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Gael De Paepe - One of the best experts on this subject based on the ideXlab platform.
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natural Isotopic Abundance 13c and 15n multidimensional solid state nmr enabled by dynamic nuclear polarization
Journal of Physical Chemistry Letters, 2019Co-Authors: Adam N Smith, Katharina Marker, Sabine Hediger, Gael De PaepeAbstract:Dynamic nuclear polarization (DNP) has made feasible solid-state NMR experiments that were previously thought impractical due to sensitivity limitations. One such class of experiments is the structural characterization of organic and biological samples at natural Isotopic Abundance (NA). Herein, we describe the many advantages of DNP-enabled ssNMR at NA, including the extraction of long-range distance constraints using dipolar recoupling pulse sequences without the deleterious effects of dipolar truncation. In addition to the theoretical underpinnings in the analysis of these types of experiments, numerous applications of DNP-enabled ssNMR at NA are discussed.
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Structural Fingerprinting of Protein Aggregates by Dynamic Nuclear Polarization-Enhanced Solid-State NMR at Natural Isotopic Abundance
Journal of the American Chemical Society, 2018Co-Authors: Adam Smith, Katharina Marker, Sabine Hediger, Talia Piretra, Jennifer Boatz, Irina Matlahov, Ravindra Kodali, Patrick Van Der Wel, Gael De PaepeAbstract:A pathological hallmark of Huntington's disease (HD) is the formation of neuronal protein deposits containing mutant huntingtin fragments with expanded polyglutamine (polyQ) domains. Prior studies have shown the strengths of solid-state NMR (ssNMR) to probe the atomic structure of such aggregates, but have required in vitro Isotopic labeling. Herein, we present an approach for the structural fingerprinting of fibrils through ssNMR at natural Isotopic Abundance (NA). These methods will enable the spectroscopic fingerprinting of unlabeled (e.g., ex vivo) protein aggregates and the extraction of valuable new long-range 13 C− 13 C distance constraints
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Interfacial Ca^2+ environments in nanocrystalline apatites revealed by dynamic nuclear polarization enhanced ^43Ca NMR spectroscopy
Nature Communications, 2017Co-Authors: Daniel Lee, César Leroy, Charlène Crevant, Laure Bonhomme-coury, Florence Babonneau, Danielle Laurencin, Christian Bonhomme, Gael De PaepeAbstract:The interfaces within bones, teeth and other hybrid biomaterials are of paramount importance but remain particularly difficult to characterize at the molecular level because both sensitive and selective techniques are mandatory. Here, it is demonstrated that unprecedented insights into calcium environments, for example the differentiation of surface and core species of hydroxyapatite nanoparticles, can be obtained using solid-state NMR, when combined with dynamic nuclear polarization. Although calcium represents an ideal NMR target here (and de facto for a large variety of calcium-derived materials), its stable NMR-active isotope, calcium-43, is a highly unreceptive probe. Using the sensitivity gains from dynamic nuclear polarization, not only could calcium-43 NMR spectra be obtained easily, but natural Isotopic Abundance 2D correlation experiments could be recorded for calcium-43 in short experimental time. This opens perspectives for the detailed study of interfaces in nanostructured materials of the highest biological interest as well as calcium-based nanosystems in general. Solid-state NMR can in principle be used to study calcium environments in biomaterials such as bones/teeth, but^43Ca lacks receptivity. Here the authors present an approach to acquire ^43Ca data for hydroxyapatite at its natural Isotopic Abundance, distinguishing between core and surface Ca sites.
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Welcoming natural Isotopic Abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP
Chemical Science, 2017Co-Authors: Katharina Marker, Sabine Hediger, Jeanmarie Mouesca, Subhradip Paul, Carlos Fernandez-de-alba, Daniel Lee, Gael De PaepeAbstract:The self-assembly of small organic molecules is an intriguing phenomenon, which provides nanoscale structures for applications in numerous fields from medicine to molecular electronics. Detailed knowledge of their structure, in particular on the supramolecular level, is a prerequisite for the rational design of improved self-assembled systems. In this work, we prove the feasibility of a novel concept of NMR-based 3D structure determination of such assemblies in the solid state. The key point of this concept is the deliberate use of samples that contain 13 C at its natural Isotopic Abundance (NA, 1.1%), while exploiting magic-angle spinning dynamic nuclear polarization (MAS-DNP) to compensate for the reduced sensitivity. Since dipolar truncation effects are suppressed to a large extent in NA samples, unique and highly informative spectra can be recorded which are impossible to obtain on an Isotopically labeled system. On the self-assembled cyclic diphenylalanine peptide, we demonstrate the detection of long-range internuclear distances up to $7 ˚ A, allowing us to observe p-stacking through 13 C-13 C correlation spectra, providing a powerful tool for the analysis of one of the most important non-covalent interactions. Furthermore, experimental polarization transfer curves are in remarkable agreement with numerical simulations based on the crystallographic structure, and can be fully rationalized as the superposition of intra-and intermolecular contributions. This new approach to NMR crystallography provides access to rich and precise structural information, opening up a new avenue to de novo crystal structure determination by NMR.
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a new tool for nmr crystallography complete 13c 15n assignment of organic molecules at natural Isotopic Abundance using dnp enhanced solid state nmr
Journal of the American Chemical Society, 2015Co-Authors: Katharina Marker, Sabine Hediger, Morgane Pingret, Jeanmarie Mouesca, Didier Gasparutto, Gael De PaepeAbstract:NMR crystallography of organic molecules at natural Isotopic Abundance (NA) strongly relies on the comparison of assigned experimental and computed NMR chemical shifts. However, a broad applicability of this approach is often hampered by the still limited 1H resolution and/or difficulties in assigning 13C and 15N resonances without the use of structure-based chemical shift calculations. As shown here, such difficulties can be overcome by 13C–13C and for the first time 15N–13C correlation experiments, recorded with the help of dynamic nuclear polarization. We present the complete de novo 13C and 15N resonance assignment at NA of a self-assembled 2′-deoxyguanosine derivative presenting two different molecules in the asymmetric crystallographic unit cell. This de novo assignment method is exclusively based on aforementioned correlation spectra and is an important addition to the NMR crystallography approach, rendering firstly 1H assignment straightforward, and being secondly a prerequisite for distance measu...
Snehasis Jana - One of the best experts on this subject based on the ideXlab platform.
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Isotopic Abundance Ratio Analysis of Biofield Energy Treated Indole using Gas Chromatography-Mass Spectrometry
2018Co-Authors: Mahendra Kumar Trivedi, Alice Branton, Dahryn Trivedi, Gopal Nayak, Kalyan Kumar Sethi, Snehasis JanaAbstract:The objective of the current experiment was to evaluate the effect of biofield energy treatment on the Isotopic Abundance ratio of PM+1/PM (2H/1H or 13C/12C or 15N/14N) in indole using the gas chromatography-mass spectrometry (GC-MS). The sample of organic compound indole was divided into two parts - one part was designated as a control sample (untreated), and another part was considered as biofield energy treated sample, which was subjected to Mr. Trivedi’s biofield energy treatment (The Trivedi Effect®). The biofield energy treated indole sample was analyzed at different time intervals and were symbolized as T1, T2, T3, and T4 to understand the effect of the biofield energy on Isotopic Abundance ratio with respect to the time. From the GC-MS spectra, the presence of the molecular ion peak C8H7N+ (m/z 117) along with major fragmented peaks C7H6+ (m/z 90), C7H5+ (m/z 89), C5H3+ (m/z 63), C4H2+ (m/z 50), C3H3+ (m/z 39), and C2H4 (m/z 28) were observed in both control and biofield treated samples. Only, the relative peak intensities of the fragmented ions in the biofield treated indole was notably changed as compared to the control sample with respect to the time. The Isotopic Abundance ratio analysis of indole using GC-MS revealed that the Isotopic Abundance ratio of PM+1/PM in the biofield energy treated indole at T1 and T2 was significantly decreased by 44.28 and 28.18% as compared to the control sample. On the contrary, the Isotopic Abundance ratio of PM+1/PM in the biofield energy treated sample at T3 and T4, was significantly increased by 41.22 and 180.88%, respectively as compared to the control sample. Overall, the Isotopic Abundance ratio of PM+1/PM (2H/1H or 13C/12C or 15N/14N) was significantly altered in the biofield energy treated indole as compared to the control with respect to the time. The biofield treated indole with the altered Isotopic Abundance ratio might have altered the physicochemical properties and rate of reaction. This biofield energy treated indole might be more useful as a chemical intermediate in the production of pharmaceuticals, chemicals, plastics, dyes, and perfumes.
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Determination of Isotopic Abundance of 13C/12C or 2H/1H and 18O/16O in Biofield Energy Treated 1-Chloro-3-Nitrobenzene (3-CNB) Using Gas Chromatography-Mass Spectrometry
Science Journal of Analytical Chemistry, 2016Co-Authors: Mahendra Kumar Trivedi, Alice Branton, Dahryn Trivedi, Gopal Nayak, Parthasarathi Panda, Snehasis JanaAbstract:1-Chloro-3-nitrobenzene (3-CNB) is an aromatic halo-amine compound used as chemical intermediate for the production of several fine chemicals like pharmaceuticals, dyes, agricultural chemicals, etc. The stable isotope ratio analysis has drawn attention in numerous fields such as agricultural, food authenticity, biochemistry, etc. The objective of the current research was to investigate the impact of the biofield energy treatment on the Isotopic Abundance ratios of PM+1/PM, PM+2/PM and PM+3/PM in 3-CNB using gas chromatography - mass spectrometry (GC-MS). The sample, 3-CNB was divided into two parts - one part was denoted as control and another part was referred as biofield energy treated sample that was treated with biofield energy (The Trivedi Effect®). T1, T2, T3, and T4 were represented to different time interval analysis of the biofield treated 3-CNB. The GC-MS spectra of the both control and biofield treated 3-CNB indicated the presence of molecular ion peak [M+] at m/z 157 (calculated 156.99 for C6H4ClNO2) along with same pattern of fragmentation. The relative intensities of the parent molecule and other fragmented ions of the biofield treated 3-CNB were improved as compared to the control 3-CNB. The percentage change of the Isotopic Abundance ratio of PM+1/PM was significantly increased in the biofield treated 3-CNB at T1, T2 and T3 by 11.62, 18.50, and 29.82%, respectively with respect to the control 3-CNB. Accordingly, the Isotopic Abundance ratio of PM+2/PM in the biofield treated 3-CNB at T2 and T3 was significantly improved by 15.22 and 35.09%, respectively as compared to the control sample. The Isotopic Abundance ratios of PM+1/PM and PM+2/PM in the biofield treated 3-CNB at T1 and T4 were changed as compared to the control sample. The percentage change of the Isotopic Abundance ratio of PM+3/PM was enhanced in the biofield treated 3-CNB at T1, T2, T3, and T4 by 4.67, 18.69, 31.31 and 6.08%, respectively as compared to the control 3-CNB. The Isotopic Abundance ratios of PM+1/PM, PM+2/PM and PM+3/PM in the biofield treated 3-CNB changed with the time. So, the biofield energy treated 3-CNB might exhibit the altered isotope effects such as altered physicochemical and thermal properties, binding energy, and the rate of the chemical reaction as compared to the control sample. The biofield energy treated 3-CNB might assist in designing for the synthesis of pharmaceuticals, agricultural chemicals, dyes, corrosion inhibitors and other several useful industrial chemicals.
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Isotopic Abundance Ratio Analysis of 1,2,3-Trimethoxybenzene (TMB) After Biofield Energy Treatment (The Trivedi Effect®) Using Gas Chromatography-Mass Spectrometry
American Journal of Applied Chemistry, 2016Co-Authors: Mahendra Kumar Trivedi, Alice Branton, Dahryn Trivedi, Gopal Nayak, Parthasarathi Panda, Snehasis JanaAbstract:1,2,3-Trimethoxybenzene (TMB) is one of the most versatile chemical used for the synthesis of several pharmaceuticals, dyes, polymers, organic compounds, etc. The stable isotope ratio analysis has increased attention day-by-days in several fields such as agricultural, food authenticity, biochemistry, medical research, etc. The current study was aimed to evaluate the effect of the biofield energy treatment on the Isotopic Abundance ratios of 13C/12C or 2H/1H or 17O/16O (PM+1/PM) and 18O/16O (PM+2/PM) in TMB using Gas chromatography - mass spectrometry (GC-MS) technique. TMB was divided into two parts - one part was denoted as control and another part was referred as biofield energy treated sample that was received through Mr. Trivediꞌs unique biofield energy (The Trivedi Effect®). The GC-MS of the biofield treated TMB was characterized at different time intervals considered as T1, T2, T3, and T4 to examine the impact of the biofield energy treatment on Isotopic Abundance ratio with respect to the time. The GC-MS spectra of the both control and biofield treated TMB exhibited the presence of molecular ion peak [M+] at m/z 168 (calculated 168.08 for C9H12O3) along with similar pattern of fragmentation. The relative peak intensities of the fragmented ions in the biofield treated TMB, particularly at T2 and T3 was altered from the control sample. The Isotopic Abundance ratio analysis in the biofield treated TMB exhibited that the Isotopic Abundance ratio of PM+1/PM in the biofield treated TMB at T2 and T3 was significantly enhanced by 128.13 and 117.99%, respectively with respect to the control sample. Consequently, the percentage change in Isotopic Abundance ratio of PM+2/PM was significantly increased in the biofield treated TMB at T2 and T3 by 125.93 and 116.67%, respectively as compared with the control TMB. The Isotopic Abundance ratios (PM+1/PM and PM+2/PM) in the biofield treated TMB at T1 and T4 was altered with respect to the control TMB. In summary, 13C, 2H, and 17O contributions from (C9H12O3)+ to m/z 169 and 18O contribution from (C9H12O3)+ to m/z 170 for the biofield treated TMB, particularly at T2 and T3 were significantly improved and biofield treated TMB might exhibit changed isotope effects as compared to the control sample. The biofield treated TMB might assist to develop new chemicals and pharmaceuticals through using its kinetic isotope effects like understanding the reaction mechanism, the enzymatic transition state and all aspects of enzyme mechanisms.
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Gas Chromatography-Mass Spectrometric Analysis of Isotopic Abundance of 13C, 2H, and 18O in Biofield Energy Treated p-tertiary Butylphenol (PTBP)
American Journal of Chemical Engineering, 2016Co-Authors: Mahendra Kumar Trivedi, Alice Branton, Dahryn Trivedi, Gopal Nayak, Parthasarathi Panda, Snehasis JanaAbstract:p-tert-Butyphenol (PTBP) is a phenolic monomer used in the synthesis of numerous industrially useful chemicals. The current research work aimed to evaluate the effect of the biofield energy treatment on the Isotopic Abundance ratios of PM+1/PM and PM+2/PM in PTBP using gas chromatography - mass spectrometry (GC-MS). The sample, PTBP was distributed into two parts - one part was designated as control PTBP and another part was considered as biofield energy treated PTBP. The biofield energy treatment was achieved through unique biofield energy transmission process by Mr. Trivedi (also known as The Trivedi Effect®). T1, T2, T3, and T4 were indicated to the different time interval analysis of the biofield treated PTBP. The GC-MS spectra of the both control and biofield treated PTBP showed the presence of molecular ion peak [M+] at m/z 150 (calculated 150.10 for C10H14O) along with eight major fragmented peaks at m/z 135, 107, 95, 91, 77, 65, 41, and 39, which might be due to C10H15+, C7H7O+ or C8H11+, C6H7O+, C7H7+, C6H5+, C5H5+, C3H5+, and C3H3••+ ions, respectively. The relative intensities of the parent molecule and other fragmented ions of the biofield treated PTBP were altered as compared to the control PTBP. The percentage in the Isotopic Abundance ratio of PM+1/PM was enhanced in the biofield treated PTBP at T2, T3 and T4 by 1.60%, 3.57%, and 120.13%, respectively while it was decreased by 4.14% in the treated sample at T1 with respect to the control PTBP. Consequently, the Isotopic Abundance ratio of PM+2/PM was increased in the biofield treated PTBP at T1, T3, and T4 by 1.28%, 2.56%, and 123.08%, respectively with respect to the control sample. On the other hand, it was reduced in the biofield treated sample at T2 by 1.28% as compared to the control PTBP. Concisely, 13C, 2H, and 17O contributions from (C10H14O)+ to m/z 151 and 18O contribution from (C10H14O)+ to m/z 152 in the biofield treated PTBP were changed with respect to the control sample and was found to have time dependent effect. The biofield energy treated PTBP might display isotope effects such as different physicochemical and thermal properties, rate of the reaction, selectivity and binding energy due to the changed Isotopic Abundance ratio as compared to the control sample. Biofield treated PTBP could be valuable for the designing new chemicals and pharmaceuticals through using its kinetic isotope effects.
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Gas Chromatography-Mass Spectrometry Based Isotopic Abundance Ratio Analysis of Biofield Energy Treated Methyl-2-napthylether (Nerolin)
American Journal of Physical Chemistry, 2016Co-Authors: Mahendra Kumar Trivedi, Alice Branton, Dahryn Trivedi, Gopal Nayak, Kalyan Kumar Sethi, Snehasis JanaAbstract:Methyl-2-napthylether (nerolin) is an organic compound and has the applications in pharmaceutical, and perfume industry. The stable isotope ratio analysis is increasing importance in various field of scientific research. The objective of the current study was to evaluate the effect of the biofield energy treatment on the Isotopic Abundance ratios of PM+1/PM (2H/1H or 13C/12C or 17O/16O) and PM+2/PM (18O/16O) in nerolin using the gas chromatography-mass spectrometry (GC-MS). The compound nerolin was divided into two parts - one part was control sample (untreated), and another part was considered as biofield energy treated sample which was received the biofield energy treatment through the unique biofield energy transmission process by Mr. Mahendra Kumar Trivedi (also known as The Trivedi Effect®). The biofield energy treated nerolin was analyzed at different time intervals and were represented as T1, T2, T3, and T4 in order to understand the effect of the biofield energy treatment on Isotopic Abundance ratio with respect to the time. From the GC-MS spectral analysis, the presence of the molecular ion peak C11H10O+ (m/z 158) along with major fragmented peaks C10H7O- (m/z 143), C10H8 (m/z 128), C9H7+ (m/z 115), C7H5+ (m/z 89), C5H3+ (m/z 63), C4H3+ (m/z 51), and C3H3+ (m/z 39) were observed in both control and biofield treated samples. Only, the relative peak intensities of the fragmented ions in the biofield treated nerolin was notably changed as compared to the control sample with respect to the time. The Isotopic Abundance ratio analysis of nerolin using GC-MS revealed that the Isotopic Abundance ratio of PM+1/PM in the biofield energy treated nerolin at T1, T2, T3, and T4 was increased by 2.38, 138.10, 13.10, and 32.14%, as compared to the control sample. Likewise, the Isotopic Abundance ratio of PM+2/PM at T1, T2, T3, and T4 was increased by 2.38, 138.10, 13.10, and 32.14%, respectively in the biofield treated nerolin as compared to the control sample. Overall, the Isotopic Abundance ratios of PM+1/PM (2H/1H or 13C/12C or 17O/16O) and PM+2/PM (18O/16O) were significantly increased in the biofield energy treated sample as compared to the control sample with respect to the time. It is concluded that Mr. Trivedi’s biofield energy treatment has the significant impact on alteration in Isotopic Abundance of nerolin as compared to the control sample. The biofield treated nerolin might display different altered physicochemical properties and rate of reaction and could be an important intermediate for the production of pharmaceuticals, chemicals, and perfumes in the industry.
Katharina Marker - One of the best experts on this subject based on the ideXlab platform.
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natural Isotopic Abundance 13c and 15n multidimensional solid state nmr enabled by dynamic nuclear polarization
Journal of Physical Chemistry Letters, 2019Co-Authors: Adam N Smith, Katharina Marker, Sabine Hediger, Gael De PaepeAbstract:Dynamic nuclear polarization (DNP) has made feasible solid-state NMR experiments that were previously thought impractical due to sensitivity limitations. One such class of experiments is the structural characterization of organic and biological samples at natural Isotopic Abundance (NA). Herein, we describe the many advantages of DNP-enabled ssNMR at NA, including the extraction of long-range distance constraints using dipolar recoupling pulse sequences without the deleterious effects of dipolar truncation. In addition to the theoretical underpinnings in the analysis of these types of experiments, numerous applications of DNP-enabled ssNMR at NA are discussed.
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Structural Fingerprinting of Protein Aggregates by Dynamic Nuclear Polarization-Enhanced Solid-State NMR at Natural Isotopic Abundance
Journal of the American Chemical Society, 2018Co-Authors: Adam Smith, Katharina Marker, Sabine Hediger, Talia Piretra, Jennifer Boatz, Irina Matlahov, Ravindra Kodali, Patrick Van Der Wel, Gael De PaepeAbstract:A pathological hallmark of Huntington's disease (HD) is the formation of neuronal protein deposits containing mutant huntingtin fragments with expanded polyglutamine (polyQ) domains. Prior studies have shown the strengths of solid-state NMR (ssNMR) to probe the atomic structure of such aggregates, but have required in vitro Isotopic labeling. Herein, we present an approach for the structural fingerprinting of fibrils through ssNMR at natural Isotopic Abundance (NA). These methods will enable the spectroscopic fingerprinting of unlabeled (e.g., ex vivo) protein aggregates and the extraction of valuable new long-range 13 C− 13 C distance constraints
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Welcoming natural Isotopic Abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP
Chemical Science, 2017Co-Authors: Katharina Marker, Sabine Hediger, Jeanmarie Mouesca, Subhradip Paul, Carlos Fernandez-de-alba, Daniel Lee, Gael De PaepeAbstract:The self-assembly of small organic molecules is an intriguing phenomenon, which provides nanoscale structures for applications in numerous fields from medicine to molecular electronics. Detailed knowledge of their structure, in particular on the supramolecular level, is a prerequisite for the rational design of improved self-assembled systems. In this work, we prove the feasibility of a novel concept of NMR-based 3D structure determination of such assemblies in the solid state. The key point of this concept is the deliberate use of samples that contain 13 C at its natural Isotopic Abundance (NA, 1.1%), while exploiting magic-angle spinning dynamic nuclear polarization (MAS-DNP) to compensate for the reduced sensitivity. Since dipolar truncation effects are suppressed to a large extent in NA samples, unique and highly informative spectra can be recorded which are impossible to obtain on an Isotopically labeled system. On the self-assembled cyclic diphenylalanine peptide, we demonstrate the detection of long-range internuclear distances up to $7 ˚ A, allowing us to observe p-stacking through 13 C-13 C correlation spectra, providing a powerful tool for the analysis of one of the most important non-covalent interactions. Furthermore, experimental polarization transfer curves are in remarkable agreement with numerical simulations based on the crystallographic structure, and can be fully rationalized as the superposition of intra-and intermolecular contributions. This new approach to NMR crystallography provides access to rich and precise structural information, opening up a new avenue to de novo crystal structure determination by NMR.
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a new tool for nmr crystallography complete 13c 15n assignment of organic molecules at natural Isotopic Abundance using dnp enhanced solid state nmr
Journal of the American Chemical Society, 2015Co-Authors: Katharina Marker, Sabine Hediger, Morgane Pingret, Jeanmarie Mouesca, Didier Gasparutto, Gael De PaepeAbstract:NMR crystallography of organic molecules at natural Isotopic Abundance (NA) strongly relies on the comparison of assigned experimental and computed NMR chemical shifts. However, a broad applicability of this approach is often hampered by the still limited 1H resolution and/or difficulties in assigning 13C and 15N resonances without the use of structure-based chemical shift calculations. As shown here, such difficulties can be overcome by 13C–13C and for the first time 15N–13C correlation experiments, recorded with the help of dynamic nuclear polarization. We present the complete de novo 13C and 15N resonance assignment at NA of a self-assembled 2′-deoxyguanosine derivative presenting two different molecules in the asymmetric crystallographic unit cell. This de novo assignment method is exclusively based on aforementioned correlation spectra and is an important addition to the NMR crystallography approach, rendering firstly 1H assignment straightforward, and being secondly a prerequisite for distance measu...
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A New Tool for NMR Crystallography: Complete C-13/N-15 Assignment of Organic Molecules at Natural Isotopic Abundance Using DNP-Enhanced Solid-State NMR
Journal of the American Chemical Society, 2015Co-Authors: Katharina Marker, Sabine Hediger, Morgane Pingret, Jeanmarie Mouesca, Didier Gasparutto, Gael De PaepeAbstract:NMR crystallography of organic molecules at natural Isotopic Abundance (NA) strongly relies on the comparison of assigned experimental and computed NMR chemical shifts. However, a broad applicability of this approach is often hampered by the still limited H-1 resolution and/or difficulties in assigning C-13 and N-15 resonances without the use of structure-based chemical shift calculations. As shown here, such difficulties can be overcome by C-13-C-13 and for the first time N-15-C-13 correlation experiments, recorded with the help of dynamic nuclear polarization. We present the complete de novo C-13 and N-15 resonance assignment at NA of a self-assembled 2'-deoxyguanosine derivative presenting two different molecules in the asymmetric crystallographic unit cell. This de novo assignment method is exclusively based on aforementioned correlation spectra and is an important addition to the NMR crystallography approach, rendering firstly H-1 assignment straightforward, and being secondly a prerequisite for distance measurements with solid-state NMR.
Mahendra Kumar Trivedi - One of the best experts on this subject based on the ideXlab platform.
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Isotopic Abundance Ratio Analysis of Biofield Energy Treated Indole using Gas Chromatography-Mass Spectrometry
2018Co-Authors: Mahendra Kumar Trivedi, Alice Branton, Dahryn Trivedi, Gopal Nayak, Kalyan Kumar Sethi, Snehasis JanaAbstract:The objective of the current experiment was to evaluate the effect of biofield energy treatment on the Isotopic Abundance ratio of PM+1/PM (2H/1H or 13C/12C or 15N/14N) in indole using the gas chromatography-mass spectrometry (GC-MS). The sample of organic compound indole was divided into two parts - one part was designated as a control sample (untreated), and another part was considered as biofield energy treated sample, which was subjected to Mr. Trivedi’s biofield energy treatment (The Trivedi Effect®). The biofield energy treated indole sample was analyzed at different time intervals and were symbolized as T1, T2, T3, and T4 to understand the effect of the biofield energy on Isotopic Abundance ratio with respect to the time. From the GC-MS spectra, the presence of the molecular ion peak C8H7N+ (m/z 117) along with major fragmented peaks C7H6+ (m/z 90), C7H5+ (m/z 89), C5H3+ (m/z 63), C4H2+ (m/z 50), C3H3+ (m/z 39), and C2H4 (m/z 28) were observed in both control and biofield treated samples. Only, the relative peak intensities of the fragmented ions in the biofield treated indole was notably changed as compared to the control sample with respect to the time. The Isotopic Abundance ratio analysis of indole using GC-MS revealed that the Isotopic Abundance ratio of PM+1/PM in the biofield energy treated indole at T1 and T2 was significantly decreased by 44.28 and 28.18% as compared to the control sample. On the contrary, the Isotopic Abundance ratio of PM+1/PM in the biofield energy treated sample at T3 and T4, was significantly increased by 41.22 and 180.88%, respectively as compared to the control sample. Overall, the Isotopic Abundance ratio of PM+1/PM (2H/1H or 13C/12C or 15N/14N) was significantly altered in the biofield energy treated indole as compared to the control with respect to the time. The biofield treated indole with the altered Isotopic Abundance ratio might have altered the physicochemical properties and rate of reaction. This biofield energy treated indole might be more useful as a chemical intermediate in the production of pharmaceuticals, chemicals, plastics, dyes, and perfumes.
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Evaluation of Isotopic Abundance Ratio and Structural Properties of Magnesium Gluconate After Treatment with the Energy of Consciousness Using LC-MS and NMR Spectroscopy
Advances in Bioscience and Bioengineering, 2017Co-Authors: Mahendra Kumar Trivedi, Alice Branton, Dahryn Trivedi, Gopal Nayak, Cathryn Dawn Nykvist, Celine Lavelle, Daniel Paul Przybylski, Dianne Heather Vincent, Dorothy Felger, Douglas Jay KonersmanAbstract:The current research work was aimed to investigate the impact of The Trivedi Effect® - Energy of Consciousness Healing Treatment (Biofield Energy Healing) on the structural properties and Isotopic Abundance ratio (PM+1/PM) of magnesium gluconate using LC-MS and NMR spectroscopy. Magnesium gluconate was divided into two parts. One part was denoted as the control, while the another part was defined as The Trivedi Effect® Treated sample, which received the Biofield Energy Healing Treatment remotely from eighteen renowned Biofield Energy Healers. The total ion chromatogram of the control sample showed two peaks at Rt of 1.81 and 2.06 min, whereas the treated sample displayed peaks at Rt of 1.79 and 2.04 min. The ESI-MS spectra of the control and the treated samples revealed the presence of the mass for magnesium gluconate ion in two forms at m/z 447 (adduct form with methanol) and 415 (protonated ion) in positive ionization mode. But, it showed the mass for the gluconate ion at m/z 195 in the negative ionization mode. The fragmentation pattern of magnesium gluconate in the treated sample was notably altered compared with the control sample. The proton and carbon signals for CH, CH2 and CO groups in the proton and carbon NMR spectra were found almost similar for the control and treated samples. The LC-MS based Isotopic Abundance ratio analysis indicated that the PM+1/PM (2H/1H or 13C/12C or 17O/16O or 25Mg/24Mg) in the treated magnesium gluconate ion at m/z 415 was significantly decreased by 79.24% compared with the control sample. Similarly, the Isotopic Abundance ratio of PM+1/PM (2H/1H or 13C/12C or 17O/16O) in the gluconate ion was decreased by 6.62% in the treated sample compared with the control sample. The treated magnesium gluconate might be beneficial in the nutraceutical and/or pharmaceutical industries for designing various forms of formulations, which could be providing better therapeutic response against various diseases such as diabetes mellitus, allergy, aging, inflammatory diseases, immunological disorders, and other chronic infections. Consequently, The Trivedi Effect® - Energy of Consciousness Healing Treated magnesium gluconate would be more helpful for understanding the enzymatic reactions as well as assist in the designing of the novel potent enzyme inhibitors by applying its kinetic isotope effects.
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Mass Spectrometry Analysis of Isotopic Abundance of 13C, 2H, or 15N in Biofield Energy Treated Aminopyridine Derivatives
viXra, 2016Co-Authors: Mahendra Kumar Trivedi, Alice Branton, Dahryn Trivedi, Gopal NayakAbstract:2-Aminopyridine (2-AP) and 2,6-diaminopyridine (2,6-DAP) are two derivatives of aminopyridines that act as an important organic intermediates, mostly used in medicines, dyes and organic sensors. The aim of the study was to evaluate the impact of biofield energy treatment on Isotopic Abundance ratios of 2H/1H, 13C/12C, or 15N/14N, in aminopyridine derivatives using gas chromatography-mass spectrometry (GC-MS). The 2-AP and 2,6-DAP samples were divided into two parts: control and treated. The control sample remained as untreated, while the treated sample was further divided into four groups as T1, T2, T3, and T4. The treated group was subjected to Mr. Trivedi’s biofield energy treatment. The GC-MS spectra of 2-AP and 2,6- DAP showed five and six m/z peaks respectively due to the molecular ion peak and fragmented peaks of aminopyridine derivatives. The Isotopic Abundance ratio of 2H/1H, 13C/12C, or 15N/14N were calculated for both the derivatives and significant alteration was found in the treated samples as compared to the respective control. The Isotopic Abundance ratio of 2H/1H, 13C/12C, or 15N/14N in treated samples of 2-AP was decreased by 55.83% in T1 and significantly increased by 202.26% in T4. However, in case of 2,6-DAP, the Isotopic Abundance ratio of 2H/1H, 13C/12C, and 15N/14N, in the treated sample showed a significant increase (up to 370.54% in T3) with respect to the control. GC-MS data suggested that the biofield energy treatment on aminopyridine derivatives had significantly altered the Isotopic Abundance of 2H, 13C, or 15N in the treated 2-AP and 2,6- DAP as compared to the control.
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Determination of Isotopic Abundance of 13C/12C or 2H/1H and 18O/16O in Biofield Energy Treated 1-Chloro-3-Nitrobenzene (3-CNB) Using Gas Chromatography-Mass Spectrometry
Science Journal of Analytical Chemistry, 2016Co-Authors: Mahendra Kumar Trivedi, Alice Branton, Dahryn Trivedi, Gopal Nayak, Parthasarathi Panda, Snehasis JanaAbstract:1-Chloro-3-nitrobenzene (3-CNB) is an aromatic halo-amine compound used as chemical intermediate for the production of several fine chemicals like pharmaceuticals, dyes, agricultural chemicals, etc. The stable isotope ratio analysis has drawn attention in numerous fields such as agricultural, food authenticity, biochemistry, etc. The objective of the current research was to investigate the impact of the biofield energy treatment on the Isotopic Abundance ratios of PM+1/PM, PM+2/PM and PM+3/PM in 3-CNB using gas chromatography - mass spectrometry (GC-MS). The sample, 3-CNB was divided into two parts - one part was denoted as control and another part was referred as biofield energy treated sample that was treated with biofield energy (The Trivedi Effect®). T1, T2, T3, and T4 were represented to different time interval analysis of the biofield treated 3-CNB. The GC-MS spectra of the both control and biofield treated 3-CNB indicated the presence of molecular ion peak [M+] at m/z 157 (calculated 156.99 for C6H4ClNO2) along with same pattern of fragmentation. The relative intensities of the parent molecule and other fragmented ions of the biofield treated 3-CNB were improved as compared to the control 3-CNB. The percentage change of the Isotopic Abundance ratio of PM+1/PM was significantly increased in the biofield treated 3-CNB at T1, T2 and T3 by 11.62, 18.50, and 29.82%, respectively with respect to the control 3-CNB. Accordingly, the Isotopic Abundance ratio of PM+2/PM in the biofield treated 3-CNB at T2 and T3 was significantly improved by 15.22 and 35.09%, respectively as compared to the control sample. The Isotopic Abundance ratios of PM+1/PM and PM+2/PM in the biofield treated 3-CNB at T1 and T4 were changed as compared to the control sample. The percentage change of the Isotopic Abundance ratio of PM+3/PM was enhanced in the biofield treated 3-CNB at T1, T2, T3, and T4 by 4.67, 18.69, 31.31 and 6.08%, respectively as compared to the control 3-CNB. The Isotopic Abundance ratios of PM+1/PM, PM+2/PM and PM+3/PM in the biofield treated 3-CNB changed with the time. So, the biofield energy treated 3-CNB might exhibit the altered isotope effects such as altered physicochemical and thermal properties, binding energy, and the rate of the chemical reaction as compared to the control sample. The biofield energy treated 3-CNB might assist in designing for the synthesis of pharmaceuticals, agricultural chemicals, dyes, corrosion inhibitors and other several useful industrial chemicals.
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Gas Chromatography-Mass Spectrometric Analysis of Isotopic Abundance of 13C, 2H, and 18O in Biofield Energy Treated p-tertiary Butylphenol (PTBP)
American Journal of Chemical Engineering, 2016Co-Authors: Mahendra Kumar Trivedi, Alice Branton, Dahryn Trivedi, Gopal Nayak, Parthasarathi Panda, Snehasis JanaAbstract:p-tert-Butyphenol (PTBP) is a phenolic monomer used in the synthesis of numerous industrially useful chemicals. The current research work aimed to evaluate the effect of the biofield energy treatment on the Isotopic Abundance ratios of PM+1/PM and PM+2/PM in PTBP using gas chromatography - mass spectrometry (GC-MS). The sample, PTBP was distributed into two parts - one part was designated as control PTBP and another part was considered as biofield energy treated PTBP. The biofield energy treatment was achieved through unique biofield energy transmission process by Mr. Trivedi (also known as The Trivedi Effect®). T1, T2, T3, and T4 were indicated to the different time interval analysis of the biofield treated PTBP. The GC-MS spectra of the both control and biofield treated PTBP showed the presence of molecular ion peak [M+] at m/z 150 (calculated 150.10 for C10H14O) along with eight major fragmented peaks at m/z 135, 107, 95, 91, 77, 65, 41, and 39, which might be due to C10H15+, C7H7O+ or C8H11+, C6H7O+, C7H7+, C6H5+, C5H5+, C3H5+, and C3H3••+ ions, respectively. The relative intensities of the parent molecule and other fragmented ions of the biofield treated PTBP were altered as compared to the control PTBP. The percentage in the Isotopic Abundance ratio of PM+1/PM was enhanced in the biofield treated PTBP at T2, T3 and T4 by 1.60%, 3.57%, and 120.13%, respectively while it was decreased by 4.14% in the treated sample at T1 with respect to the control PTBP. Consequently, the Isotopic Abundance ratio of PM+2/PM was increased in the biofield treated PTBP at T1, T3, and T4 by 1.28%, 2.56%, and 123.08%, respectively with respect to the control sample. On the other hand, it was reduced in the biofield treated sample at T2 by 1.28% as compared to the control PTBP. Concisely, 13C, 2H, and 17O contributions from (C10H14O)+ to m/z 151 and 18O contribution from (C10H14O)+ to m/z 152 in the biofield treated PTBP were changed with respect to the control sample and was found to have time dependent effect. The biofield energy treated PTBP might display isotope effects such as different physicochemical and thermal properties, rate of the reaction, selectivity and binding energy due to the changed Isotopic Abundance ratio as compared to the control sample. Biofield treated PTBP could be valuable for the designing new chemicals and pharmaceuticals through using its kinetic isotope effects.
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natural Isotopic Abundance 13c and 15n multidimensional solid state nmr enabled by dynamic nuclear polarization
Journal of Physical Chemistry Letters, 2019Co-Authors: Adam N Smith, Katharina Marker, Sabine Hediger, Gael De PaepeAbstract:Dynamic nuclear polarization (DNP) has made feasible solid-state NMR experiments that were previously thought impractical due to sensitivity limitations. One such class of experiments is the structural characterization of organic and biological samples at natural Isotopic Abundance (NA). Herein, we describe the many advantages of DNP-enabled ssNMR at NA, including the extraction of long-range distance constraints using dipolar recoupling pulse sequences without the deleterious effects of dipolar truncation. In addition to the theoretical underpinnings in the analysis of these types of experiments, numerous applications of DNP-enabled ssNMR at NA are discussed.
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Structural Fingerprinting of Protein Aggregates by Dynamic Nuclear Polarization-Enhanced Solid-State NMR at Natural Isotopic Abundance
Journal of the American Chemical Society, 2018Co-Authors: Adam Smith, Katharina Marker, Sabine Hediger, Talia Piretra, Jennifer Boatz, Irina Matlahov, Ravindra Kodali, Patrick Van Der Wel, Gael De PaepeAbstract:A pathological hallmark of Huntington's disease (HD) is the formation of neuronal protein deposits containing mutant huntingtin fragments with expanded polyglutamine (polyQ) domains. Prior studies have shown the strengths of solid-state NMR (ssNMR) to probe the atomic structure of such aggregates, but have required in vitro Isotopic labeling. Herein, we present an approach for the structural fingerprinting of fibrils through ssNMR at natural Isotopic Abundance (NA). These methods will enable the spectroscopic fingerprinting of unlabeled (e.g., ex vivo) protein aggregates and the extraction of valuable new long-range 13 C− 13 C distance constraints
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Welcoming natural Isotopic Abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP
Chemical Science, 2017Co-Authors: Katharina Marker, Sabine Hediger, Jeanmarie Mouesca, Subhradip Paul, Carlos Fernandez-de-alba, Daniel Lee, Gael De PaepeAbstract:The self-assembly of small organic molecules is an intriguing phenomenon, which provides nanoscale structures for applications in numerous fields from medicine to molecular electronics. Detailed knowledge of their structure, in particular on the supramolecular level, is a prerequisite for the rational design of improved self-assembled systems. In this work, we prove the feasibility of a novel concept of NMR-based 3D structure determination of such assemblies in the solid state. The key point of this concept is the deliberate use of samples that contain 13 C at its natural Isotopic Abundance (NA, 1.1%), while exploiting magic-angle spinning dynamic nuclear polarization (MAS-DNP) to compensate for the reduced sensitivity. Since dipolar truncation effects are suppressed to a large extent in NA samples, unique and highly informative spectra can be recorded which are impossible to obtain on an Isotopically labeled system. On the self-assembled cyclic diphenylalanine peptide, we demonstrate the detection of long-range internuclear distances up to $7 ˚ A, allowing us to observe p-stacking through 13 C-13 C correlation spectra, providing a powerful tool for the analysis of one of the most important non-covalent interactions. Furthermore, experimental polarization transfer curves are in remarkable agreement with numerical simulations based on the crystallographic structure, and can be fully rationalized as the superposition of intra-and intermolecular contributions. This new approach to NMR crystallography provides access to rich and precise structural information, opening up a new avenue to de novo crystal structure determination by NMR.
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a new tool for nmr crystallography complete 13c 15n assignment of organic molecules at natural Isotopic Abundance using dnp enhanced solid state nmr
Journal of the American Chemical Society, 2015Co-Authors: Katharina Marker, Sabine Hediger, Morgane Pingret, Jeanmarie Mouesca, Didier Gasparutto, Gael De PaepeAbstract:NMR crystallography of organic molecules at natural Isotopic Abundance (NA) strongly relies on the comparison of assigned experimental and computed NMR chemical shifts. However, a broad applicability of this approach is often hampered by the still limited 1H resolution and/or difficulties in assigning 13C and 15N resonances without the use of structure-based chemical shift calculations. As shown here, such difficulties can be overcome by 13C–13C and for the first time 15N–13C correlation experiments, recorded with the help of dynamic nuclear polarization. We present the complete de novo 13C and 15N resonance assignment at NA of a self-assembled 2′-deoxyguanosine derivative presenting two different molecules in the asymmetric crystallographic unit cell. This de novo assignment method is exclusively based on aforementioned correlation spectra and is an important addition to the NMR crystallography approach, rendering firstly 1H assignment straightforward, and being secondly a prerequisite for distance measu...
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A New Tool for NMR Crystallography: Complete C-13/N-15 Assignment of Organic Molecules at Natural Isotopic Abundance Using DNP-Enhanced Solid-State NMR
Journal of the American Chemical Society, 2015Co-Authors: Katharina Marker, Sabine Hediger, Morgane Pingret, Jeanmarie Mouesca, Didier Gasparutto, Gael De PaepeAbstract:NMR crystallography of organic molecules at natural Isotopic Abundance (NA) strongly relies on the comparison of assigned experimental and computed NMR chemical shifts. However, a broad applicability of this approach is often hampered by the still limited H-1 resolution and/or difficulties in assigning C-13 and N-15 resonances without the use of structure-based chemical shift calculations. As shown here, such difficulties can be overcome by C-13-C-13 and for the first time N-15-C-13 correlation experiments, recorded with the help of dynamic nuclear polarization. We present the complete de novo C-13 and N-15 resonance assignment at NA of a self-assembled 2'-deoxyguanosine derivative presenting two different molecules in the asymmetric crystallographic unit cell. This de novo assignment method is exclusively based on aforementioned correlation spectra and is an important addition to the NMR crystallography approach, rendering firstly H-1 assignment straightforward, and being secondly a prerequisite for distance measurements with solid-state NMR.