Interpretation Of Nuclear Magnetic Resonance Research Articles

Glycolipids Derived from the Korean Endemic Plant Aruncus aethusifolius Inducing Glucose Uptake in Mouse Skeletal Muscle C2C12 Cells.

Aruncus spp. has been used as a traditional folk medicine worldwide for its anti-inflammatory, hemostatic, and detoxifying properties. The well-known species A. dioicus var. kamtschaticus has long been used for multifunctional purposes in Eastern Asia. Recently, it was reported that its extract has antioxidant and anti-diabetic effects. In this respect, it is likely that other Aruncus spp. possess various biological activities; however, little research has been conducted thus far. The present study aims to biologically identify active compounds against diabetes in the Korean endemic plant A. aethusifolius and evaluate the underlying mechanisms. A. aethusifolius extract enhanced glucose uptake without toxicity to C2C12 cells. A bioassay-guided isolation of A. aethusifolius yielded two pure compounds, and their structures were characterized as glycolipid derivatives, gingerglycolipid A, and (2S)-3-linolenoylglycerol-O-β-d-galactopyranoside by an interpretation of nuclear magnetic resonance and high-resolution mass spectrometric data. Both compounds showed glucose uptake activity, and both compounds increased the phosphorylation levels of insulin receptor substrate 1 (IRS-1) and 5'-AMP-activated protein kinase (AMPK) and protein expression of peroxisome proliferator-activated receptor γ (PPARγ). Gingerglycolipid A docked computationally into the active site of IRS-1, AMPK1, AMPK2, and PPARγ (-5.8, -6.9, -6.8, and -6.8 kcal/mol).

Isolation of Macrocyclic Trichothecene Mycotoxins from the Lethal Toxic Mushroom Podostroma cornu-damae and Their Cytotoxic Activities

Podostroma cornu-damae, one of the lethal toxic mushrooms, is known to contain macrocyclic trichothecene mycotoxins exhibiting potent cytotoxic effects, attracting attention as an important research subject for scientists interested in natural product chemistry and toxicity research. To investigate the mycotoxins from the toxic mushroom P. cornu-damae and evaluate their cytotoxic activities, the fungus was large-cultured on solid plates and successively extracted to acquire a crude methanol (MeOH) extract. After performing successive separation and purification processes, a total of eight macrocyclic trichothecenes were isolated from the MeOH extract of plate cultures of P. cornu-damae using the liquid chromatography/mass spectrometry (LC/MS)-guided isolation technique. Extensive interpretation of nuclear magnetic resonance (NMR) spectroscopic and high-resolution (HR)-electrospray ionization (ESI)-MS data allowed for the structural identification of all isolated macrocyclic trichothecenes, including satratoxin I (1), satratoxin H (2), roridin E (3), miophytocen D (4), roridin L-2 (5), trichoverritone (6), 12′-episatratoxin H (7), and roridin F (8). We conducted a cytotoxicity evaluation of compounds 1–8 against 4T1 breast cancer cells and fibroblast cell lines (L929 cells) using the Counting Kit-8 (CCK-8) cell viability assay to validate their cytotoxic potential. Our results indicated that compounds 1–6 lack anti-cancer effects on 4T1 cells and have minimal impact on the viability of the fibroblast cell line, L929 cells. In contrast, compounds 7 and 8 exhibited no cytotoxicity in normal cells (L929) and demonstrated specific cytotoxicity in breast cancer cell lines. Notably, the cytotoxic effects of compounds 7 and 8 in 4T1 cells were significantly stronger than those observed with free doxorubicin. These findings suggest that compounds 7 and 8 may possess targeted anti-cancer effects, specifically against breast cancer cells, emphasizing their efficient and selective toxicity towards breast cancer cells.

Novel Operando Nuclear Magnetic Resonance Approach for Tracking the Electrode State of Charge in Li/Na-Ion Batteries

Lithium and sodium-ion batteries have become the focal point of interest for the energy transition due to their promising applications for electric cars and energy grid storage. Operando characterization of batteries is critical to understand the degradation processes and increasing their electrochemical performance, especially in abusive conditions like during fast charges. Knowledge of the redox state of each electrode is essential to identify the origins of capacity loss in full batteries. Among the methods used for these investigations, operando Nuclear Magnetic Resonance (NMR) methods are promising since, without destroying the battery, they enable monitoring in real-time the electrochemical processes and the formation of short-lived metastable or reactive phases [1,2].Up to now, most operando NMR studies have focused on 7Li NMR spectroscopy to follow the lithiation and degradation processes in the solid electrodes of lithium-ion batteries. However, the large shifts and broadenings of the NMR spectra, which result from the redox-active paramagnetic ions (Ni2/3+, Co4+, Mn3/4+) or from the metallicity of the electrodes [3], complicate operando NMR spectra acquisition and interpretation for full batteries.Herein, we demonstrate that the 1H operando NMR signal of the liquid electrolyte solvent can be used to spy on the positive electrode evolution while benefitting from the high sensitivity of 1H liquid-state NMR compared to 7Li NMR. So far, operando NMR using the liquid electrolyte signal was mainly exploited to follow electrolyte decomposition [4] or to image indirectly dendrite formation [5]. Contrary to the lithium or sodium atoms composing the electrodes, hydrogen atoms in the electrolyte solvent are not a direct probe of the state of charge of the electrode. We demonstrate that the 1H NMR signal of the electrolyte molecules in the battery is, however, highly sensitive to the magnetic susceptibility (and therefore the redox state) of the neighboring particles of positive electrode active material.The state-of-charge (SOC) of the positive electrodes in the charging battery can be tracked indirectly through distortion in the spectrum of the dimethyl carbonate (DMC) solvent near the positive electrode. The effect of the other battery components such as current collectors, separators, or even negative electrodes is shown to be negligible compared to the perturbations induced by the positive electrode. We define specific descriptors to track the changes in the distorted 1H NMR spectrum of the battery and we correlate these changes with the state-of-charge of the positive electrode inside the battery as it is charged and discharged. This approach will enable measuring, operando, the redox state of positive electrodes in batteries, even when their 7Li signals cannot be detected by NMR. Exact knowledge of the redox state will contribute to a better exploitation of the electrochemical curves in full batteries.[1] Bagheri, K.; Deschamps, M.; Salager, E. Nuclear Magnetic Resonance for Interfaces in Rechargeable Batteries. Current Opinion in Colloid & Interface Science 2023, 64, 101675. https://doi.org/10.1016/j.cocis.2022.101675.[2] Liu, X.; Liang, Z.; Xiang, Y.; Lin, M.; Li, Q.; Liu, Z.; Zhong, G.; Fu, R.; Yang, Y. Solid‐State NMR and MRI Spectroscopy for Li/Na Batteries: Materials, Interface, and in Situ Characterization. Advanced Materials 2021, 33 (50), 2005878. https://doi.org/10.1002/adma.202005878.[3] Grey, C. P.; Dupré, N. NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries. Chemical Reviews 2004, 104 (10), 4493–4512. https://doi.org/10.1021/cr020734p.[4] Wiemers-Meyer, S.; Winter, M.; Nowak, S. NMR as a Powerful Tool to Study Lithium Ion Battery Electrolytes. Annual Reports on NMR Spectroscopy 2019, 121–162. https://doi.org/10.1016/bs.arnmr.2018.12.003.[5] Ilott, A. J.; Mohammadi, M.; Chang, H. J.; Grey, C. P.; Jerschow, A. Real-Time 3D Imaging of Microstructure Growth in Battery Cells Using Indirect MRI. Proceedings of the National Academy of Sciences 2016, 113 (39), 10779–10784. https://doi.org/10.1073/pnas.1607903113.

Subplenones A-J: Dimeric Xanthones with Antibacterial Activity from the Endophytic Fungus Subplenodomus sp. CPCC 401465.

Subplenones A-J (1-10), 10 new xanthone dimers, have been isolated and characterized from the endophytic fungus Subplenodomus sp. CPCC 401465, which resides within the Chinese medicinal plant Gentiana straminea. The isolation process was guided by antibacterial assays and molecular-networking-based analyses. The chemical structures of these compounds were elucidated through the interpretation of nuclear magnetic resonance (NMR) and high-resolution electrospray ionization mass spectrometry (HRESIMS) data. Furthermore, the relative configuration of the compounds was determined using NMR and single-crystal X-ray diffraction analyses, and the absolute configuration was established using electronic circular dichroism calculations. All of the isolated compounds exhibited significant inhibitory activity against Gram-positive bacteria. Notably, compounds 1, 5, and 7 displayed remarkable inhibitory activity against methicillin-resistant Staphylococcus aureus (MRSA) ATCC 700698, with a minimum inhibitory concentration (MIC) of 0.25 μg/mL, and against vancomycin-resistant Enterococcus faecium (VRE) ATCC 700221, with MIC values ranging from 0.5 to 1.0 μg/mL.

Experimental and simulation study on the estimation of surface relaxivity of clay minerals

Nuclear Magnetic Resonance (NMR) is an important tool for the evaluation of pore structure and petrophysical properties of reservoir rocks. Pore Surface relaxivity (ρ2), which controls the relaxation decay due to the interaction between the spins and the pore surface, is an important parameter that impacts the interpretation of NMR for petrophysical properties. Sandstone rocks have complex minerology and consist of different clay minerals. Earlier efforts have reported the surface relaxivity of different rock types such as sandstone or carbonate, but less attention was given to the estimation of individual clay minerals surface relaxivity. The surface complexity and variable mineralogy (especially paramagnetic and ferromagnetic minerals) of clays can both impact the surface relaxivity and relaxation times in clays and porous media containing clays. This study, using for the first time both simulation and experimental approaches, aims to systematically investigate the surface relaxivity of clays characterized by variable mineralogy and iron content. A glass beads sample (iron free) and 5 different pure clay minerals samples (ranked by increasing iron content: Kaolinite, Smectite, Illite, Chlorite, and Nontronite) were prepared with similar average grain sizes (500 μm). The determination of surface relaxivity requires prior measurement of pore surface-to-volume ratio (S/V) using an independent method in addition to obtaining T2 relaxation time. Two methods, among the most widely used, were used here for S/V determination including BET N2 gas adsorption and 3D micro CT imaging. The 3D images were also used to conduct NMR simulations to reproduce the experimental data. The estimated surface relaxivity values from both methods were compared and correlated to the iron content of the different clays. The surface relaxivity values obtained based on BET-derived S/V showed reasonable values (29–343 μm/s) that have a strong positive relationship with iron content of the clays. The documented equation relating surface relaxivity and iron content can be potentially utilized to predict surface relaxivity based on the compositional analysis of clays. On the other hand, digital images did not capture the surface complexity of clays thus significantly underestimated S/V which consequently resulted in overestimated surface relaxivity (898–11000 μm/s) that were physically non-feasible. Supporting the same argument, the simulated T2 relaxation distribution showed significant mismatch with the experimental data for the clay samples while an excellent match was observed for the glass beads sample. This can be attributed to the smooth surface of the glass beads, unlike the complex clays. The reported surface relaxivity values (based on BET-derived S/V) for the individual clay minerals can be used to perform NMR simulation and interpretation studies conducted on sandstone or shale formations. Careful attention should be given when performing NMR simulation on micro-CT digital images of samples containing clay due to the inadequacy of such images in capturing the complex surface and microporous nature of clays. The outcomes from this study can improve the interpretation of NMR T2 data and the determination of NMR-derived pore size distribution and petrophysical properties. The reported surface relaxivity values for clay can also inform the NMR simulation.

Methoxy 13C NMR Chemical Shift as a Molecular Descriptor in the Structural Analysis of Flavonoids and Other Phenolic Compounds

The interpretation of nuclear magnetic resonance (NMR) chemical shifts plays an increasingly important role in the structure elucidation of flavonoids. Despite the fact that the 3H signal of the methoxy (OMe) group appears as a singlet in the 1H NMR spectrum, its chemical shift is not reliably indicative of the OMe-substitution in the aromatic rings, unlike its 13C NMR chemical shift, which can be useful for the determination of the molecular structure of flavonoids. For example, the chemical shift of ortho-substitutions is at 56 ± 1 ppm for flavonoids having one OMe-substituent in either the ortho or orthó position and 61.5 ± 2 ppm for those having substituents in both ortho positions. The nuclear Overhauser effect spectroscopy ( δH-OMe→ ortho-aryl-H or adjacent substituent) and heteronuclear multiple-bond correlation ( δH-OMe→ ipso-aryl-C) data have been widely employed for the structure analysis of flavonoids and to identify the site of OMe-substitution. Thus, OMe chemical shifts can act as molecular descriptors. However, we have noticed that there are several examples that are not in accordance with this generalization, and a reinvestigation of such reported data seems to be relevant for reconsideration of assigned structures, and a few examples are cited herein.

Fast-forward modeling of borehole nuclear magnetic resonance measurements acquired in deviated wells and spatially heterogeneous formations

High-angle and horizontal (HAHz) wells are routinely drilled to enhance reservoir exposure and increase fluid productivity. The interpretation of nuclear magnetic resonance (NMR) measurements entails major technical challenges in horizontal layers penetrated by HAHz wells or through dipping formation layers penetrated by a vertical well. Three-dimensional geometric effects, coupled with spatially and petrophysically heterogeneous rocks, may bias petrophysical estimates obtained from borehole NMR measurements using methods designed for vertical wells and horizontal layers. Reliable interpretation requires an accurate and rapid forward-modeling method that integrates NMR physics and tool/instrument specifications, borehole, and 3D formation geometric properties. The latter is possible with the recent development of a forward-modeling algorithm that accurately and efficiently simulates NMR measurements based on 3D spatial sensitivity functions (SSFs). We implement and quantify this forward-modeling approximation across dipping formations penetrated by deviated wells in the presence of mud-filtrate invasion. We validate and verify the fast approximation against a 3D multiphysics model using challenging synthetic cases, in highly apparent dip wells with the varying radial front of the mud-filtrate invasion. Our work compares the effect of radial length of investigation from the three distinct NMR acquisition shells to better understand borehole NMR measurements acquired in 3D complex geometries. On average, the fast approximation via SSFs reproduces NMR measurements in 3 s of central processing unit time with maximum root-mean-square errors below 1% and can therefore be used for real-time calculations and interpretations. Modeling results indicate that thinly bedded formations and their petrophysical properties can be resolved with relatively low measurement resolution in HAHz wells and dipping formations.

Pore Size Distribution Characterization by Joint Interpretation of MICP and NMR: A Case Study of Chang 7 Tight Sandstone in the Ordos Basin

Pore size distribution characterization of unconventional tight reservoirs is extremely significant for an optimized extraction of petroleum from such reservoirs. In the present study, mercury injection capillary pressure (MICP) and low-field nuclear magnetic resonance (NMR) are integrated to evaluate the pore size distribution of the Chang 7 tight sandstone reservoir. The results show that the Chang 7 tight sandstones are characterized by high clay mineral content and fine grain size. They feature complex micro-nano-pore network system, mainly composed of regular primary intergranular pores, dissolved pores, inter-crystalline pores, and micro-fractures. Compared to the porosity obtained from MICP, the NMR porosity is closer to the gas-measured porosity (core analysis), and thus can more accurately describe the total pore space of the tight sandstone reservoirs. The pore throat distribution (PTD) from MICP presents a centralized distribution with high amplitude, while the pore size distribution (PSD) derived from NMR shows a unimodal distribution or bimodal distribution with low amplitude. It is notable that the difference between the PSD and the PTD is always related to the pore network composed of large pores connecting with narrow throats. The PSD always coincides very well with the PTD in the very tight non-reservoirs with a much lower porosity and permeability, probably due to the pore geometry that is dominated by the cylindrical pores. However, a significant inconsistency between the PSD and PTD in tight reservoirs of relatively high porosity and low permeability is usually associated with the pore network that is dominated by the sphere-cylindrical pores. Additionally, Euclidean distance between PSD and PTD shows a good positive correlation with pore throat ratio (PTR), further indicating that the greater difference of pore bodies and pore throats, the more obvious differentiation of two distributions. In summary, the MICP and NMR techniques imply the different profiles of pore structure, which has an important implication for deep insight into pore structure and accurate evaluation of petrophysical properties in the tight sandstone reservoir.

Integrated Reservoir Characterization Using Unsupervised Learning on Nuclear Magnetic Resonance (NMR) T1-T2 Logs

A novel interpretation workflow was developed using an automated unsupervised learning algorithm on nuclear magnetic resonance (NMR) T1-T2 log data to quantify fluid-filled porosity and saturation, producible oil volumes, and to characterize matrix pore sizes and formation wettability. Core porosity and saturation measurements, scanning electron microscope images (SEM), Rock-Eval pyrolysis, wettability measurements, and mercury injection capillary pressure (MICP) tests are compared with the NMR interpretation for calibration and validation. Understanding in-situ fluid types and volumetrics is key for reservoir characterization. The traditional static formation evaluation model based on triple-combo logs (density, neutron, resistivity, and gamma ray) has been widely used to characterize formations to provide cost-effective answers of lithology, total porosity, and water saturation. Nevertheless, the dynamic result from production often shows quite a different water cut than total water saturation because the static model cannot distinguish immobile hydrocarbons from producible oil. NMR log data show unique signatures of formation fluids, such as gas, immobile hydrocarbon, producible oil, T1-T2 immobile, and free water. The NMR data also provide a method to interpret fluid and matrix properties, including fluid viscosity, pore geometry, and fluid-pore interaction. However, due to the downhole environment and the resolution limitation of the logging tool, the signatures of the fluids are not always well separated. It is challenging to visually separate the signal contributions of different formation fluids on T1-T2 maps. An automated unsupervised learning algorithm based on non-negative matrix factorization (NMF) and hierarchical clustering (Venkataramanan et al., 2018) is implemented in the new workflow to separate T1-T2 signatures of different pore fluids, enabling fluid typing and providing quantitative fluid-filled porosities and associated saturations. T1-T2 signatures of separated fluids are used to characterize fluid mobility, pore sizes, and formation wettability. The new approach is successfully applied to multiple wells for a field case study to characterize the saturation and producibility of hydrocarbon and water, which routine petrophysical models are unable to distinguish. Results are corroborated with dynamic production data showing high free water and high residual oil. This is also validated by routine and special core analyses. Integration of NMR, MICP, and SEM gives pore-body and pore-throat-size distributions with body-to-throat ratio (BTR), increasing the precision of estimated formation permeability. A high T1/T2 ratio of the oil suggests that the formation is partially oil-wet. The wettability results from NMR are consistent with the core wettability test and production results. Understanding which portion of a reservoir contains mobile fluids impacts target zone selection and reserves estimation.

New phenylalkanoids from the rhizome of Cnidium officinalis Makino

Cnidium officinalis rhizomes were immersed in 80% MeOH. The extract was fractionated to water, n-butanol, and ethyl acetate fractions (Fr). Open column chromatography was repeatedly carried out on n-butanol and ethyl acetate Fr using silica gel, octadecyl silica gel, and Sephadex LH-20 as the stationary phase affording five phenyl alkanoids 1–5 including two new ones. The molecular structures including stereochemistry were decided based on spectroscopic interpretation of nuclear magnetic resonance, mass spectrometry, and infrared spectroscopy as well as chemical reaction. Three known compounds, coniferyl alcohol methyl ether (1), vanillin (2), and coniferyl aldehyde (3), were reported in the beginning for this plant by authors. Two new phenyl alkanoids were named, 7-methoxyeugenol and cnidiumoside.

Rapid modeling of borehole measurements of nuclear magnetic resonance via spatial sensitivity functions

Borehole measurements of nuclear magnetic resonance (NMR) are routinely used to estimate in situ rock and fluid properties. Conventional NMR interpretation methods often neglect bed-boundary and layer-thickness effects in the calculation of fluid volumetric concentrations and NMR relaxation-diffusion correlations. Such effects introduce notable spatial averaging of intrinsic rock and fluid properties across thinly bedded formations or in the vicinity of boundaries between layers exhibiting large property contrasts. Forward modeling and inversion methods can mitigate the aforementioned effects and improve the accuracy of true layer properties in the presence of mud-filtrate invasion and borehole environmental effects across spatially complex formations. We have developed a fast and accurate algorithm to simulate borehole NMR measurements using the concept of spatial sensitivity functions (SSFs) that honor NMR physics and incorporate tool, borehole, and formation geometry. Tool sensitivity maps are derived from a 3D multiphysics forward model that couples NMR tool properties, magnetization evolution, and electromagnetic propagation. In addition, a multifluid relaxation model based on Brownstein-Tarr’s equation is introduced to estimate layer NMR porosity decays and relaxation-diffusion correlations from pore-size-dependent rock and fluid properties. The latter model is convolved with the SSFs to reproduce borehole NMR measurements. The results indicate that NMR spatial sensitivity is controlled by porosity, electrical conductivity, excitation pulse duration, and tool geometry. We benchmark and verify the SSF-derived forward approximation against 3D multiphysics simulations for a series of synthetic cases with variable bed thickness and petrophysical properties, and in the presence of mud-filtrate invasion in a vertical well. Results indicate that the approximation can be executed in a few seconds in a central processing unit, by a factor of 1000 times faster than rigorous multiphysics calculations, with maximum root-mean-square errors of 1%.

Consoramides A–C, New Zwitterionic Alkaloids from the Fungus Irpex consors

In our ongoing search for new secondary metabolites from fungi, a basidiomycete fungus Irpex consors was selected for mycochemical investigation, and three new zwitterionic alkaloids (1-3) and five known compounds (4-8) were isolated from the culture broth (16 l) of I. consors. The culture filtrate was fractionated by a series of column chromatography including Diaion HP-20, silica gel, and Sephadex LH-20, Sep-Pak C18 cartridge, medium pressure liquid chromatography (MPLC), and high pressure liquid chromatography (HPLC) to yield eight compounds (1-8). The structures of the isolated compounds were elucidated by the interpretation of nuclear magnetic resonance (NMR) spectra and high-resolution mass spectrometry (HR-MS). Their antioxidant and antibacterial activities were examined. The zwitterionic structures of three new sesquiterpene alkaloids (1-3) were determined together with five known compounds identified as stereumamide E (4), stereumamide G (5), stereumamide H (6), stereumamide D (7), and sterostrein H (8). This is the first report of the zwitterionic alkaloids in the culture broth of I. consors. Three new zwitterionic alkaloids were named as consoramides A–C (1-3).

Pore-Structure Characterization of a Complex Carbonate Reservoir in South Iraq Using Advanced Interpretation of NMR Logs

The Rumaila Field is in southeast Iraq and contains multiple reservoir intervals, including the Upper Cretaceous Mishrif carbonate reservoir, one of the major reservoirs in the world, that has been producing for more than 50 years. One of the key challenges in the Mishrif is to characterize the pore-structure distinction between primary and secondary porosity. The secondary porosity in the form of large pores, if present, dominates the petrophysical properties, especially permeability. Advanced logs, e.g., nuclear magnetic resonance (NMR) and image logs, can be used to understand the variations in pore structure, both qualitatively and quantitatively. In this paper, we focused primarily on four new wells with very comprehensive logging and coring programs. NMR logs were acquired using different tools and pulse sequences. This resulted in uncertainty in porosity and T2 distributions and, consequently, complications in the NMR interpretation. We observed two key issues: porosity deficit due to lack of polarization and T2 distribution truncation due to the low number of echoes. We used a single pore model to reproduce the NMR response in different pore sizes and fluid types for different pulse sequences. The results showed that the NMR response, especially in water-filled (water-based-mud filtrate) large pores, is sensitive to polarization time, echo spacing, and tool gradient strength. NMR log data confirmed the modeling results. We recommended an optimum pulse sequence and tool characteristics to fully capture the heterogeneous rock and fluid system in this carbonate reservoir. NMR logs, when available, were the primary tools to identify the large pores. We present a consistent workflow for NMR log analysis that was developed to identify and quantify large pores and extended to all wells in the field. We used advanced NMR interpretation techniques, e.g., factor analysis (NMR FA) (Jain et al., 2013), in a series of oil wells drilled with water-based mud. Using factor analysis, we identified a cutoff value of 847 ms for large pore volumes. In this manuscript, we also present an integration of laboratory measurements, e.g., NMR, mercury intrusion capillary pressure (MICP) data, whole-core CT scanning, and thin-section analysis, in our interpretation workflow. We also compared the large pore volume from image logs with NMR logs and other laboratory data and observed very consistent results. All the available information was integrated to build an “NMR-based” petrophysical model for porosity, rock type, permeability, and saturation determination. The NMR-based model was very comparable with the classic flow zone indicator (FZI) rock typing. The results of this study were used to modify the NMR acquisition program in the field and to build a petrophysical model based on only NMR and image log measurements for carbonate reservoirs. In this paper, we will discuss NMR modeling and corresponding log data from various wells to confirm the results. Furthermore, we will present a novel interpretation workflow integrating laboratory measurements and log data, which led to the modification of the NMR acquisition program in the field and the creation of a data-driven petrophysical model based on only NMR and image log measurements for carbonate reservoirs.

A New Multiphysics Method for Simultaneous Assessment of Permeability and Saturation-Dependent Capillary Pressure in Hydrocarbon-Bearing Rocks

Summary Cost-effective exploitation of heterogeneous/anisotropic reservoirs (e.g., carbonate formations) relies on accurate description of pore structure, dynamic petrophysical properties (e.g., directional permeability, saturation-dependent capillary pressure), and fluid distribution. However, techniques for reliable quantification of permeability still rely on model calibration using core measurements. Furthermore, the assessment of saturation-dependent capillary pressure has been limited to experimental measurements, such as mercury injection capillary pressure (MICP). The objectives of this paper include developing a new multiphysics workflow to quantify rock-fabric features (e.g., porosity, tortuosity, and effective throat size) from integrated interpretation of nuclear magnetic resonance (NMR) and electric measurements; introducing rock-physics models that incorporate the quantified rock fabric and partial water/hydrocarbon saturation for assessment of directional permeability and saturation-dependent capillary pressure; and validating the reliability of the new workflow in the core-scale domain. To achieve these objectives, we introduce a new multiphysics workflow integrating NMR and electric measurements, honoring rock fabric, and minimizing calibration efforts. We estimate water saturation from the interpretation of dielectric measurements. Next, we develop a fluid-substitution algorithm to estimate the T2 distribution corresponding to fully water-saturated rocks from the interpretation of NMR measurements. We use the estimated T2 distribution for assessment of porosity, pore-body-size distribution, and effective pore-body size. Then, we develop a new physically meaningful resistivity model and apply it to obtain the constriction factor and, consequently, throat-size distribution from the interpretation of resistivity measurements. We estimate tortuosity from the interpretation of dielectric-permittivity measurements at 960 MHz by applying the concept of capacitive formation factor. Finally, throat-size distribution, porosity, and tortuosity are used to calculate directional permeability and saturation-dependent capillary pressure. We test the reliability of the new multiphysics workflow in the core-scale domain on rock samples at different water-saturation levels. The introduced multiphysics workflow provides accurate description of the pore structure in partially water-saturated formations with complex pore structure. Moreover, this new method enables real-time well-log-based assessment of saturation-dependent capillary pressure and directional permeability (in presence of directional electrical measurements) in reservoir conditions, which was not possible before. Quantification of capillary pressure has been limited to measurements in laboratory conditions, where the differences in stress field reduce the accuracy of the estimates. We verified that the estimates of permeability, saturation-dependent capillary pressure, and throat-size distribution obtained from the application of the new workflow agreed with those experimentally determined from core samples. We selected core samples from four different rock types, namely Edwards Yellow Limestone, Lueders Limestone, Berea Sandstone, and Texas Cream Limestone. Finally, because the new workflow relies on fundamental rock-physics principles, permeability and saturation-dependent capillary pressure can be estimated from well logs with minimum calibration efforts, which is another unique contribution of this work.

Carbon Atoms Speaking Out: How the Geometric Sensitivity of 13C Chemical Shifts Leads to Understanding the Colour Tuning of Phycocyanobilin in Cph1 and AnPixJ.

We present a combined quantum mechanics/molecular mechanics (QM/MM) molecular dynamics–statistical approach for the interpretation of nuclear magnetic resonance (NMR) chemical shift patterns in phycocyanobilin (PCB). These were originally associated with colour tuning upon photoproduct formation in red/green-absorbing cyanobacteriochrome AnPixJg2 and red/far-red-absorbing phytochrome Cph12. We pursue an indirect approach without computation of the absorption frequencies since the molecular geometry of cofactor and protein are not accurately known. Instead, we resort to a heuristic determination of the conjugation length in PCB through the experimental NMR chemical shift patterns, supported by quantum chemical calculations. We have found a characteristic correlation pattern of C chemical shifts to specific bond orders within the -conjugated system, which rests on the relative position of carbon atoms with respect to electron-withdrawing groups and the polarisation of covalent bonds. We propose the inversion of this regioselective relationship using multivariate statistics and to apply it to the known experimental NMR chemical shifts in order to predict changes in the bond alternation pattern. Therefrom the extent of electronic conjugation, and eventually the change in absorption frequency, can be derived. In the process, the consultation of explicit mesomeric formulae plays an important role to qualitatively account for possible conjugation scenarios of the chromophore. While we are able to consistently associate the NMR chemical shifts with hypsochromic and bathochromic shifts in the P and P, our approach represents an alternative method to increase the explanatory power of NMR spectroscopic data in proteins.

Antimicrobial Chlorinated 3-Phenylpropanoic Acid Derivatives from the Red Sea Marine Actinomycete Streptomyces coelicolor LY001.

The actinomycete strain Streptomyces coelicolor LY001 was purified from the sponge Callyspongia siphonella. Fractionation of the antimicrobial extract of the culture of the actinomycete afforded three new natural chlorinated derivatives of 3-phenylpropanoic acid, 3-(3,5-dichloro-4-hydroxyphenyl)propanoic acid (1), 3-(3,5-dichloro-4-hydroxyphenyl)propanoic acid methyl ester (2), and 3-(3-chloro-4-hydroxyphenyl)propanoic acid (3), together with 3-phenylpropanoic acid (4), E-cinnamic acid (5), and the diketopiperazine alkaloids cyclo(l-Phe-trans-4-OH-l-Pro) (6) and cyclo(l-Phe-cis-4-OH-d-Pro) (7) were isolated. Interpretation of nuclear magnetic resonance (NMR) and high-resolution electrospray ionization mass spectrometry (HRESIMS) data of 1–7 supported their assignments. Compounds 1–3 are first candidates of the natural chlorinated phenylpropanoic acid derivatives. The production of the chlorinated derivatives of 3-phenylpropionic acid (1–3) by S. coelicolor provides insight into the biosynthetic capabilities of the marine-derived actinomycetes. Compounds 1–3 demonstrated significant and selective activities towards Escherichia. coli and Staphylococcus aureus, while Candida albicans displayed more sensitivity towards compounds 6 and 7, suggesting a selectivity effect of these compounds against C. albicans.

Effects of gas pressurization on the interpretation of NMR hydrocarbon measurements in organic rich shales

The estimation of total hydrocarbons (HCs) in place is one of the most important economic challenges in unconventional resource plays. Nuclear magnetic resonance (NMR) has proven to be a valuable tool in directly quantifying both hydrocarbons and brines in the laboratory and the field. Some major applications of NMR interpretation include pore body size distributions, wettability, fluid types, and fluid properties. However, for tight formations, the effects of the factors on NMR relaxation data are intertwined. One purpose of this study is to review the interpretation of NMR response of HCs in a tight rock matrix through illustrated examples. When comparing NMR data between downhole wireline and laboratory measurement, three important elements need to be considered: 1) temperature differences, 2) system response differences, and 3) pressure (mainly due to the lost gasses.) The effect of temperature on HCs would be presented with experimental results for bulk fluids. Whereas, the effect of pressure is investigated by injecting gas back into rock matrix saturated with original fluids. The experiments were performed within an NMR transparent Daedalus ZrO2 pressure cell, which operates at pressures up to 10,000 psi. The results show that, at ambient temperature and pressure, NMR responds to a fraction of HCs, which is volatile enough to be observed as an NMR relaxation sequence. The invisible fraction of HCs to NMR sequence at ambient condition can be up to 20% of the total extractable HCs. Molecular relaxation is impacted by fluid viscosity, pore size, and surface affinity. In other words, the fluid with higher viscosity (either due to temperature or gas loss), presenting in smaller pore, or highly affected by the pore surface, will relax faster, and would be partially invisible to NMR, especially in the field. This is critical to the interpretation of NMR response for liquid rich source rocks, in which all of the above molecular relaxing restrictions can be found. Thus, engineers can underestimate movable HCs by using routine core analysis data.

A new acyclic peroxide from Aspergillus nidulans SD-531, a fungus obtained from deep-sea sediment of cold spring in the South China Sea

A new acyclic peroxide derivative asperoxide A (1), along with 13 known compounds, namely, microperfuranone (2), 9-hydroxymicroperfuranone (3), gibellulin A (4), lecanoric acid (5), terrequinone A (6), sterigmatocystin (7), isosecosterigmatocystin (8), arugosin C (9), curvularin (10), 3,3′-diindolylmethane (11), austinol (12), austin (13), and dehydroaustin (14), were isolated and identified from the culture extract of Aspergillus nidulans SD-531, a fungus obtained from the deep-sea sediment of cold spring in the South China Sea. Their structures were determined based on detailed interpretation of nuclear magnetic resonance (NMR) spectroscopic and mass spectrometry data analysis. All the isolated compounds were evaluated for antimicrobial activities against human and aquatic bacteria as well as plant pathogenic fungi. Compounds 1-28, 10, and 11 exhibited antimicrobial activities against some of the tested strains with minimum inhibitory concentration (MIC) values ranging from 2 to 64 μg/mL. Compounds 4 and 6 displayed strongest activities among the tested samples and might be used as promising molecules for the development of natural antimicrobial agents.

Joint Interpretation of Electrical Resistivity andT2 NMR Measurements To Estimate Wettability and Water Saturation

SummaryThe wettability of rocks can be assessed from interpretation of borehole geophysical measurements, such as electrical resistivity and nuclear magnetic resonance (NMR). These wettability models often require additional inputs (e.g., water saturation, porosity, and pore-geometry- related parameters), which are difficult to obtain independently. Consequently, a multiphysics workflow that integrates resistivity and NMR measurements can reduce the number of input parameters, resulting in a more accurate and robust wettability assessment. The objectives of this paper are to introduce a new workflow for joint interpretation of resistivity and NMR measurements to simultaneously estimate wettability and water saturation, and to verify the reliability of wettability and water-saturation estimates by comparison with experimentally measured contact angles, Amott Indices, and gravimetrically assessed water saturation.This new workflow for assessing wettability and water saturation combines nonlinear resistivity- and NMR-based rock physics models. The inputs to the resistivity-based wettability model include the resistivity of the rock–fluid system and brine, porosity, and pore-geometry-related parameters. The NMR-based wettability model requires the transverse (T2) response of the rock–fluid system, saturating fluids, and water-wet water-saturated and hydrocarbon-wet hydrocarbon-saturated rocks. To verify the reliability of the new integrated workflow, we perform resistivity and NMR measurements on core samples from different rock types, covering a range of wettability and water-saturation levels. These measurements are inputs to the nonlinear models, which are simultaneously solved to estimate wettability and water saturation for each core sample. We verify the reliability of wettability estimates by comparison with the Amott Index (IA) and contact-angle measurements, and the water-saturation estimates by comparison with the gravimetric water-saturation estimates.We successfully verified the reliability of the new method for this joint interpretation of resistivity and NMR measurements to estimate wettability and water saturation of limestone and sandstone core samples. For water-saturation levels ranging from irreducible water saturation to residual oil saturation, we observed an average relative error of 11% between the gravimetrically assessed and the model-estimated water saturation. It is challenging to estimate water saturation in rocks with multimodal pore-size distribution uniquely from the interpretation of NMR measurements. One contribution of the introduced workflow is improving the accuracy of water-saturation estimates (in addition to wettability) in rocks with complex pore structure and wettability states. For the wettability ranging from hydrocarbon-wet to water-wet, we observed an average absolute difference of 0.15 between the experimentally measured IA and the model-estimated wettability. These model-estimated wettability values were also consistent with the contact-angle measurements. It should be noted that the new workflow relies on physically meaningful and measurable parameters, which minimizes calibration efforts. Furthermore, the multiphysics workflow eliminates the nonuniqueness associated with wettability and water-saturation estimates obtained from independent interpretation of NMR and resistivity measurements.

A proposed NMR solution for multi-phase flow fluid detection

In the petroleum industry, detection of multi-phase fluid flow is very important in both surface and down-hole measurements. Accurate measurement of high rate of water or gas multi-phase flow has always been an academic and industrial focus. NMR is an efficient and accurate technique for the detection of fluids; it is widely used in the determination of fluid compositions and properties. This paper is aimed to quantitatively detect multi-phase flow in oil and gas wells and pipelines and to propose an innovative method for online nuclear magnetic resonance (NMR) detection. The online NMR data acquisition, processing and interpretation methods are proposed to fill the blank of traditional methods. A full-bore straight tube design without pressure drop, a Halbach magnet structure design with zero magnetic leakage outside the probe, a separate antenna structure design without flowing effects on NMR measurement and automatic control technology will achieve unattended operation. Through the innovation of this work, the application of NMR for the real-time and quantitative detection of multi-phase flow in oil and gas wells and pipelines can be implemented.