Bizarre Parosteal Osteochondromatous Proliferation (Nora's Lesion) Affecting Carpal Bones of the Hand in a Middle-Aged Female: A Case Report.

A 45-year-old woman complained of left wrist pain and swelling for two years accompanied by limited dorsiflexion. Plain X-rays revealed an abnormal bony mass in the carpal bones, further evaluated using computed tomography and magnetic resonance imaging. Upon confirmation of the benign nature surgical excisional biopsy of the lesion, the histopathology confirmed the diagnosis of Bizarre parosteal osteochondromatous proliferation (BPOP). The patient has remained pain-free and actively involved in her routine for the past two years. BPOP, affecting the carpal bones of the hand, are exceptionally rare occurrence. Attentive preoperative evaluation helps in diagnosis and to initiate measures to avoid recurrence.

Exploring the role of NIR spectroscopy in quantifying and verifying honey authenticity: A review.

Honey, recognized for its diverse flavors and nutritional benefits, confronts challenges in maintaining authenticity and quality due to factors like adulteration and mislabelling. This review undertakes a comprehensive exploration of the utility of Near-Infrared (NIR) spectroscopy as a non-destructive analytical method for concurrently evaluating both honey quantity and authenticity. The primary purpose of this investigation is to delve into the various applications of NIR spectroscopy in honey analysis, with a specific focus on its capability to identify and quantify significant quality parameters such as sugar content, moisture levels, 5-HMF, and proline content. Results from the study underscore the effectiveness of NIR spectroscopy, especially when integrated with advanced chemometrics models. This combination not only facilitates quantification of diverse quality parameters but also enhances the classification of honey based on geographical and botanical origin. The technology emerges as a potent tool for detecting adulteration, addressing critical challenges in preserving the authenticity and quality of honey products. The impact of this critical analysis extends to shedding light on the current state, challenges, and future prospects of applying NIR spectroscopy in the honey industry. This analysis outlines the current challenges and future prospects of NIR spectroscopy in the honey industry. Emphasizing its potential to improve consumer confidence and food safety, the research has broader implications for authenticity and quality assurance in honey. Integrating NIR spectroscopy into industry practices could establish stronger quality control measures, benefiting both producers and consumers globally.

Diagnosis of Infarcted Breast Lesions on FNAC, a Blustering Fool: Short Case Series.

Introduction: Fine-needle aspiration cytology (FNAC) is often used as a screening tool. Cytopathologist should be aware of various mimickers of the malignancy. One of these is infarction of benign breast lesions. Careful examination of cytomorphological features will avoid the misdiagnosis of malignancy in such cases. Material and Methods: Six cases were diagnosed as benign breast lesion for 4 years and 5 months in our newly established tertiary referral center. Histopathology follow-up was available in one case. Results: Of six cases, three cases (50%) were reported as fibroadenoma with infarction, two cases (33%) as benign breast lesion with infarction favor fibroadenoma, and one as breast lesion with infarction favor phyllodes tumor in view of recurrence. Most were in the second or third decade of their life. All cases showed dyscohesive cells with pyknotic nuclei. Monolayered sheets of necrotic cells were seen in the four cases (66%). Viable cells were seen in four cases. Conclusions: FNAC provides a rapid and accurate diagnosis of benign breast lesions with infarction in the hands of experienced pathologists who can help in better patient care. Small-sized uniform pyknotic nuclei of dyscohesive cells and regular nuclear membranes help to differentiate them from inflammatory and malignant lesions.

Acute Myocardial Infarction in a Patient With Focal Segmental Glomerulosclerosis Tip Lesion: Hit With a Double Whammy.

Nephrotic syndrome is associated with venous and arterial thrombotic complications and is related to the imbalance between pro-thrombotic and anti-thrombotic factors. With an underlying nephrotic syndrome, arterial thromboses are infrequent, and coronary artery thromboses are much rarer. We present the case of a young male, with nephrotic syndrome, who suffered an acute anterior wall ST-segment elevation myocardial infarction. He was subsequently diagnosed to have focal segmental glomerulosclerosis (FSGS)-tip lesion. The patient was successfully managed with thrombolysis, steroids, anticoagulation, antiplatelets, and statins.

Insights into the structure and Ion transport of pectin-[BMIM][PF6] electrolytes.

We investigate the effect of pectin on the structure and ion transport properties of the room-temperature ionic liquid electrolyte 1-n-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) using molecular dynamics simulations. We find that pectin induces intriguing structural changes in the electrolyte that disrupt large ionic aggregates and promote the formation of smaller ionic clusters, which is a promising finding for ionic conductivity. Due to pectin in [BMIM][PF6] electrolytes, the diffusion coefficient of cations and anions is observed to decrease by a factor of four for a loading of 25 wt. % of pectin in [BMIM][PF6] electrolyte. A strong correlation between the ionic diffusivities (D) and ion-pair relaxation timescales (τc) is observed such that D ∼ τc-0.75 for cations and D ∼ τc-0.82 for anions. The relaxation timescale exponents indicate that the ion transport mechanisms in pectin-[BMIM][PF6] electrolytes are slightly distinct from those found in neat [BMIM][PF6] electrolytes (D∼τc-1). Since pectin marginally affects ionic diffusivities at the gain of smaller ionic aggregates and viscosity, our results suggest that pectin-ionic liquid electrolytes offer improved properties for battery applications, including ionic conductivity, mechanical stability, and biodegradability.

LDPE-Natural Rubber Composite Film as Active Packaging: A Paradigm Shift in Oxygen Scavengers.

Oxygen scavenging films, an emerging type of active packaging, play a crucial role in preserving the freshness and quality of food products. In this study, we proposed an extruded film made of low-density polyethylene (LDPE) with 5% natural rubber (NR) as the oxygen scavenging film. Characterization of the film revealed that its morphological and barrier properties remained intact, while the elongation attribute was enhanced. The obtained film was standardized for activation scavenging kinetics by varying the UV dose (time and distance). At the optimal UV dose, the film exhibited a total scavenging capacity of 61 cc/g. To assess the film's functionality, FTIR spectra were analyzed before and after exposure to oxygen, confirming the film's ability to scavenge oxygen based on observed peaks at 1718 and 3425 cm-1. Considering that bread and khoa (fatty food) are sensitive to oxygen, they were selected for testing the application of the oxygen scavenging film. Sensory analysis of bread samples, including appearance and mold formation, as well as microbial load studies, indicated that the shelf life of bread increased from 2-3 days (control) to 4-5 days when packed in the NR-based film and stored at 27 ± 2 °C. Similarly, when applied to khoa, the film extended its shelf life by 3 days compared to the control while maintaining sensory attributes and preserving nutritional value, such as fatty acids. In general, the developed oxygen scavenging film effectively prevents the detrimental effects of oxygen on food products, leading to an extension of their shelf life. This has significant implications for the food industry, as it helps mitigate the negative consequences of oxygen exposure and enhances the product shelf life.

Pulped natural/honey robusta coffee fermentation metabolites, physico-chemical and sensory profiles.

The pulped natural/honey coffee (HC) of Coffea canephora (Robusta) is an innovative modified semi-dry technique. Studies have focused on HC and washed coffee (WC) fermentation, microbial metabolites, quality of green and roasted, using 1H NMR, GC-MS, and sensory investigation. Pipecolate and 3-hydroxy-3-methyglutarate have been identified for the first time. Principal Component Analysis (PCA) variability of the roasted beans, with PC 1 depicting 87.4 % and 12.6 % PC 2 respectively highlights the impact of major sugars and secondary metabolites acquired through HC. The HC fermentation (192 h) influenced carbohydrates, organic acids, and secondary metabolites besides flavor precursors compared to WC (72 h). Although HC and WC beans share similar physical qualities, enhanced volatile compounds, enriched concentration, organoleptics with pleasant, sweet, tea rose and chocolaty flavors attributes were embodied in HC than WC. The pulped natural post-harvest technique in robusta is a value addition with quality that can fetch a better premium.

Detection of barley malt syrup as an adulterant in honey by 1H NMR profile.

Currently, Barley Malt Syrup (BMS) is one of the forms of growing adulteration in honey. However, there have been no reports regarding its identification by NMR. In this aspect, we proposed a 1H NMR profiling method to discriminate between authentic and honey adulterated with BMS. The authenticated honey samples were artificially adulterated with varying percentages of BMS. It was found that a marker peak primarily falling around the 5.40 ppm region exhibited discrimination between pure and adulterated samples. Furthermore, NMR data of the samples were analyzed using statistical models. The findings demonstrate that NMR sugar profiles region, when combined with PCA analysis, can effectively detect varying degrees of adulteration. Despite qualitative nature of the outcomes, spiking studies have revealed that approach can reliably identify sugar addition at levels as low as 5-10%. Overall, NMR-based approach proves to be effective in detecting BMS as an adulterant in honey.

Enabling honey quality and authenticity with NMR and LC-IRMS based platform.

Honey has been known for economically motivated adulteration around the world, because of its high demand and short supply. As consequence increasing honey production using the deliberate addition of sugar syrups while claiming a fictitious origin and diversifying it to increase its value. Generally, honey testing is supervised by a set of guidelines and quality parameters to ensure its quality and authenticity. As per the many regulatory bodies, current honey scams have been challenging to identify with conventional methods, so quality control labs require sophisticated technology. With these paradigm shifts, the aim of the present review is focused on the authenticity of honey through two important cutting-edge methods viz LC-IRMS and NMR. The LC-IRMS aids in the detection of added C3 and C4 sugars. Whereas NMR has provided a potent solution by allowing the classification of botanical varieties and geographical origin along with the quantification of a set of quality parameters in a single experiment.

Selective Homodecoupled 1D-1H NMR Experiment for Unravelling Enantiomers.

1H NMR spectroscopy is a quick and easy tool to resolve enantiomers. However, the paradigm of resolution of enantiomers by 1H NMR is a difficult task due to the minor chemical shift differences and overlap of the resonances of the enantiomers. In the current study, we have performed the conventional selective homodecoupling 1D-1H NMR experiment to achieve chiral resolutions. The predominant features of the proposed methods are (a) high sensitivity as opposed to routinely employed pure shift NMR experiments, (b) easy optimization like conventional 1D-1H NMR, and (c) an artifact-free spectrum. The application of the method has been exhibited in the measurement of proton chemical shift differences between diastereomers and enantiomer excess (ee). The broad use of the proposed method was demonstrated by employing the six samples utilizing the chiral solvating and derivatizing agents.

Existence of ß-diketone form of curcuminoids revealed by NMR spectroscopy.

Curcumin (CUR), demethoxycurcumin (DMC) and bisdemethoxycurcumin (BDMC) - the class of natural compound derived from turmeric can exist as keto-enol and ß-diketone tautomer form. The structure and dynamics of particular relevance CUR is reported in prior studies, whereas DMC and BDMC, by far, have not been scrutinized. In the present studies, we have investigated the detailed molecular structure of CUR, DMC and BDMC by employing NMR spectroscopy as a key tool. The bridging carbon as methylene in ß-diketone form and methine in keto-enol form shows significant difference in NMR spectrum. The results justified that Curcuminoids (CC) has nearly 3% of ß-diketone tautomer in DMSO solvent at 298 K. Further, results revealed that ß-diketone form was favoured in alkaline pH condition whereas acidic and neutral pH conditions favour keto-enol tautomer. However, at higher temperature equilibrium shift towards ß-diketone tautomer. Moreover, this is the first report by NMR for observing the presence of ß-diketone tautomer.

Facile NMR approach for profiling curcuminoids present in turmeric.

Curcumin, together with demethoxycurcumin and bisdemethoxycurcumin as a whole called curcuminoids, is an active phytochemical constituent present in the turmeric. When it comes to their analysis, most will rely on UV-Visible spectroscopy, HPLC and LC-MS methods. Looking to improve productivity, time and simplicity, we are proposing a 1H NMR based approach for curcuminoids analysis and its applications to different geographical regions. In the present work, sample preparation protocol is reported for the simultaneous determination of curcuminoids using 1H NMR. For the quantification of curcuminoids, 6-7 ppm vinylic proton region in the 1H NMR spectrum was used, where acetone was observed as the suitable solvent in terms of curcuminoids solubility and proper resolution of peak. The result shows that curcumin (46.8-59.50%) was major among all varieties, followed by DMC (22.15-27.70%) and BDMC (17.52-30.29%) except in Andhrapradesh variety, where BDMC (30.29%) was more than DMC (22.89%). These studies were further supported by HPLC analysis.

A cost-effective polyethylene glycol-based method for the isolation of functional edible nanoparticles from ginger rhizomes.

Edible nanoparticles (ENPs) are nano-sized vesicles derived from edible plants. These ENPs are loaded with plant derived microRNAs, protein, lipids and phytochemicals. Recently, ginger derived ENPs was shown to prevent inflammatory bowel diseases and colon cancer, in vivo, highlighting their therapeutic potential. Conventionally, differential centrifugation with an ultra-centrifugation step is employed to purify these ENPs which imposes limitation on the cost-effectiveness of their purification. Herein, we developed polyethylene glycol-6000 (PEG6000) based ginger ENP purification (PEG-ENPs) method, which eliminates the need for expensive ultracentrifugation. Using different PEG6000 concentrations, we could recover between 60% to 90% of ENPs compared to ultracentrifugation method. PEG-ENPs exhibit near identical size and zeta potential similar to ultra-ENPs. The biochemical composition of PEG-ENPs, such as proteins, lipids, small RNAs and bioactive content is comparable to that of ultra-ENPs. In addition, similar to ultra-ENPs, PEG-ENPs are efficiently taken up by the murine macrophages and protects cells from hydrogen peroxide induced oxidative stress. Since PEG has been approved as food additive, the PEG method described here will provide a cost-effective alternative to purify ENPs, which can be directly used as a dietary supplement in therapeutic formulations.

R-VAPOL-phosphoric acid based 1H and 13C-NMR for sensing of chiral amines and acids.

Enantiomers have significant importance in pharmaceuticals, biology and modern chemistry and therefore distinguishing and quantifying the enantiomeric forms is of utmost importance. Herein, we propose diphenyl-3,3'-biphenanthryl-4,4'-diyl phosphate (R-VAPOL-PA) as a promising chiral solvating agent to discriminate amines and acids of poly-functional groups such as chiral amines, amino alcohols and hydroxy acids. The methodological approach involves using the nature of hydrogen bonds and ion pairs as a mode of weak interactions to form diastereomers where the probe is associated with enantiomers. The resulting diastereomer difference in the NMR spectrum enables the chiral discrimination with a complete baseline peak separation and an accurate enantiomeric excess (ee) analysis. We also carried out density functional theory (DFT) calculations to understand the complex formation to explain enantiodiscrimination by analysing the formation and stability of different chiral complexes. The binding energy differences between enantiomeric forms revealed by DFT calculations are qualitatively in agreement with the diastereomer difference in the NMR spectrum and unequivocally establishes the suggested experimental protocol of R-VAPOL-PA-based enantiomeric discrimination.

Spice fixed oils as a new source of γ-oryzanol: nutraceutical characterization of fixed oils from selected spices.

γ-Oryzanol is an important group of nutraceuticals that play a key role in addressing metabolic disorders. This study, for the first time, examined volatile-free spice fixed oils (FOs) as an alternate plant source for γ-oryzanol and other nutraceuticals (phenolics, flavonoids, phytosterols, and tocopherols) using HPLC, HR-MS and NMR. The in vitro antioxidant activities of FOs were also analysed. The selected spices were Alpinia galanga, Cinnamomum zeylanicum, Trigonella foenum-graecum, Foeniculum vulgare and Myristica fragrans. The major polyphenols and flavonoids quantified were gallic, protocatechuic, vanillic, syringic, para-coumaric, ferulic, rutin, trans-cinnamic, and quercetin. T. foenum-graecum FOs recorded high levels of ergosterol (48.56 mg/100 g) and stigmasterol (247.36 mg/100 g). The fucosterol levels were high in A. galanga (268.31 mg/100 g) FOs, whereas C. zeylanicum FOs showed high content of ß-sitosterols (7037.77 mg/100 g). C. zeylanicum and T. foenum-graecum FOs recorded high α-tocopherol content (47.55 and 15.96 mg/100 g respectively). C. zeylanicum FOs showed high levels of three ferulates, namely, cycloartenyl ferulate, 24-methylene cycloartenyl ferulate and ß-sitosteryl ferulate, whose contents were 89.42, 170.23 and 50.23 mg/100 g respectively which was confirmed by HRMS with a molecular mass (m/z) of 601.45, 615.47, and 589.45 respectively. Further, γ-oryzanol ferulates in C. zeylanicum FOs were confirmed by 1H-NMR analysis. The acidified methanolic extractives of FOs showed high free radical scavenging activity and antioxidant potential. These spice FOs have excellent antioxidant activities, and are novel potential functional ingredients against lifestyle disorders.

BDPA-Nitroxide Biradicals Tailored for Efficient Dynamic Nuclear Polarization Enhanced Solid-State NMR at Magnetic Fields up to 21.1 T.

Dynamic nuclear polarization (DNP) solid-state nuclear magnetic resonance (NMR) has developed into an invaluable tool for the investigation of a wide range of materials. However, the sensitivity gain achieved with many polarizing agents suffers from an unfavorable field and magic angle spinning (MAS) frequency dependence. We present a series of new hybrid biradicals, soluble in organic solvents, that consist of an isotropic narrow electron paramagnetic resonance line radical, α,γ-bisdiphenylene-ß-phenylallyl (BDPA), tethered to a broad line nitroxide. By tuning the distance between the two electrons and the substituents at the nitroxide moiety, correlations between the electron-electron interactions and the electron spin relaxation times on one hand and the DNP enhancement factors on the other hand are established. The best radical in this series has a short methylene linker and bears bulky phenyl spirocyclohexyl ligands. In a 1.3 mm prototype DNP probe, it yields enhancements of up to 185 at 18.8 T (800 MHz 1H resonance frequency) and 40 kHz MAS. We show that this radical gives enhancement factors of over 60 in 3.2 mm sapphire rotors at both 18.8 and 21.1 T (900 MHz 1H resonance frequency), the highest magnetic field available today for DNP. The effect of the rotor size and of the microwave irradiation inside the MAS rotor is discussed. Finally, we demonstrate the potential of this new series of polarizing agents by recording high field 27Al and 29Si DNP surface enhanced NMR spectra of amorphous aluminosilicates and 17O NMR on silica nanoparticles.

Dynamic Nuclear Polarization-Enhanced Biomolecular NMR Spectroscopy at High Magnetic Field with Fast Magic-Angle Spinning.

Dynamic nuclear polarization (DNP) is a powerful way to overcome the sensitivity limitation of magic-angle-spinning (MAS) NMR experiments. However, the resolution of the DNP NMR spectra of proteins is compromised by severe line broadening associated with the necessity to perform experiments at cryogenic temperatures and in the presence of paramagnetic radicals. High-quality DNP-enhanced NMR spectra of the Acinetobacter phage 205 (AP205) nucleocapsid can be obtained by combining high magnetic field (800 MHz) and fast MAS (40 kHz). These conditions yield enhanced resolution and long coherence lifetimes allowing the acquisition of resolved 2D correlation spectra and of previously unfeasible scalar-based experiments. This enables the assignment of aromatic resonances of the AP205 coat protein and its packaged RNA, as well as the detection of long-range contacts, which are not observed at room temperature, opening new possibilities for structure determination.

Insight into old and new pure shift nuclear magnetic resonance methods for enantiodiscrimination.

Enantiodiscrimination and their quantification using nuclear magnetic resonance (NMR) spectroscopy has always been a subject of great interest. Proton is the nucleus of choice for enantiodiscrimination due to its high sensitivity and ubiquitous presence in nature. Despite its advantages, enantiodiscrimination suffers from extensive signal splitting by the proton-proton scalar couplings, which give complex multiplets that spread over a frequency range of some tens of hertz. These multiplets often overlap, further complicating interpretation of the spectra and quantifications. In the present review, we discuss some of the recent developments in the pure shift 1 H NMR based methods for enantiomer resolution and enantiodiscrimination. We also compare various pure shift methods used for enantiodiscrimination and measurement of enantiomeric excess, considering the fact that conventional 1 H NMR fails to provide any detailed insight.

Dynamic Nuclear Polarization Efficiency Increased by Very Fast Magic Angle Spinning.

Dynamic nuclear polarization (DNP) has recently emerged as a tool to enhance the sensitivity of solid-state NMR experiments. However, so far high enhancements (>100) are limited to relatively low magnetic fields, and DNP at fields higher than 9.4 T significantly drops in efficiency. Here we report solid-state Overhauser effect DNP enhancements of over 100 at 18.8 T. This is achieved through the unexpected discovery that enhancements increase rapidly with increasing magic angle spinning (MAS) rates. The measurements are made using 1,3-bisdiphenylene-2-phenylallyl dissolved in o-terphenyl at 40 kHz MAS. We introduce a source-sink diffusion model for polarization transfer which is capable of explaining the experimental observations. The advantage of this approach is demonstrated on mesoporous alumina with the acquisition of well-resolved DNP surface-enhanced 27Al cross-polarization spectra.

Donor-acceptor stacking arrangements in bulk and thin-film high-mobility conjugated polymers characterized using molecular modelling and MAS and surface-enhanced solid-state NMR spectroscopy.

Conjugated polymers show promising properties as cheap, sustainable and solution-processable semiconductors. A key challenge in the development of these materials is to determine the polymer chain structure, conformation and packing in both the bulk polymer and in thin films typically used in devices. However, many characterisation techniques are unable to provide atomic-level structural information owing to the presence of disorder. Here, we use molecular modelling, magic-angle spinning (MAS) and dynamic nuclear polarisation surface-enhanced NMR spectroscopy (DNP SENS) to characterise the polymer backbone group conformations and packing arrangement in the high-mobility donor-acceptor copolymer diketopyrrolo-pyrrole-dithienylthieno[3,2-b]thiophene (DPP-DTT). Using conventional 1H and 13C solid-state MAS NMR coupled with density functional theory calculations and molecular dynamics simulations, we find that the bulk polymer adopts a highly planar backbone conformation with a laterally-shifted donor-on-acceptor stacking arrangement. DNP SENS enables acquisition of 13C NMR data for polymer films, where sensitivity is limiting owing to small sample volumes. The DNP signal enhancement enables a two-dimensional 1H-13C HETCOR spectrum to be recorded for a drop-cast polymer film, and a 13C CPMAS NMR spectrum to be recorded for a spin-coated thin-film with a thickness of only 400 nm. The results show that the same planar backbone structure and intermolecular stacking arrangement is preserved in the films following solution processing and annealing, thereby rationalizing the favourable device properties of DPP-DTT, and providing a protocol for the study of other thin film materials.