geometric and Electronic Shell Closure

Understanding the stability and reactivity of silver clusters toward oxygen provides insights to design new materials of coinage metals with atomic precision. Herein, we report a systematic study o...

Quantification of Amyloid-β in Plasma by Simple and Highly Sensitive Immunoaffinity Enrichment and LC-MS/MS Assay.

Numerous immunoassays have been developed to quantify amyloid β1-40 (Aβ40) and amyloid β1-42 (Aβ42). Nevertheless, given the low concentration of Aβ and the high levels of interfering factors in plasma, quantification of plasma Aβ is still challenging. To overcome the problems related to the specificity of Aβ immunoassays, this study aimed to develop an immunoaffinity enrichment and LC-MS/MS (IA-MS) assay. We developed an IA-MS assay using antibody-labeled magnetic beads for purification and LC-MS/MS for Aβ quantification. To avoid the loss of Aβ due to aggregation in acidic buffer, we used alkaline elution buffer for immunoaffinity enrichment. The concentrations of the Aβs in plasma samples were measured, and the correlation between the plasma and cerebrospinal fluid (CSF) Aβ42/Aβ40 ratio was also evaluated. The intensities of the Aβ mass peaks were significantly higher with the alkaline elution buffer than with the acidic elution buffer (Aβ40: 3.6-fold, Aβ42: 5.4-fold). This assay exhibited high reproducibility (intra-assay and inter-assay precision, %CV <15), and the working ranges of Aβ40 and Aβ42 were determined to be 21.7 to 692.8 pg/mL and 5.6 to 180.6 pg/mL, respectively. The concentrations of Aβ40 and Aβ42 in plasma were measured by IA-MS, and the plasma Aβ42/Aβ40 ratio was correlated with the CSF Aβ42/Aβ40 ratio (rs = 0.439, P < 0.01). The IA-MS assay has sufficient analytic performance for measuring endogenous Aβ40 and Aβ42 in plasma. This assay can lead to new lines of clinical discovery related to amyloid pathology.

Chromatographic and Spectroscopic Evaluation of the Consciousness Energy Healing Treated Ashwagandha Root Extract

Ashwagandha (Withania somnifera) extract is a popular health supplement, used in many nutraceutical and pharmaceutical formulations for good health benefits along with the prevention and treatment of various human diseases. The purpose of this study was to evaluate the impact of The Trivedi Effect®-Consciousness Energy Healing Treatment on the characteristic properties of the phyto-compounds present in the ashwagandha root extract using LC-MS, GC-MS, and NMR spectroscopy. Ashwagandha root extract was divided into two parts, one part of the sample was termed as untreated/control sample, while the other part of the sample received The Trivedi Effect®-Biofield Energy Healing Treatment remotely by a renowned Biofield Energy Healer, Mr. Mahendra Kumar Trivedi and termed as Biofield Energy Treated sample. The LC-ESI-MS data revealed that the chromatographic peak area% of the phytoconstituents present in the treated sample was significantly altered in the range of 31.13% to 20.61% compared to the control sample. Similarly, the average peak area of the treated sample was significantly improved by 20.61% compared to the control sample. A total of 14 withanolides such as viscosa lactone B, dihydrowithanolide D, withanolide A, withanolide B, etc. were proposed with m/z 489, 473, 471, and 455 at the retention times (Rt ) of 13.2, 14.5, 14.8, and 18.2 minutes, respectively. At Rt 13.2 minutes (m/z: 489), the peak area% and mass peak intensity of the phytocompound in the treated ashwagandha were significantly increased by 2.57% and 14.83%, respectively compared with the control sample. Similarly, at Rt 14.5 minutes (m/z: 473), peak area% was increased by 3.76%, but the mass peak intensity was significantly decreased by 26.48% in the treated sample compared with the control sample. At Rt 14.8 minutes (m/z: 471), peak area % was same, but the mass peak intensity was increased by 2.74% in the treated ashwagandha compared with the control sample. Subsequently, at Rt 18.2 minutes (m/z: 455), peak area% was increased 1.01%, whereas the peak intensity was significantly decreased by 10.90% in case of the treated sample compared to the control sample. These findings intensify to assume that The Trivedi Effect®-Consciousness Energy Healing Treatment might be responsible for the overall improvement of relative concentrations and altered relative abundance of the phytoconstituents in the ashwagandha root extract compared to the control sample. This Biofield Energy Treated ashwagandha root extract would be helpful to design better nutraceutical/pharmaceutical formulations against inflammatory diseases, immunological disorders, sexual disorders, arthritis, stress, cancer, diabetes, aging, and other chronic infections.

Impact of Consciousness Energy Healing Treatment on the Isotopic Abundance Ratio of Sulfamethoxazole Using LC-MS and GC-MS Spectrometry

Sulfamethoxazole is a sulfonamide bacteriostatic antibiotic which is commonly used for the treatment of infections caused by bacteria. In this study, the impact of the Trivedi Effect®-Biofield Energy Healing Treatment on the structural properties and the isotopic abundance ratio of sulfamethoxazole was studied using LC-MS and GC-MS spectroscopy. Sulfamethoxazole sample was divided into two parts, one part of sulfamethoxazole was considered as control (no Biofield Energy Treatment was provided), while the second part was received the Consciousness Energy Healing Treatment remotely by a famous Biofield Energy Healer, Dahryn Trivedi and termed as a treated sample. The LC-MS spectra of both the samples at retention time (Rt ) 2.5 minutes exhibited the mass of the deprotonated molecular ion peak at m/z 252 [M-H]- . The peak area of the treated sulfamethoxazole was significantly increased by 42.96% compared to the control sample. The LC-MS based isotopic abundance ratio of PM+1/ PM in the treated sulfamethoxazole was significantly decreased by 49.56% compared with the control sample. Thus, 13C, 2 H, 15N, 17O, and 33S contributions from (C10H10N3 O3 S)- to m/z 253 in the treated sample were significantly decreased compared with the control sample. The GC-MS peak area% of the treated sample was significantly increased by 80.3% compared to the control sample. The GC-MS based isotopic abundance ratio of PM+1/PM and PM+2/PM in the treated sulfamethoxazole was significantly altered by 119.53% and -25.48%, respectively compared with the control sample. Hence, 13C, 2 H, 15N, 17O, 18O, 33S, and 34S contributions from (C10H11N3 O3 S)+ to m/z 254 and 255 in the treated sample were significantly altered compared with the control sample. The isotopic abundance ratios of PM+1/PM (2 H/1 H or 13C/12C or 15N/14N or 17O/16O or 33S/32S) and PM+2/ PM (18O/16O or 34S/32S) in the treated sulfamethoxazole were significantly altered compared to the control sample. It can be assumed that the changes in peak area%, isotopic abundance, and mass peak intensities could be due to changes in nuclei possibly through the interference of neutrino particles via the Trivedi Effect®. The new form of sulfamethoxazole would be more efficacious pharmaceutical formulations that might offer better solubility, dissolution, absorption, bioavailability and therapeutic response against urinary tract infections, tuberculosis, traveler’s diarrhoea, ear infections, shigellosis, bronchitis, and pneumocystis jiroveci pneumonia, etc.

Analysis of Isotopic Abundance Ratio of Consciousness Energy Healing Treated Metronidazole Using LC-MS and GC-MS Spectrometry

Metronidazole is an antibiotic and useful for the antibacterial and antiprotozoal medication. This study was performed to investigate the impact of the Trivedi Effect®-Biofield Energy Healing Treatment on the structural properties and the isotopic abundance ratio of metronidazole using LC-MS and GC-MS spectroscopy. Metronidazole sample was divided into two parts, one part of metronidazole was considered as control (no Biofield Energy Treatment was provided), while the second part was treated with the Trivedi Effect®-Consciousness Energy Healing Treatment remotely by a renowned Biofield Energy Healer, Alice Branton and termed as a treated sample. The LC-MS spectra of both the samples of metronidazole at the retention time (Rt) 2.61 minutes exhibited the mass of the protonated molecular ion peak at m/z 172 M+H+ (calculated for C6H10N3O3+, 172.07). The LC-MS based isotopic abundance ratio of PM+1/PM (2H/1H or 13C/12C or 15N/214N or 17O/16O) in the treated metronidazole was significantly increased by 8.24% compared with the control sample. Thus,13C, 2H, 15N,and17O contributions from (C6H10N3O3)+ to m/z 173 in the treated sample were significantly increased compared with the control sample. The GC-MS based isotopic abundance ratio of PM+1/PM in the treated metronidazole was significantly increased by 5.92% compared with the control sample. Hence,13C, 2H, 15N, and217O contributions from (C6H9N3O3)+ to m/z 172 in the Biofield Energy Treated sample were significantly increased compared with the control sample. However, the isotopic abundance ratio of PM+2/PM in the treated metronidazole was significantly decreased by 18.2% compared with the control sample. Hence,18O contributions from (C6H9N3O3)+ to m/z 173 in the treated sample were significantly decreased compared with the control sample. The isotopic abundance ratio of PM+1/PM (2H/1H or 13C/12C or 15N/14N or 17O/16O) and PM+2/PM (18O/16O) in the treated metronidazole was significantly altered compared to the control sample. From the results, it can be hypothesized that the changes in isotopic abundance and mass peak intensities could be due to changes in nuclei possibly through the interference of neutrino particles via the Trivedi Effect® - Consciousness Energy Healing Treatment. The new form of treated metronidazole would be better designing novel pharmaceutical formulations that might offer better therapeutic response against bacterial and protozoal infection in the vagina (bacterial vaginosis), stomach (giardiasis, trichomoniasis, pseudomembranous colitis), joints (pelvic inflammatory disease), liver, skin, brain, and respiratory tract, aspiration pneumonia, rosacea, intra-abdominal infections, lung abscess, fungating wounds, periodontitis, amoebiasis, oral infections, etc.

Precursor Intensity-Based Label-Free Quantification Software Tools for Proteomic and Multi-Omic Analysis within the Galaxy Platform.

For mass spectrometry-based peptide and protein quantification, label-free quantification (LFQ) based on precursor mass peak (MS1) intensities is considered reliable due to its dynamic range, reproducibility, and accuracy. LFQ enables peptide-level quantitation, which is useful in proteomics (analyzing peptides carrying post-translational modifications) and multi-omics studies such as metaproteomics (analyzing taxon-specific microbial peptides) and proteogenomics (analyzing non-canonical sequences). Bioinformatics workflows accessible via the Galaxy platform have proven useful for analysis of such complex multi-omic studies. However, workflows within the Galaxy platform have lacked well-tested LFQ tools. In this study, we have evaluated moFF and FlashLFQ, two open-source LFQ tools, and implemented them within the Galaxy platform to offer access and use via established workflows. Through rigorous testing and communication with the tool developers, we have optimized the performance of each tool. Software features evaluated include: (a) match-between-runs (MBR); (b) using multiple file-formats as input for improved quantification; (c) use of containers and/or conda packages; (d) parameters needed for analyzing large datasets; and (e) optimization and validation of software performance. This work establishes a process for software implementation, optimization, and validation, and offers access to two robust software tools for LFQ-based analysis within the Galaxy platform.

Agro Residues of Dendranthema x grandiflorum as Raw Material for a Potential Larvicidal Product

Residues of the chrysanthemum agroindustry from different cultivars of Dendranthema x grandiflorum are sold in the Vitoria (Espirito Santo State, Brazil) marketplaces. Because of the large of varieties of this hybrid species, this study aimed to confirm the chemical similarity of the residual material collected in one year at the commercial places in neighborhoods of the city (Vitoria) for using it as an homogenous raw material to prepare larvicidal products. Dichloromethane and methanol extracts were produced from 27 samples. Medium infrared (MIR) spectra were obtained in triplicate for the 54 extracts. MIR data were analyzed by principal components analysis (PCA), which divided the samples into two groups (GA1 and GA2) for dichloromethane extracts and into four groups (GB1, GB2, GB3 and GB4) for methanol extracts. The methanol extracts, we could see clear separation among the groups based on their classes of substances. The dichloromethane ones, it was possible to identify separation between GA1 and GA2 by classes of triterpene esters and diacylglycerols based on their mass peak intensities. Mixtures obtained from dichloromethane extracts (FA) and methanol extracts (FB) were assayed on Aedes aegypti larvae at the concentration 15 ppm. FB mixtures no larval mortality was observed, but FA mixtures were 100% active, possibly by the presence of fatty acids, triterpenes, steroids and alkamides in the samples of this group. These results show that residues of different varieties of the hybrid Dendranthema x grandiflorum generate chemically similar extracts, particularly for the lipophilic ones (FA), which can be used as a homogeneous raw material to obtain biologically active products, notably larvicides products.

Quantitative analysis of pesticide residues in tea by gas chromatography–tandem mass spectrometry with atmospheric pressure chemical ionization

In this study, gas chromatography–tandem mass spectrometry (GC–MS/MS) using an atmospheric pressure chemical ionization (APCI) source was applied for the quantitative analysis of pesticide residues in tea. To determine the optimum ionization conditions for multiresidue analysis, the full-scan mass spectra and peak intensities of pesticides were compared in the presence and absence of water as a modifier. When water was added as a modifier in the ion source, most of the target compounds formed [M+H]+ ions and exhibited enhanced intensities. However, compounds consisting of only carbon, hydrogen, and chlorine, such as aldrin, γ-hexachlorocyclohexane, and p,p′-dichlorodiphenyldichloroethane, typically formed M+· or fragment ions, whose intensities were significantly decreased by the addition of water. GC–MS/MS methods using APCI (without modifier addition) and electron ionization (EI) were validated for 16 pesticides in tea at spiking levels of 0.01 and 0.1 mg/kg. Unlike EI, signal suppression was observed for most compounds at a spiking level of 0.01 mg/kg using APCI; however, dilution of the samples minimized this effect. Using APCI, the trueness of the target compounds ranged from 77% to 121% at both spiking levels, except for pyrethrins owing to matrix effects, with relative standard deviations of less than 14%. For most compounds, these results were comparable with those obtained using EI. However, because the use of APCI limited fragmentation, this ionization technique offered significantly higher sensitivity and specificity than EI. Using APCI, linear calibration curves with coefficients of determination greater than 0.998 were obtained in the range of 0.0005–0.5 μg/mL for all compounds. These findings indicated that GC–MS/MS with APCI is applicable for the routine monitoring of pesticide residues, even in complex samples such as tea.

Consciousness Energy Healing Treatment and Its Impact on the Structural Properties and Isotopic Abundance Ratios of Thiamine

Thiamine (vitamin B1 ) is an essential water soluble vitamin required in all living cells for many cellular functions. The objective of the study was to investigate the impact of the Trivedi Effect® -Consciousness Energy Healing Treatment on the isotopic abundance ratios (PM+1/PM and PM+2/PM) and structural properties of thiamine hydrochloride using LC-MS, GC-MS, and NMR spectroscopy. Thiamine sample was divided into two parts, one part of the sample was termed as untreated/control thiamine, while the other part of the sample received the Trivedi Effect® -Biofield Energy Healing Treatment remotely by a renowned Biofield Energy Healer, Mr. Mahendra Kumar Trivedi and designated as Biofield Energy Treated thiamine. The LC-ESI-MS analysis of both the thiamine samples showed the mass of parent molecular ion at m/z 265.03 (calcd for C12H17N4 OS+ , 265.11) at the retention times (Rt ) 1.51 minutes with similar fragmentation pattern. But, the relative peak intensities of the treated sample were significantly improved compared to the control sample. The isotopic abundance ratios of PM+1/PM (2 H/1 H or 13C/12C or 15N/14N or 17O/16O or 33S/32S) and PM+2/PM (18O/16O or 34S/32S) were significantly increased by 43.60% and 42.68%, respectively in the treated thiamine compared to the control sample. Therefore, 2 H, 13C, 15N, 17O, and 33S contributions from C12H17N4 OS+ to the isotopic m/z 266 and 18O and 34S contributions to the isotopic m/z 267 was significantly increased in the treated sample compared with the control sample. The GC-MS mass peak intensity of the treated sample (52940.7) was significantly increased by 131.01% compared to the control sample (22917.04). The proton and carbon signals for CH3 , CH2 , NH2 , CH, =C=, and C-OH groups in the 1 H and 13C NMR spectra of the control and treated samples were similar. The increased mass peak intensities and isotopic abundance ratios in thiamine might be due to the Trivedi Effect® -Consciousness Energy Healing Treatment via the possible mediation of neutrinos, which may change the intra-atomic bond strength, its physical stability, kinetic isotope effects of the treated thiamine. Thus, the Trivedi Effect® -Consciousness Energy Healing Treated thiamine would be advantageous for designing better nutraceuticals and pharmaceutical formulations which might provide better therapeutic response against vitamin B1 deficiency and related disorders, including beriberi, Korsakoff’s syndrome, Parkinson’s and Alzheimer’s diseases, maple syrup urine disease, Leigh’s disease, optic neuropathy, alcoholism, and aging.

Supporting the Teaching of Infrared Spectroscopy Concepts Using a Physical Model

A physical model has been designed to help students visualize concepts involved when solving infrared spectra. The physical model uses balls and springs to incorporate the harmonic oscillator model and Hooke’s law to study dynamic vibrations within diatomic molecules. Various concepts are addressed with the model to abstract principles about how bonds interact with infrared light as well as how reduced mass, bond order, electronegativity, bond dipole, and bond polarity influence peak position and peak intensity in a spectrum. The model has a corresponding activity developed to maximize applicable heuristics and deter the need for memorization based on functional groups or surface features. The model has been thoroughly tested in organic chemistry laboratories where students have successfully used the concepts to justify peak position and explain peak intensity in infrared spectra.

Changes in Dissolved Organic Matter Composition and Disinfection Byproduct Precursors in Advanced Drinking Water Treatment Processes.

Molecular changes in dissolved organic matter (DOM) from treatment processes at two drinking water treatment plants in Japan were investigated using unknown screening analysis by Orbitrap mass spectrometry. DOM formulas with carbon, hydrogen and oxygen (CHO-DOM) were the most abundant class in water samples, and over half of them were commonly found at both plants. Among the treatment processes, ozonation induced the most drastic changes to DOM. Mass peak intensities of less saturated CHO-DOM (positive (oxygen subtracted double bond equivalent per carbon (DBE-O)/C)) decreased by ozonation, while more saturated oxidation byproducts (negative (DBE-O)/C) increased and new oxidation byproducts (OBPs) were detected. By Kendrick mass analysis, ozone reactions preferred less saturated CHO-DOM in the same alkylation families and produced more saturated alkylation families of OBPs. Following ozonation, biological activated carbon filtration effectively removed <300 Da CHO-DOM, including OBPs. Following chlorination, over 50 chlorinated formulas of disinfection byproducts (DBPs) were found in chlorinated water samples where at least half were unknown. Putative precursors of these DBPs were determined based on electrophilic substitutions and addition reactions. Ozonation demonstrated better decomposition of addition reaction-type precursors than electrophilic substitution-type precursors; over half of both precursor types decreased during biological activated carbon filtration.

An algorithm to correct saturated mass spectrometry ion abundances for enhanced quantitation and mass accuracy in omic studies

The mass accuracy and peak intensity of ions detected by mass spectrometry (MS) measurements are essential to facilitate compound identification and quantitation. However, high concentration species can yield erroneous results if their ion intensities reach beyond the limits of the detection system, leading to distorted and non-ideal detector response (e.g. saturation), and largely precluding the calculation of accurate m/z and intensity values. Here we present an open source computational method to correct peaks above a defined intensity (saturated) threshold determined by the MS instrumentation such as the analog-to-digital converters or time-to-digital converters used in conjunction with time-of-flight MS. In this method, the isotopic envelope for each observed ion above the saturation threshold is compared to its expected theoretical isotopic distribution. The most intense isotopic peak for which saturation does not occur is then utilized to re-calculate the precursor m/z and correct the intensity, resulting in both higher mass accuracy and greater dynamic range. The benefits of this approach were evaluated with proteomic and lipidomic datasets of varying complexities. After correcting the high concentration species, reduced mass errors and enhanced dynamic range were observed for both simple and complex omic samples. Specifically, the mass error dropped by more than 50% in most cases for highly saturated species and dynamic range increased by 1–2 orders of magnitude for peptides in a blood serum sample.

A new approach for evaluating transformations of dissolved organic matter (DOM) via high-resolution mass spectrometry and relating it to bacterial activity

Streams are important sites of transformation of dissolved organic matter (DOM). The molecular characterization of DOM-quality changes requires sophisticated analytical evaluation techniques. The goal of our study was to link molecular DOM transformation with bacterial activity. We measured the degradation of leaf leachate over a gradient of bacterial production obtained by different rates of percolation of sediments in seven experimental flumes on five sampling dates. We developed a new strategy for evaluating molecular formula data sets obtained by ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS), in which the time-dependent change of component abundance was fitted by a linear regression model after normalization of mass peak intensities. All components were categorized by calculating the slope (change of percent intensity per day) in each of the seven flumes. These slopes were then related to cumulative bacterial production. The concentration of DOM decreased quickly in all flumes. Bacterial activity was higher in flumes with percolated sediment than in those without percolation, whereas plankton bacterial activity was higher in flumes without percolation or without sediment. There were no differences in molecular-DOM characteristics between flumes, but there were distinct changes over time. Positive slopes, i.e. increasing intensities over time, were found for small molecules (MW < 450 Da) and high O/C ratios, whereas decreasing intensities were observed less often and only for large molecules and low O/C ratios. The positive slopes of produced components showed a positive relationship to bacterial production for small and for oxygen-rich components. The negative slopes of degraded components were negatively related to bacterial production for large and for oxygen-deficient molecules. Overall, the approach provided new insights into the transformation of specific molecular DOM components.

LC-MS, GC-MS, and NMR Spectroscopy Based Evaluation of the Energy of Consciousness Healing Treated Withania somnifera (Ashwagandha) Root Extract

Withania somnifera root extract which contains withanolides as major active constituent and it is used traditionally for the prevention and treatment of several diseases. The objective of the current study was to investigate the impact of The Trivedi Effect® - Consciousness Energy Healing Treatment on the structural properties of the ashwagandha root extract using LC-MS, GC-MS, and NMR spectroscopy. Ashwagandha root extract was divided into two parts – one part was control (without treatment), while other part was treated with the Consciousness Energy Healing Treatment remotely by twenty renowned Biofield Energy Healers and defined as the Biofield Energy Treated sample. The LC-MS analysis revealed that the retention time of the phytoconstituents remained same in the control and Biofield Energy Treated samples, whereas the peak area% i.e. the relative amount of the phytoconstituents at respective retention time was significantly altered. The peak area% at Rt of 5.6, 6.8, 6.9, 7.2, 7.9, 8.4, 8.5, 8.6, and 9.2 minutes of the treated sample were increased significantly in the range of 1.46% to 253.06% compared to the control sample. In the contrary, the peak area% of the treated sample at Rt of 6.4 and 8.2 minutes were significantly decreased by 12.72% and 17.35%, respectively with respect to the control sample. A total of 16 withanolides such as withanoside IV, coagulin Q, viscosa lactone B, dihydrowithanolide D, withanolide A, withaferin A, withanone, withanolide D, ixocarpalactone A, withanolide sulfoxide, withanolide B, etc. were proposed with their structure from the molecular mass at m/z 783, 621, 489, 473, 767, 471, 505, and 992 at retention times of 6.4, 6.8, 7.2, 7.9, 8.2, 8.4, and 9.1 minutes, respectively with the help of LC-MS, GC-MS and NMR data of both the control and Biofield Energy Treated samples. The mass peak intensities of the Biofield Energy Treated sample were significantly changed in the range of -81.36% to 1720.90% compared with the control sample at the same retention time. These findings suggest that The Trivedi Effect® - Consciousness Energy Healing Treatment could be beneficial for altering the concentration of the phytoconstituents in the ashwagandha root extract by modifying their intrinsic physicochemical properties, which might be helpful to improve the bioavailability of active constituents of W. somnifera extract that might provide better therapeutic response against inflammatory diseases, immunological disorders, stress, arthritis, cancer, diabetes, sexual disorders, aging, and other chronic infections.