A Green Surprise: Bilateral Bilious Pleural Effusion Secondary to Esophageal Rupture-A Case Report.

Bilothorax, an exudative pleural effusion due to the accumulation of bile. It is also called cholethorax or thoracobilia and was initially reported in 1971. Here, we report a rare case of an elderly male presenting with bilateral bilothorax due to esophageal rupture. A 78-year-old man with multiple medical ailments presented to the emergency room (ER) with a severe episode of vomiting accompanied by a popping sound, respiratory distress, and right sided chest pain. The patient had tachycardia, BP of 101/89 mm Hg, and tachypnea. Computed tomography scan of the chest and abdomen revealed air adjacent to the esophagus, suggesting perforation, atelectasis of right lung, and bilateral pleural effusion (R > L). However, an esophagram did not reveal any perforation. Right-sided chest tube drained dark green bilious fluid. The day after admission, he experienced hemodynamic compromise and hypoxemia requiring intubation, along with fluids and inotropes support. Diagnosis of bilateral bilothorax complicated by hypoxemic respiratory failure with septic shock was made. Cultures were drawn, and empiric antibiotics were started. Nuclear hepatobiliary scan (HIDA) was performed to rule out a hepatobiliary fistula. Results showed reflux activity in the stomach, and distal esophageal leak was identified. Gastrojejunal stenting was performed. However, after prolonged intubation, the family decided on terminal extubation, and he died while receiving hospice care. This case highlights the rarity of bilateral bilothorax, where the HIDA scan played a crucial role in identifying an esophageal leak as the underlying cause, despite normal esophagram results. This condition necessitates prompt diagnosis and aggressive therapeutic interventions.

Free mebrofenin clearance.

OBJECTIVES: To determine if three new simplified equations for measurement of free mebrofenin clearance give similar results to the equations defined by Ekman et. al ., and to evaluate the properties of all four methods. Regional mebrofenin clearance has been used to predict future remnant liver function and liver failure after regional liver therapy, such as partial hepatic resection. METHODS: The means, standard deviations, and correlations of the free mebrofenin clearance measured by the Ekman method and the three simplified methods were compared in a consecutive series of 26 studies in 20 patients. The fractional change in the blood and free mebrofenin activities were compared, and integrals of normalized blood and free mebrofenin ("effective times") were compared. RESULTS: The average percent free mebrofenin clearance for the Ekman and the first, second and third simplified methods were 13.62 ± 2.88%/min, 12.98 ± 2.97%/min, 12.52 ± 2.81%/min and 15.03 ± 2.27%/min, respectively. The correlations of the new methods with Ekman were 0.97, 0.93 and 0.93. The fractional changes during the measurement interval for the blood and free mebrofenin activities were 0.381 ± 0.065 and 0.329 ± 0.062, difference 0.052, P < 0.5. The integrals of normalized blood and free mebrofenin activities were 2.566 ± 0.160 min and 2.661 ± 0.158 min, difference of 0.094 min and P < 0.05. CONCLUSIONS: The results of the three new methods were similar to the Ekman method. The first simplified method was identified as the lead method for clinical validation in a larger population.

Structural and molecular characterization of collagen-type I extracted from lamb feet.

This study aimed to extract collagen-I from lamb feet (LF) and examine the effects of ultrasound treatment on the structural and molecular characteristics of the collagen. Compared to ultrasonic bath treatment and conventional extraction methods, ultrasonic probe (USP) treatment significantly increased the collagen content of the extract (p < 0.05). The electrophoretic profiles confirmed the presence of α- and ß-chains, indicating it as type I. Furthermore, X-ray diffraction, Fourier-transform infrared spectroscopy, and circular dichroism spectra analyses revealed that the extraction method did not adversely affect the triple helix structure of the collagen. Moreover, the fibrillar structure of the collagen samples was verified through scanning electron microscopy analyses. Notably, the LF collagen exhibited a high thermal denaturation temperature owing to its elevated imino acid content. The collagen samples exhibited high solubility in acidic pH but low solubility in high salt concentrations. The present findings signified that sonication with USP can effectively enhance the yield of collagen from LF without compromising its quality. PRACTICAL APPLICATION: This study showed that ultrasonication enhanced the collagen concentration without disturbing the integrity of lamb feet collagen. We expect that lamb feet collagen can be used for industrial processes and consumer products thanks to unique product properties.

Optimization of single-step gelatin extraction from pink perch (Nemipterus japonicus) skin and bone obtained from surimi industry using a green solvent.

Surimi industry produces a large quantity of byproducts that are currently being utilized to produce low-value commodities. This study aims to extract gelatin from pink perch skin and bone obtained from the surimi industry using a green single-step extraction method. In addition to using a green solvent, that is, acetic acid, the new method combines the multiple steps of pre-treatment and hydrolysis into one single-step extraction process. Response surface methodology was used to optimize extraction parameters (pH, temperature, and time) to maximize yield and l-hydroxyproline (l-hyp) content. The optimum condition for gelatin extraction was obtained at pH 3, 75°C, and 30 min. At optimum conditions, gelatin yield and l-hyp content were observed to be 16.07% and 41.26 mg g-1 , respectively. The gelatin obtained at optimized condition was further compared with commercial bovine gelatin (BG) in terms of chemical composition and textural, functional, and rheological properties. The results suggested that the optimized pink perch gelatin had higher protein content (92.06%), better gel strength (251.08 g), higher imino acid (18.01%), and improved textural and functional properties than the commercially available BG. The optimized single-step gelatin extraction method from pink perch skin and bones is a promising, rapid, and efficient method for the production of good-quality gelatin, which can be further used for the development of high-value products such as food formulations. PRACTICAL APPLICATION: Fish gelatin is widely used in food product development. Most of the existing methods of the development of high-value product such as gelatin, use multi-step process and harsh mineral acid, therefore, are time-consuming and harmful to the environment. This study provides a green single-step gelatin extraction method that provides an efficient, rapid, and convenient method of gelatin extraction and a sustainable solution for fish industry byproduct utilization. The data obtained with this laboratory-scale study provides a strong basis for scale-up studies.

Fine-Tuning Electroauxiliary-Mediated Peptide Modifications Using Second-Generation Electroactive Amino Acids.

Arylthioether functional groups serve as effective electroauxiliaries for tunable oxidations. Herein, we disclose the synthesis of second-generation glutamine building blocks bearing 2,4-dimethoxythiophenyl and 2,4-dichlorothiophenyl-derived electroauxiliaries. These building blocks improve SPPS efficiency and enable fine-tuning of the electrochemical window for selective anodic oxidation reactions in comparison to first-generation 4-methoxythiophenyl- and 4-nitrothiophenyl-substituted variants. Installation onto a segment of involucrin, a protein component of human skin, emphasizes the practical application of the new building blocks for iterative functionalizations.

The use of additional imaging studies after biliary point-of-care ultrasound in the emergency department.

PURPOSE: We sought to determine the test characteristics of biliary point-of-care ultrasound (POCUS) and to assess the usefulness of obtaining radiology ultrasound (RUS) or cholescintigraphy (HIDA) after biliary POCUS. METHODS: We conducted a retrospective review of emergency department patients who underwent biliary POCUS between May 4, 2018 and November 28, 2021. To be included, patients had to have at least one of the following confirmatory evaluations (considered in this order): surgery, HIDA, RUS, or abdominal CT scan. When a discrepancy existed between the POCUS and the RUS or HIDA, they were compared to a higher criterion standard (if available). RESULTS: Using 348 patients who had a confirmatory evaluation after biliary POCUS, we found the sensitivity and specificity of biliary POCUS for gallstones to be 97.0% (95% CI 92.6 to 99.2%) and 99.5% (95% CI 97.3 to 100%), respectively. For cholecystitis, the sensitivity and specificity were 83.8% (95% CI 72.9 to 91.6%) and 98.6% (95% CI 96.4 to 99.6%), respectively. RUS and POCUS were concordant in 72 (81.8%) of 88 cases in which the patient had both studies while HIDA and POCUS were concordant in 24 (70.6%) of 34 cases. POCUS was deemed correct in at least 50% of discrepant cases with RUS and at least 30% of discrepant cases with HIDA. CONCLUSION: Biliary POCUS has excellent sensitivity and specificity for cholelithiasis; it has lower sensitivity for cholecystitis, but the specificity remains high. Performing a confirmatory RUS or cholescintigraphy after a positive biliary POCUS adds little value, but additional imaging may be useful when POCUS is negative for cholecystitis.

Recent advances in the synthesis and reactivity of MIDA boronates.

Organoboron compounds have a wide-range of applications in synthetic methodologies, natural products, and bioactive molecule synthesis. The sensitivity of boronic acid toward most synthetic reagents makes it necessary to introduce a protecting group before its utilization. Benchtop stable MIDA boronates have been found compatible with various common synthetic reagents which opens the doors for the synthesis of various small building blocks, natural products, and bioactive compounds. MIDA boronate compounds have been extensively utilized in Suzuki Miyaura coupling and Iterative cross-coupling reactions for the total synthesis of bioactive molecules and polymerization reactions. Different MIDA boronate compounds like vinyl, acyl, formyl, acrylic, and α-carbonyl MIDA boronates also act as novel synthetic building blocks for various synthetic transformations in organic synthesis. This paper summarizes the importance of MIDA boronate compounds in various aspects of organic chemistry.

Quantitative Assessment of Liver Impairment in Chronic Viral Hepatitis with [99mTc]Tc-Mebrofenin: A Noninvasive Attempt to Stage Viral Hepatitis-Associated Liver Fibrosis.

Background and objectives-Chronic viral hepatitis B and C infections are one of the leading causes of chronic liver impairment, resulting in liver fibrosis and liver cirrhosis. An early diagnosis with accurate liver fibrosis staging leads to a proper diagnosis, thus tailoring correct treatment. Both invasive and noninvasive techniques are used in the diagnosis and staging of chronic liver impairment. Those techniques include liver biopsy, multiple serological markers (as either single tests or combined panels), and imaging examinations, such as ultrasound or magnetic resonance elastography. Nuclear medicine probes may also be employed in staging liver fibrosis, although the literature scarcely reports this. The purpose of our study was to investigate whether a dynamic liver scintigraphy with [99mTc]Tc-mebrofenin has any value in staging or grading chronic liver damage. Materials and Methods-We prospectively enrolled patients with chronic viral hepatitis B and C infection referred for liver biopsy. All patient underwent dynamic liver scintigraphy with 99mTc-mebrofenin prior to liver biopsy. Dynamic liver scintigraphy was performed immediately after intravenous tracer injection for 30 min scanning time. Multiple scintigraphy parameters were calculated (whole liver lobe and focal area time to peak (TTP), 30 min to peak ratio (30/peak), whole lobe and focal area slope index in 350 s (slope_350). Liver biopsy took place shortly after imaging. Results-We found that many dynamic scintigraphic parameters are positively or negatively associated with different stages of liver fibrosis. The main parameters that showed most value are the ratio between 30 min and the peak of the dynamic curve (30/peak_dex (ratio)), and liver clearance corrected for body surface area and liver area (LCL_m2_dm2 (%/min/m2/dm2)). Conclusions-Our present study proves that conducting dynamic liver scintigraphies with [99mTc]Tc-mebrofenin has potential value in staging liver fibrosis. The benefits of this method, including whole liver imaging and direct imaging of the liver function, provide an advantage over presently used quantitative imaging modalities.

Electrosynthesis of (hetero)aryl nitriles from α-imino-oxy acids via oxidative decarboxylation/N-O cleavage.

A new method for the synthesis of (hetero)aryl nitriles via iminyl radicals has been developed through the electrochemical oxidative decarboxylation of α-imino-oxy acids. This protocol provides an efficient approach to nitriles with a broad range of functional-group tolerance under ambient conditions and can be applied for one-pot gram-scale synthesis.

Pediatric Normokinetic Biliary Dyskinesia: Pain with Cholecystokinin on Hepatobiliary Iminodiacetic Acid Scan Predictive of Symptom Resolution After Cholecystectomy.

Introduction: Biliary dyskinesia is typically defined as a gallbladder ejection fraction (EF) <35% on hepatobiliary iminodiacetic acid scan with cholecystokinin stimulation (CCK-HIDA) testing. Cholecystectomy often leads to resolution of associated biliary colic symptoms. Alternatively, there is a subset of symptomatic patients with normal gallbladder EF on CCK-HIDA. It has been proposed that pain with CCK injection is more predictive of symptom resolution after cholecystectomy than low gallbladder EF. We reviewed our experience with pediatric patients with positive CCK provocation testing and a normal gallbladder EF in the absence of gallstones. Materials and Methods: We retrospectively reviewed the records of all pediatric patients with normal hepatobiliary iminodiacetic acid EFs (35%-80%) and pain with CCK injection at a tertiary care center between 2016 and 2020. Age, gender, body mass index (BMI), CCK-HIDA results, and pathology analysis were noted. Short- and long-term resolution of symptoms was determined by patient self-reporting at a mean of 3 weeks and 46 months, respectively. Results: Seventeen patients met inclusion criteria. Average age was 15.1 years (range, 12-17 years) with median BMI 24.9 (± 4.9 kg/m2). Mean CCK-HIDA EF was 56.3% (± 11.4%). In total, 62.5% of patients had evidence of chronic cholecystitis and/or cholesterolosis on pathology analysis. Of patients available for short-term and long-term postoperative follow-up, 80% and 83% reported complete or near complete resolution of symptoms, respectively. Conclusions: Normokinetic biliary dyskinesia is poorly understood but appears to be associated with chronic inflammation and cured by surgical intervention. Laparoscopic cholecystectomy results in resolution of symptoms for a majority of patients and should be considered in those with pain with CCK injection despite normal imaging studies. Clinical Trial Registration Number: 1657640-2.

Chiral secondary amino acids, their importance, and methods of analysis.

Naturally occurring secondary amino acids, with proline as the main representative, contain an alpha-imino group in a cycle that is typically four-, five-, and six-membered. The unique ring structure exhibits exceptional properties-conformational rigidity, chemical stability, and specific roles in protein structure and folding. Many proline analogues have been used as valuable compounds for the study of metabolism of both prokaryotic and eukaryotic cells and for the synthesis of compounds with desired biological, pharmaceutical, or industrial properties. The D-forms of secondary amino acids play different roles in living organisms than the L-forms. They have different metabolic pathways, biological, physiological, and pharmacological effects, they can be indicators of changes and also serve as biomarkers of diseases. In the scientific literature, the number of articles examining D-amino acids in biological samples is increasing. The review summarises information on the occurrence and importance of D- and L-secondary amino acids-azetidic acid, proline, hydroxyprolines, pipecolic, nipecotic, hydroxypipecolic acids and related peptides containing these D-AAs, as well as the main analytical methods (mostly chromatographic) used for their enantiomeric determination in different matrices (biological samples, plants, food, water, and soil).

Cisplatin-Chelated Iminodiacetic Acid-Conjugated Hyaluronic Acid Nanogels for the Treatment of Malignant Pleural Mesothelioma in Mice.

Malignant pleural mesothelioma (MPM) is one of the intractable cancers that require a more effective therapeutic strategy for clinical practice. Hyaluronic acid (HA) nanogels were prepared by the chelation of cisplatin (CDDP) with different molecular weights of iminodiacetic acid-conjugated hyaluronic acid (HA-IDA). The sizes of the 100, 850, and 2000 kDa HA nanogels were 33, 43, and 44 nm, respectively. MSTO-211H, a human MPM cell line, was more effective in taking up all three HA nanogels compared to AB22, a mouse MPM cell line. In addition, the 850 kDa HA nanogel showed higher anticancer activity against AB22 and MSTO-211H than 100 and 2000 kDa HA nanogels. Furthermore, all the HA nanogels showed a milder cytotoxic effect on normal Met-5A mesothelial cells compared to that exhibited by free CDDP. Finally, the 850 kDa HA nanogel was administrated intrapleurally into both the MSTO-211H xenograft and AB22 allograft mouse models of MPM using an injectable HA-based hydrogel. HA nanogels showed a significant therapeutic effect in both the xenograft and allograft models.

Subdomain Adaptation With Manifolds Discrepancy Alignment.

Reducing domain divergence is a key step in transfer learning. Existing works focus on the minimization of global domain divergence. However, two domains may consist of several shared subdomains, and differ from each other in each subdomain. In this article, we take the local divergence of subdomains into account in transfer. Specifically, we propose to use the low-dimensional manifold to represent the subdomain, and align the local data distribution discrepancy in each manifold across domains. A manifold maximum mean discrepancy (M3D) is developed to measure the local distribution discrepancy in each manifold. We then propose a general framework, called transfer with manifolds discrepancy alignment (TMDA), to couple the discovery of data manifolds with the minimization of M3D. We instantiate TMDA in the subspace learning case considering both the linear and nonlinear mappings. We also instantiate TMDA in the deep learning framework. Experimental studies show that TMDA is a promising method for various transfer learning tasks.

Pictorial Summary of Congenital Gallbladder and Biliary Duct Anomalies Presentation on HIDA Imaging.

Hepatobiliary iminodiacetic acid (HIDA) scan is one of the principal imaging modalities for the evaluation of the gallbladder and biliary tree. Congenital biliary anomalies are rare and can be difficult to recognize on HIDA scan. They may also mimic other biliary pathology. The purpose of this article is to review the spectrum of congenital gallbladder and biliary anomalies and describe their imaging appearance on HIDA scan. In addition, the diagnostic utility of functional imaging with HIDA when evaluating biliary tract anomalies is described.

Phosphonomethyl iminodiacetic acid functionalized metal organic framework supported PAN composite beads for selective removal of La(III) from wastewater: Adsorptive performance and column separation studies.

The rare earth elements being toxic in nature are being accumulated in water bodies as their industrial usage is growing exponentially, thus their efficient separation holds an immense significance. Herein, ligand functionalized metal organic framework (MOF), Phosphonomethyl iminodiacetic acid coordinated at Fe-BTC, was synthesized post-synthetically and incorporated subsequently in polyacrylonitrile polymer to prepare the composite beads via nonsolvent induced-phase-inversion technique for selective adsorption of La(III) from the wastewater in batch and dynamic column mode. XPS NMR, and FTIR were used to establish the interaction between functionalized ligand and unsaturated metal nodes of MOF. The adsorption capacity was 232.5 mg/g and 77.51 mg/g at 298 K of the functionalized MOF and composite beads respectively. Adsorption kinetics followed a pseudo-second order rate equation, and isotherm indicated the best fitting with Langmuir model. The dynamic behavior of the adsorption column packed with MOF/Polymer beads was fairly described by the Thomas model. The breakthrough time of 23.2 h could be attained with 12 cm of bed height and 10 ml/min of flow rate. These MOF/Polymer beads shown the selectivity of La over transitional metals were recycled over 5 times with about 15% loss of adsorption capacity. The findings provide suggestive insights of the potential use of functionalized MOF towards the separation of the rare earth element.

Iminodiacetic acid (IDA)-generated mesoporous nanopolymer: a template to relate surface area, hydrophilicity, and glycopeptides enrichment.

A three-step strategy is introduced to develop inherent iminodiacetic (IDA)-functionalized nanopolymer. SEM micrographs show homogenous spherical beads with a particle size of 500 nm. Further modification to COOH-functionalized 1,2-epoxy-5-hexene/DVB mesoporous nanopolymer enriches glycopeptides via hydrophilic interactions followed by their MS determination. Significantly high BET surface area 433.4336 m2 g-1 contributes to the improved surface hydrophilicity which is also shown by high concentration of ionizable carboxylic acids, 14.59 ± 0.25 mmol g-1. Measured surface area is the highest among DVB-based polymers and in general much higher in comparison to the previously reported BET surface areas of co-polymers, terpolymers, MOFs, and graphene-based composites. Thirty-one, 19, and 16 N-glycopeptides are enriched/identified by nanopolymer beads from tryptic digests of immunoglobulin G, horseradish peroxidase, and chicken avidin, respectively, without additional desalting steps. Material exhibits high selectivity (1:400 IgG:BSA), sensitivity (down to 0.1 fmol), regeneration ability up to three cycles, and batch-to-batch reproducibility (RSD > 1%). Furthermore, from 1 µL of digested human serum, 343 N-glycopeptide characteristics of 134 glycoproteins including 30 FDA-approved serum biomarkers are identified via nano-LC-MS/MS. The developed strategy to self-generate IDA on polymeric surface with improved surface area, porosity, and ordered morphology is insignia of its potential as chromatographic tool contributing to future developments in large-scale biomedical glycoproteomics studies.

A conjoint multi metal-ion iminodiacetic acid monolith microfluidic chip for structural-based protein pre-fractionation.

PDMS-based multichannel microfluidic chip was designed and fabricated in a simple approach using readily available tools. UV-initiated in situ polymerization of poly(2-hydroxy ethyl methacrylate-co-di(ethylene glycol) diacrylate-co-N,N'-diallyl l-tartardiamide) in an Eppendorf tube was achieved within 40 min. This polymerization process was successfully translated to a microfluidic chip format without any further modifications. Iminodiacetic acid was successfully immobilized on aldehyde functional monoliths via Schiff base reaction and confirmed by FT-IR spectroscopy. Four transition metal ions (Co (II), Zn (II), Ni (II), and Cu (II)) were chelated individually on four IDA-monolith microfluidic chips. The conjoint metal-ion monolith microfluidic chip has displayed high permeability (9.40 × 10-13  m2 ) and a porosity of 32.8%. This affinity microfluidic chip has pre-fractioned four human plasma proteins (fibrinogen, immunoglobulin, transferrin, and human serum albumin) based on their surface-exposed histidine surface topography. A protein recovery of approximately 95% (Bradford assay data) was achieved. The multimonolith microchip can be reusable even after three protein adsorption-desorption cycles.

Hydrogean Peroxide Inducible Acid-Activatable Prodrug for Targeted Cancer Treatment.

Because some of the potentially most useful boronic acids are inherently unstable in blood plasma and exhibit poor selective retention in tumours, 2-heterocyclic N-methyliminodiacetic acid (MIDA) boronates provide a stable, spacious and highly effective harbor for prodrug conjugates. Herein we report MIDA boronates in conjunction with naphthalene-based fluorophores as suitable compounds for tumour diagnosis by virtue of their remarkable specificity and uniform benchtop stability. The shielding group was found to be effective at imparting stability under physiological conditions (pH 7.4), with rapid release of the drug upon exposure to the acidic microenvironment of the tumor. This approach significantly enhanced the efficiency of drug release and was found to exhibit fewer side effects, thus indicating its great potential for precision therapeutics.

Collagens made from giant salamander (Andrias davidianus) skin and their odorants.

Two collagens were made from giant salamander (Andrias davidianus) skin by using acid and pepsin extraction methods. The yields of acid-soluble and pepsin-soluble collagens were 26.9 and 58.7%, respectively. The results of spectrum, electrophoresis and amino acid analysis showed that they were type 1 collagen with two α and one ß peptides and high imino acid content. They had low solubility at a pH above 6 or salt concentration over 5%. The pepsin-soluble collagen had a better emulsion activity index. The odorants in raw skin and collagens were identified and evaluated using gas-chromatography mass-spectrometer and olfactometry methods and sensory analysis. The fishy and fatty off-odors in skin were not perceivable in the collagens. Sour, ammonia-like, and acrid off-odors were found in the collagens due to acid and enzymatic hydrolysis and protein degradation. The off-odor intensity of pepsin-soluble collagen was low. It could be considered a good and safe collagen material.

Using D- and L-Amino Acid Oxidases to Generate the Imino Acid Substrate to Measure the Activity of the Novel Rid (Enamine/Imine Deaminase) Class of Enzymes.

This chapter describes a method to assay the activity of reactive intermediate deaminases (Rid), a large family of conserved soluble enzymes, which have been proposed to prevent damages from metabolic intermediates such as the highly reactive and unstable compounds enamines/imines. In this method, the flavin adenine dinucleotide-dependent L- or D-amino acid oxidases generate an imino acid starting from a L- or D- amino acid, respectively. This reaction is coupled to the hydrolysis of the imino acid to the corresponding α-keto acid and ammonium ion catalyzed by a Rid enzyme. The spectrophotometric assay consists of measuring the decrease of the initial rate of formation of the semicarbazone, derived from the spontaneous reaction of the imino acid and semicarbazide, caused by the presence of the Rid enzyme. The set-up and testing of this method imply a preliminary characterization of the ability of the amino acid oxidase to release the imino acid required for the subsequent reactions. To this purpose, the activity of the L- or D-amino acid oxidases with different amino acids can be measured as production of hydrogen peroxide or formation of semicarbazone in parallel assays. The advantages and limitations of this assay of Rid activity are discussed.