Major Fragments Research Articles

On the Systematics of Mass Spectrometry: A New Graph-Theoretical Method

The systematic background of mass spectrometry (MS) was established by using the Valency Interaction Formula theory in an efficient manner. A new graph theoretical method was developed as a pure quantum mechanical survey and applied on a variety of molecules and assemblies to elucidate the quantum mechanical systematics behind mass spectrometry. The topological indexes and graph theoretical methods in chemistry and physics as the striking features of this new method was applied onto the mass spectra of several molecules and assemblies due to the insufficiencies of the obselete fragmentation procedures. These fundamental topological indexes were determined to make quick deductions pictorially on the mass spectra of molecules. The major fragmentation pathways for several molecules, as the striking features of Mass Spectometry, were examined in a pure theoretical way and a priori decomposition products were predicted. The systematic theory was provided in the light of our examination and a great deal of qualitative information was obtained just by knowing which interactions are soft among the others. The results are of general validity in comparison with the experimental data.

How Biotic Differentiation of Human Impacted Nutrient Poor Deciduous Forests Can Affect the Preservation Status of Mountain Forest Vegetation

A significant loss of biodiversity resulting from human activity has caused biotic homogenisation to become the dominant process shaping forest communities. In this paper, we present a rare case of biotic differentiation in European temperate deciduous forest herb layer vegetation. The process is occurring in nutrient poor oak-hornbeam forests in mountain areas (Polish Eastern Carpathians, Central Europe) where non-timber use was converted into conventional forest management practice. This change contributed to increases in the nitrogen content and pH reaction of the soil that, contrary to predominant beliefs on the negative impact of habitat eutrophication on diversity, did not result in a decrease in the latter. We discuss possible reasons for this phenomenon that indicate the important role of tree stand composition (an increasing admixture of beech worsening the trophic properties of the soil). The second issue considered involves the effect of the changes in herb species composition of oak-hornbeam forest on its distinctiveness from the beech forest predominating in the Polish Eastern Carpathians. Unfortunately, despite the increase in the species compositional dissimilarity of oak-hornbeam forest, a reduction in their distinctiveness in relation to the herb species composition of beech forest was found. Such a phenomenon is an effect of the major fragmentation of oak-hornbeam forests, a spread of beech forest-type species, and forest management that gives preference to beech trees. Consequently, it can be expected that changes occurring in oak-hornbeam forest vegetation will contribute to a decrease in the forest vegetation variability at the regional scale.

Electron-Induced Fragmentation of Methylated Formamides

At an electron ionization of 70eV, all cationic fragments for N,N-dimethylformamide (DMF) and N-methylformamide (NMF) were detected with a quadrupole mass spectrometer and confirmed using isotopically-labelled molecules. Ion efficiency curves near the threshold region (5–20eV) for all of the major cationic fragments were measured and fit with a Wannier-type function to determine their appearance energies (AEs). Possible reaction pathways for the formation of each observed cation were proposed, and the corresponding enthalpies (ΔH⁰s) of reaction were evaluated from quantum chemical calculations using the Gaussian09 computational quantum chemistry package. Our results suggest that hydrogen loss for both molecules occurs primarily from the carbonyl carbon. We confirm that hydrogen transfer from the carbonyl site to the nitrogen site occurs during amide bond cleavage. The resultant cations, C2H6N+ and CH4N+, and their further fragments, formed by losing an H atom, H2, or C2H2, were first identified in mass spectra and were further probed by comparing the AEs with calculated ΔH⁰s of all possible formation pathways. Additionally, we suggest that hydrogen transfer also occurs when the N-CH3 bond breaks in DMF. This detailed study of the simplest molecule with the peptide linkage contributes to our understanding of electron impact on peptide-like molecules.

Exploring Protein Stability by Comparative Molecular Dynamics Simulations of Homologous Hyperthermophilic, Mesophilic, and Psychrophilic Proteins

In the present studies, we analyzed the influence of temperature on the stability and dynamics of the α subunit of tryptophan synthase (TRPS) from hyperthermophilic, mesophilic, and psychrophilic homologues at different temperatures by molecular dynamics simulations. Employing different indicators such as root-mean-square deviations, root-mean-square fluctuations, principal component analysis, and free energy landscapes, this study manifests the diverse behavior of these homologues with changes in temperature. Especially, an enhancement in the collective motions, classified as representative motions, is observed at high temperature. Similarly, the criterion for the selection of electrostatic interactions in terms of their life span (duty cycle) has indeed helped in identifying the short- and long-lived electrostatic interactions and how they affect the protein's overall stability at different temperatures. Rigidity and flexibility patterns of the homologous proteins are examined using FIRST software along with the calculation of duty cycles with various threshold limits at different temperatures. Rigid cluster decomposition in TRPS of psychrophilic, mesophilic, and hyperthermophilic origin identifies the flexible and rigid regions in the protein. Early loss of rigidity is observed in mesophilic TRPS via loss of contact between the major fragments of the protein compared with the other homologues. In spite of the high similarity of their three-dimensional structures, the overall responses of the three proteins to varying temperatures are significantly different.

GC–MS, MS/MS and GC–IR Analysis of a Series of Methylenedioxyphenyl-Aminoketones: Precursors, Ring Regioisomers and Side-Chain Homologs of 3,4-Methylenedioxypyrovalerone

A combination of GC-MS, MS/MS and GC-IR techniques were used to characterize the ring substitution pattern, the alkyl side-chain and the cyclic tertiary amine portions of a series of six homologous and regioisomeric methylenedioxyphenyl-aminoketones related to the designer drug, 3,4-methylenedioxypyrovalerone (MDPV). Chromatographic retention increases with the hydrocarbon content of the alkyl side-chain and the 3,4-methylenedioxy substitution pattern shows higher retention than the corresponding 2,3-methylenedioxy isomer. The aminoketones show major peaks in their mass spectra corresponding to the homologous series of iminium cation fragments from the loss of the regioisomeric methylenedioxybenzoyl radical species. Deuterium labeling experiments confirm the iminium cation base peaks to undergo the loss of a hydrocarbon molecular fragment to yield product ions characteristic of the side-chain andpyrrolidine ring portion of the parent cathinone derivative. The mass spectra for the designer drug MDPV and its regioisomeric 2,3-methylenedioxy isomer show equivalent fragments including the base peak at m/z 126 and major product ion fragments at m/z 84. The ring substitution pattern for these two isomers was differentiated by characteristic absorption bands in the 1,500 -1,200 cm-1 range in their vapor phase IR. These characteristic bands can also be used to identify the aromatic ring substitution pattern in the regioisomeric precursor ketones.

Future of Islamic Civilization, Emerging Issues and New Horizons: A Study of Malaysian Islamic Movements

This paper investigates four dimensions of Islamic Movements in Malaysian context. The first one is about the impacts of Islamic Movements instigating the development of Islamic civilization in Malaysia. Second one deals with emerging issues and modern trends in their futuristic approach and strategy. Third one evaluates sanity and diversity in issues and conflicts both in local and global perspectives. Finally, it examines the Western response and transformational role of the external world. General elections 2013 in Malaysia has marked a huge sign on the future politics of the country. National Front (BN: Barisan Nasional) faced major setback of fifty years in the history of Malaysian politics, government was unable to amend the constitution due to the absence of two third majority in the parliament because opposition collation Pakatan Rakayat (PR) grown more than fifty percent votes and more seats in federal and state legislative assemblies. Islamic Party of Malaysia (PAS) is one of the major fragments of opposition alliance. Among other Islamic organizations of the country PAS has achieved better growth and proved itself a distinguished Muslim political power of the country. Political process seems to be a better and safe way to achieve their ultimate goal of Islamic Resurgence for prominent Islamic movements of the world including PAS. We observe lot of bindings, barriers and challenges for them in different countries like, Egypt, Algeria, and Tunisia etc. The paper analyses ideological commonalities of different Islamic Movements of the world and concludes that specific circumstances demand certain approaches and finds out that Islamic movements asserting on peaceful process to attain massive support andhandlings challenges both from world powers, Muslim secularists and radical youth groups.

Muramyl peptides activate innate immunity conjointly via YB1 and NOD2.

Bacterial cell wall muramyl dipeptide (MDP) and glucosaminyl-MDP (GMDP) are potent activators of innate immunity. Two receptor targets, NOD2 and YB1, have been reported; we investigated potential overlap of NOD2 and YB1 pathways. Separate knockdown of NOD2 and YB1 demonstrates that both contribute to GMDP induction of NF-κB expression, a marker of innate immunity, although excess YB1 led to induction in the absence of NOD2. YB1 and NOD2 co-migrated on sucrose gradient centrifugation, and GMDP addition led to the formation of higher molecular mass complexes containing both YB1 and NOD2. Co-immunoprecipitation demonstrated a direct interaction between YB1 and NOD2, a major recombinant fragment of NOD2 (NACHT-LRR) bound to YB1, and complex formation was stimulated by GMDP. We also report subcellular colocalization of NOD2 and YB1. Although YB1 may have other binding partners in addition to NOD2, maximal innate immunity activation by muramyl peptides is mediated via an interaction between YB1 and NOD2.

A novel capped Pd nano-particle GC–MS technique for the identification of terpenoid sulfoxides in petroleum condensates

Capped palladium (Pd) nano-particle column chromatography was first used to separate a novel series of high molecular weight terpenoid sulfoxides (HMTSs) from petroleum condensate oil within the heterocyclic polyaromatic sulfur compound (S-PAH) fraction. The separation technique was based on complex formation between nano-sized heavy charged Pd2+ ions and sulfoxide ligands. HMTSs were identified by interpretation of GC–MS fragmentation patterns. The infrared spectra of the pre-isolated S-PAH fraction confirmed the presence of sulfoxide groups with an absorption band at 1264cm−1. The novel HMTS series included three members with the general formula C20H34OSR (main compound C25H44OS). The mass spectra of these three compounds were characterized by a major fragment ion at m/z 322. We identified a relationship between oil emergence and HTMS structure, indicating a base cross-linked macromolecular structure for the tested petroleum condensates and volatile oils. Atomic emission detection (AED) was unable to detect HMTS in spite of its sulfur atoms, most likely due to the high carbon to sulfur atom ratio producing quenching.

N-[18F]-FluoropropylJDTic for κ-opioid receptor PET imaging: Radiosynthesis, pre-clinical evaluation, and metabolic investigation in comparison with parent JDTic

IntroductionTo image kappa opioid receptor (KOR) for preclinical studies, N-fluoropropylJDTic 9 derived from the best-established KOR antagonist JDTic, was labeled with fluorine-18. MethodsRadiosynthesis of [18F]9 was achieved according to an automated two-step procedure from [18F]-fluoride. Peripheral and cerebral distributions were determined by ex vivo experiments and by PET imaging in mouse. Radiometabolism studies were performed both in vivo in mice and in vitro in mouse and human liver microsomes. Identification of the major metabolic fragmentations was carried out by UPLC-MS analysis of enzymatic cleavage of non-radioactive ligand 9. Microsomal metabolic degradation of parent JDTic was also achieved for comparison. ResultsThe radiotracer [18F]9 was produced after 140±5min total synthesis time (2.2±0.4% not decay corrected radiochemical yield) with a specific activity of 41–89GBq/μmol (1.1–2.4Ci/μmol). Peripheral and regional brain distributions of [18F]9 were consistent with known KOR locations but no significant specific binding in brain was shown. [18F]9 presented a typical hepatobiliary and renal elimination, and was rapidly metabolized. The in vivo and in vitro radiometabolic profiles of [18F]9 were similar. Piperidine 12 was identified as the major metabolic fragment of the non-radioactive ligand 9. JDTic 7 was found to be much more stable than 9. ConclusionAlthough the newly proposed radioligand [18F]9 was concluded to be not suitable for KOR PET imaging due to the formation of brain penetrating radiometabolites, our findings highlight the metabolic stability of JDTic and may help in the design of novel JDTic derivatives for in vivo applications.

Deamidation Reactions of Asparagine- and Glutamine-Containing Dipeptides Investigated by Ion Spectroscopy

Deamidation is a major fragmentation channel upon activation by collision induced dissociation (CID) for protonated peptides containing glutamine (Gln) and asparagine (Asn) residues. Here, we investigate these NH3-loss reactions for four Asn- and Gln-containing protonated peptides in terms of the resulting product ion structures using infrared ion spectroscopy with the free electron laser FELIX. The influence of the side chain length (Asn versus Gln) and of the amino acid sequence on the deamidation reaction has been examined. Molecular structures for the product ions are determined by comparison of experimental IR spectra with spectra predicted by density functional theory (DFT). The reaction mechanisms identified for the four dipeptides AlaAsn, AsnAla, AlaGln, and GlnAla are not the same. For all four dipeptides, primary deamidation takes place from the amide side chain (and not from the N-terminus) and, in most cases, resembles the mechanisms previously identified for the protonated amino acids asparagine and glutamine. Secondary fragmentation reactions of the deamidation products have also been characterized and provide further insight in – and confirmation of – the identified mechanisms. Overall, this study provides a comprehensive molecular structure map of the deamidation chemistry of this series of dipeptides. Graphical ᅟ Electronic supplementary materialThe online version of this article (doi:10.1007/s13361-016-1462-5) contains supplementary material, which is available to authorized users.

Interleukin-1α induces focal degradation of biglycan and tissue degeneration in an in-vitro ovine meniscal model

We have developed an ovine meniscal explant model where the focal degradative events leading to characteristic fragmentation patterns of biglycan in human OA of the knee and hip, and evident in animal models of knee OA and IVD degeneration are reproduced in culture. Lateral and medial menisci were dissected into outer, mid and inner zones and established in explant culture±IL-1 (10ng/ml). The biglycan species present in conditioned media samples and in GuHCl extracts of tissues were examined by Western blotting using two C-terminal antibodies PR-85 and EF-Bgn. Clear differences were evident in the biglycan species in each meniscal tissue zone with the medial outer meniscus having lower biglycan levels and major fragments of 20, 28, 33 and 36, 39kDa. Similar fragmentation was detected in articular cartilage samples, 42-45kDa core protein species were also detected. Biglycan fragmentation was not as extensive in the IL-1 stimulated meniscal cultures with 36, 39, 42 and 45kDa biglycan species evident. Thus the medial meniscus outer zone displayed the highest levels of biglycan processing in this model and correlated with a major zone of meniscal remodelling in OA in man. Significantly, enzymatic digests of meniscal tissues with MMP-13, ADAMTS-4 and ADAMTS-5 have also generated similar biglycan species in-vitro. Zymography confirmed that the medial outer zone was the region of maximal MMP activity. This model represents a convenient system to recapitulate matrix remodelling events driven by IL-1 in pathological cartilages and in animal models of joint degeneration.

First observation of methane photochemical generation from an N,N-dimethylamino-substituted arene: the case of 4-(N,N-dimethylamino)benzaldehyde (DMABA)

The first observation of methane photochemical production from an N,N-dimethylamino-substituted arene (DMABA: 4-(N,N-dimethylamino)benzaldehyde) is described. UV irradiation (λ>298 nm) of DMABA isolated in a solid low temperature (10 K) argon matrix was found to lead to major unimolecular fragmentation of the compound to methane and 4-(methylideneamino)benzaldehyde (4MAB). This reaction channel was found to be strongly preferred over the photochemical decarbonylation, which is usually found as the major photochemical transformation undergone by matrix-isolated benzaldehydes. New structural and spectroscopic data for both the reactant molecule (DMABA) and its major observed photoproduct (4MAB) are also presented. The experimentally obtained results are supported by an extensive set of quantum chemical calculations undertaken using both ab initio (MP2) and density functional theory (DFT) methods.

Identification of five pyrrolidinyl substituted cathinones and the collision‐induced dissociation of electrospray‐generated pyrrolidinyl substituted cathinones

This article reports on the analytical properties of five pyrrolidinyl substituted cathinones: α-pyrrolidinononaphenone (α-PNP, 1), 4-chloro-α-pyrrolidinopropiophenone (4-Cl-α-PPP, 2), 4-chloro-α-pyrrolidinovalerophenone (4-Cl-α-PVP, 3), 5-dihydrobenzofuranpyrovalerone (5-DBFPV, 4), and 2-(pyrrolidin-1-yl)-1-(5,6,7,8-tetrahydronaphthalen-2-yl)hexan-1-one (β-THNPH, 5). These identifications were based on liquid chromatography-quadrupole time-of-flight-mass spectrometry (LC-QTOF-MS), gas chromatography-mass spectrometry (GC-MS) and nuclear magnetic resonance spectroscopy (NMR). To our knowledge, no analytical data about α-PNP, 4-Cl-α-PPP, 4-Cl-α-PVP, and β-THNPH have appeared until now, making this the first report on these compounds. Moreover, in order to study the collision-induced dissociation (CID) characteristic fragmentation routes of pyrrolidinyl substituted cathinones, a total number of 13 pyrrolidinyl substituted cathinones were selected and discussed. The major fragmentation pathways under CID mode are produced, leading to the formation of characteristic ions. Product ions of [M-C4 H9 N]+ and Cn H2n N+ indicate the presence of pyrrolidinyl substitution. Characteristic fragments are also produced via the cleavages of the CH-N(CH2 )4 bond and the CO-CHN bond. Copyright © 2016 John Wiley & Sons, Ltd.

A multifaceted computational report on the variants effect on KIR2DL3 and IFNL3 candidate gene in HCV clearance.

HCV infection causes acute and chronic liver diseases including, cirrhosis and hepatocellular carcinoma. Following HCV infection, spontaneous clearance occurs in approximately 20% of the population dependant upon HCV genotype. In this study, functional and non-functional variant analysis was executed for the classical and the latest HCV clearance candidate genes namely, KIR2DL3 and IFNL3. Initially, the functional effects of non-synonymous SNPs were assigned on exposing to homology based tools, SIFT, PolyPhen-2 and PROVEAN. Further, UTR and splice sites variants were scanned for the gene expression and regulation changes. Subsequently, the haplotype and CNV were also identified. The mutation H77Y of KIR2DL3 and R157Q, H156Y, S63L, R157W, F179V, H128R, T101M, R180C, and F176I of IFNL3 results in conservation, RMSD, total energy, stability, and secondary structures revealed a negative impact on the structural fitness. UTRscan and the splice site result indicate functional change, which may affect gene regulation and expression. The graphical display of selected population shows alleles like rs270779, rs2296370, rs10423751, rs12982559, rs9797797, and rs35987710 of KIR2DL3 and rs12972991, rs12980275, rs4803217, rs8109886, and rs8099917 of IFNL3 are in high LD with a measure of [Formula: see text] broadcasting its protective effect in HCV clearance. Similarly, CNV report suggests major DNA fragment loss that could have a profound impact on the gene expression affecting the overall phenotype. This roundup report specifies the effect of NK cell receptor, KIR2DL3 and IFNL3 variants that can have a better prospect in GWAS and immunogenetic studies leading to better understanding of HCV clearance and progression.

Sequence analysis of the pyruvylated galactan sulfate-derived oligosaccharides by negative-ion electrospray tandem mass spectrometry

Five sulfated oligosaccharide fragments, F1–F5, were prepared from a pyruvylated galactan sulfate from the green alga Codium divaricatum, by partial depolymerization using mild acid hydrolysis and purification with gel-permeation chromatography. Negative-ion electrospray tandem mass spectrometry with collision-induced dissociation (ES-CID-MS/MS) is attempted for sequence determination of the sulfated oligosaccharides. The sequence of F1 with homogeneous disaccharide composition was first characterized to be Galp-(4SO4)-(1 → 3)-Galp by detailed nuclear magnetic resonance spectroscopic analyses. The fragmentation pattern of F1 in the product ion spectra was established on the basis of negative-ion ES-CID MS/MS, which was then applied to sequence analysis of other sulfated oligosaccharides. The sequences of F2 and F3 were deduced to be Galp-(4SO4)-(1 → 3)-Galp-(1 → 3)-Galp-(1 → 3)-Galp and 3,4-O-(1-carboxyethylidene)-Galp-(6SO4)-(1 → 3)-Galp, respectively. The sequences of major fragments in F4 and F5 were also deduced. The investigation demonstrated that negative-ion ES-CID-MS/MS was an efficient method for the sequence analysis of the pyruvylated galactan sulfate-derived oligosaccharides which revealed the patterns of substitution and glycosidic linkages. The pyruvylated galactan sulfate-derived oligosaccharides were novel sulfated oligosaccharides different from other algal polysaccharide-derived oligosaccharides.

Dissociation Behavior of a TEMPO-Active Ester Cross-Linker for Peptide Structure Analysis by Free Radical Initiated Peptide Sequencing (FRIPS) in Negative ESI-MS.

We have synthesized a homobifunctional amine-reactive cross-linking reagent, containing a TEMPO (2,2,6,6-tetramethylpiperidine-1-oxy) and a benzyl group (Bz), termed TEMPO-Bz-linker, to derive three-dimensional structural information of proteins. The aim for designing this novel cross-linker was to facilitate the mass spectrometric analysis of cross-linked products by free radical initiated peptide sequencing (FRIPS). In an initial study, we had investigated the fragmentation behavior of TEMPO-Bz-derivatized peptides upon collision activation in (+)-electrospray ionization collision-induced dissociation tandem mass spectrometry (ESI-CID-MS/MS) experiments. In addition to the homolytic NO-C bond cleavage FRIPS pathway delivering the desired odd-electron product ions, an alternative heterolytic NO-C bond cleavage, resulting in even-electron product ions mechanism was found to be relevant. The latter fragmentation route clearly depends on the protonation of the TEMPO-Bz-moiety itself, which motivated us to conduct (-)-ESI-MS, CID-MS/MS, and MS3 experiments of TEMPO-Bz-cross-linked peptides to further clarify the fragmentation behavior of TEMPO-Bz-peptide molecular ions. We show that the TEMPO-Bz-linker is highly beneficial for conducting FRIPS in negative ionization mode as the desired homolytic cleavage of the NO-C bond is the major fragmentation pathway. Based on characteristic fragments, the isomeric amino acids leucine and isoleucine could be discriminated. Interestingly, we observed pronounced amino acid side chain losses in cross-linked peptides if the cross-linked peptides contain a high number of acidic amino acids. Graphical Abstract ᅟ.

Photodissociation dynamics of the methyl perthiyl radical at 248 and 193 nm using fast-beam photofragment translational spectroscopy.

The photodissociation dynamics of the methyl perthiyl radical (CH3SS) have been investigated using fast-beam coincidence translational spectroscopy. Methyl perthiyl radicals were produced by photodetachment of the CH3SS(-) anion followed by photodissociation at 248 nm (5.0 eV) and 193 nm (6.4 eV). Photofragment mass distributions and translational energy distributions were measured at each dissociation wavelength. Experimental results show S atom loss as the dominant (96%) dissociation channel at 248 nm with a near parallel, anisotropic angular distribution and translational energy peaking near the maximal energy available to ground state CH3S and S fragments, indicating that the dissociation occurs along a repulsive excited state. At 193 nm, S atom loss remains the major fragmentation channel, although S2 loss becomes more competitive and constitutes 32% of the fragmentation. The translational energy distributions for both channels are very broad at this wavelength, suggesting the formation of the S2 and S atom products in several excited electronic states.

What Matters Most? Factors Influencing International Students’ Satisfaction towards Cafeteria Foods

The Malaysian government is focusing on developing education tourism to boost tourist arrivals. Apart from acquiring education, students’ well-being in terms of food-consumption is a major fragment in a student’s life. This paper puts emphasize on evaluating tourist resources as a component of tourism development through identification of international students’ demands on food and how the foodservice suppliers should adjust to this. In particular, it will address international students’ satisfaction towards cafeteria foods in university foodservice in Malaysia via extracting the salient factors that matters most in their evaluation of quality food and food price. Qualitative approach via open ended comment cards were distributed among 55 international students during April 2013 and content analysis was done on the feedbacks gathered. Based on the findings, majority of international students were dissatisfied with the taste, nutrition, hygiene, temperature, freshness and price of the food served by the cafeterias. This study will add to the under-researched area of foodservice sector academically and practically via identification of factors which international students’ think are important as quality food with acceptable price towards their satisfaction in cafeteria dining. This will benefit the university foodservice operators in providing best practices as one of the tourism suppliers in enhancing tourism development. DOI: 10.5901/mjss.2016.v7n4p295

Evaluation of Isotopic Abundance Ratio in Biofield Energy Treated Nitrophenol Derivatives Using Gas Chromatography-Mass Spectrometry

Nitrophenols are the synthetic organic chemicals used for the preparation of synthetic intermediates, organophosphorus pesticides, and pharmaceuticals. The objective of the present study was to evaluate the effect of biofield energy treatment on the isotopic abundance ratios of PM+1/PM, and PM+2/PM in o- and m-nitrophenol using the gas chromatography-mass spectrometry. The o- and m-nitrophenol were divided into two parts - one part was control sample, and another part was considered as biofield energy treated sample, which received Mr. Trivedi’s biofield energy treatment (The Trivedi Effect® ). The biofield energy treated nitrophenols having analyzed at different time intervals were designated as T1, T2, T3, and T4. The GCMS analysis of both the control and biofield treated samples indicated the presence of the parent molecular ion peak of o- and mnitrophenol (C6H5NO3 + ) at m/z 139 along with major fragmentation peaks at m/z 122, 109, 93, 81, 65, and 39. The relative peak intensities of the fragmented ions in the biofield treated o- and m-nitrophenol were notably changed as compared to the control sample with respect to the time. The isotopic abundance ratio analysis using GC-MS revealed that the isotopic abundance ratio of PM+1/PM in the biofield energy treated o-nitrophenol at T2 and T3 was significantly increased by 14.48 and 86.49%, respectively as compared to the control sample. Consequently, the isotopic abundance ratio of PM+2/PM in the biofield energy treated sample at T2 and T3 was increased by 11.36, and 82.95%, respectively as compared to the control sample. Similarly, in m-nitrophenol, the isotopic abundance ratio of PM+1/PM in the biofield energy treated sample at T1, T3, and T4 was increased by 5.82, 5.09, and 6.40%, respectively as compared to the control sample. Subsequently, the isotopic abundance ratio of PM+2/PM at T1, T2, T3 and T4 in the biofield energy treated m-nitrophenol was increased by 6.33, 3.80, 16.46, and 16.46%, respectively as compared to the control sample. Overall, the isotopic abundance ratios of PM+1/PM (2H/1H or 13C/12C or 15N/14N or 17O/16O), and PM+2/PM (18O/16O) were altered in the biofield energy treated o- and m-nitrophenol as compared to the control increased in most of the cases. The biofield treated o- and m-nitrophenol that have improved isotopic abundance ratios might have altered the physicochemical properties and could be useful in pharmaceutical and chemical industries as an intermediate in the manufacturing of pharmaceuticals and other useful chemicals for the industrial application.

A Liquid Chromatography‐Quadrupole‐Time of Flight Mass Spectrometry (LC‐Q‐TOF MS) Study for Analyzing 35 Corticosteroid Compounds: Elucidation of MS/MS Fragmentation Pathways

Corticosteroids have been often found to be added to a dietary supplement for the purpose of illegally improving the effect of their products. Thus, it is imperative to develop or improve a method that enables one to rapidly and reliably analyze corticosteroids in health or dietary supplements, for the safety management purpose. In the present study, results from liquid chromatography‐quadrupole time‐of‐flight mass spectrometry (LC‐Q‐TOF‐MS) experiments for the selected 35 corticosteroid compounds are presented, which can be useful for the qualitative screening of corticosteroids in health or dietary supplements. Specifically, retention times, accurate mass data of the protonated steroids, m/z values of major fragment ions are given for the 35 corticosteroids. Further, fragmentation pathways for the selected steroids are also suggested. Based on the suggested fragmentation pathways, it was shown that an unknown steroid compound can be readily identified using the knowledge of a group of unique and specific common skeletal fragments. The high selectivity and sensitivity of the LC‐Q‐TOF‐MS/MS results combined with the knowledge of the fragmentation pathways can offer a new opportunity for rapid and accurate screening of corticosteroids, thus preventing health‐related incidents involving adulterated products and clamping down on illegally circulated health products.