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In the search for pharmaceutically active compounds from natural products, it is crucial and challenging to develop separation or purification methods that target not only structurally similar compounds but also those with specific pharmaceutical functions. The adsorption-based method is widely employed in this field and holds potential for this application, given the diverse range of functional monomers that can be chosen based on structural or functional selectivity. In this work, an imidazolium ionic liquid (IL) modified paper membrane was synthesized via microwave reaction. Caffeic acid (CA), with potential interactions with imidazolium IL and a representative component of phenolic acids in Taraxaci Herba, was chosen as a target compound. After optimization of synthesis and extraction parameters, the resulting extraction membrane could be used to quantitatively analyze CA at ng/ml level, and to extract CA's analogues from the sample matrix. Cheminformatics confirmed the presence of structural and functional similarity among these extracted compounds. This study offers a novel approach to preparing a readily synthesized extraction membrane capable of isolating compounds with structural and functional analogies, as well as developing a membrane solid-phase extraction-based analytical method for natural products., (© 2024 John Wiley & Sons Ltd.)

Direct air capture (DAC) is a sustainable technology to alleviate the greenhouse effect and a reliable pathway to acquire inexhaustible CO2 for the production of costly chemicals and energy products. Current DAC technologies with amine‐related sorbents rely on chemisorption, while they consume intensive energy for CO2 release and sorbent regeneration by heating. Developing new DAC processes with weak, reversible adsorption can substantially reduce the regeneration energies. Herein, the design of CO2 breathing paper (CBP) is demonstrated toward spontaneous CO2 extraction from ambient air and solar‐driven regeneration. The CBP is fabricated by coupling 2‐ethyl‐4‐methylimidazole to carbon nanotube paper on the basis of density functional theory calculations. At ambient conditions, CBP spontaneously captures atmospheric CO2 with a capacity of 0.14–1.75 mmol g–1 at 0–35 °C through non‐covalent electrostatic interaction. Upon exposure to sunlight, all adsorbed CO2 can be released and converted to concentrated gas for storage. Attractively, the efficiency of solar‐driven CO2 release is much higher than the traditional temperature‐swing method owing to the IR sensitivity of CO2. Besides the reversibility, the mild conditions also ensure the durability of CBP. These findings suggest that the CBP is a promising candidate for cost‐effective DAC. [ABSTRACT FROM AUTHOR]

Weighing paper-assisted magnetic ionic liquid headspace single-drop microextraction using microwave distillation followed by gas chromatography-mass spectrometry was successfully developed to determine the essential oil components in lavender. The magnetic ionic liquid 1-octyl-3-methylimidazolium tetrachloroferrate was successfully synthesized and used as the optimal extraction solvent. An aliquot of 9 μL of magnetic ionic liquid could be stably suspended on the weighing paper for long time extraction. The increase of the extractant volume resulted in a significantly enhanced in extracting efficiency of the weighing paper-assisted magnetic ionic liquid headspace single-drop microextraction than traditional headspace single-drop microextraction method. In this experiment, the optimal conditions were 1-octyl-3-methylimidazolium tetrachloroferrate as the extraction solvent, extraction time of 12 min, microwave power of 600 W, cyclohexane as back-extractant and sample amount of 30 mg. The developed method was successfully applied to analyze 16 lavender samples from three different harvest years. A total of 39 compounds in lavender were identified and the principal component analysis provided a clear separation between those lavender samples harvested in different years. The results indicated that the proposed weighing paper-assisted magnetic ionic liquid headspace single-drop microextraction is a novel, fast, simple and sensitive microextration technique for the determination of the essential oil components in lavender., (© 2020 Wiley-VCH GmbH.)

A new planar sorptive phase based on the simple immobilization of polymeric ionic liquids on paper is proposed. The sorptive phase can develop hydrophobic or mixed-mode (combining hydrophobic and ion exchange) interactions with the target analytes. The polymer is prepared by the Radziszewski reaction, which takes place in aqueous media, and it has been thoroughly characterized by different techniques including infrared spectroscopy, matrix-assisted laser desorption/ionization coupled to high-resolution mass spectrometry and proton nuclear magnetic resonance. Three different strategies aimed to immobilize the polymeric ionic liquid on paper have been evaluated. Among them, simple thermal curing at 120 °C was selected. The as-prepared paper has been evaluated for the extraction of several non-steroidal anti-inflammatory drugs from urine, the analytes being finally determined by liquid chromatography with tandem mass spectrometry. The method detection limits were 3.8, 7.2, 6.8, 9.4, 15.7, and 5.1 μg/L for indomethacin, diclofenac, tolmetin, ketoprofen, naproxen, and ibuprofen, respectively. Calibration models were linear (R 2  > 0.9949) up to 1000 μg/L. The intra-day precision, expressed as relative standard deviation and calculated at three different concentrations levels (limit of quantification, 250 μg/L, and 1000 μg/L), varied between 1.1 and 13%. The accuracy, calculated as relative recovery, was in the range from 72 to 95%, thus being considered appropriate. The easiness of polymeric ionic liquid paper synthesis and the multi-sample extraction protocol designed allows the processing of a high number of samples at the same time., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Based on the tunability of ionic liquids (ILs) according to the specific requirement of an application, 1-dodecylimidazolium chloride with amphiphilic structures was chemically fabricated on the surface of filter papers (DIL-FPs) for the first time. After synthesis, DIL-FPs was characterized by scanning electronic microscopy, energy dispersive X-ray spectroscopy and Fourier-transform infrared spectroscopy. DIL-FPs was used as a novel thin-film microextraction (TFME) phase for the preconcentration of amphiphilic bisphenol A from plant oil samples. The related extraction variables were studied in a spiked sunflower seed oil. Under the optimal conditions, the linear range was 5.0 - 1000 μg L -1 with a correlation coefficient of 0.9976. The limit of detection (S/N = 3) and the enrichment factor of the proposed method were 2.7 μg L -1 and 118, respectively. The intra-day precision and inter-day precision for six repeated determinations were 2.3 and 4.9%, respectively. These plant oil samples used in this work were free of bisphenol A contaminations. The recovery study carried out in different plant oil samples and mean recoveries ranged from 77.16 to 97.10%. The developed DIL-FPs extraction film phase followed by HPLC-UV provides a potential pretreatment strategy for the analysis of weak organic acid compounds in plant oil samples.

Cellulose extracted from printed paper wastes were selectively depolymerized under controlled conditions into cello-oligomers of controllable chain lengths via dissolution in an ionic liquid, 1-allyl-3-methylimidazolium chloride (AMIMCl), and in the presence of an acid catalyst, Amberlyst 15DRY. The depolymerization process was optimized against reaction temperature, concentration of acid catalyst, and reaction time. Despite rapid initial depolymerization process, the rate of cellulose depolymerization slowed down gradually upon prolonged reaction time, with 75.0 wt% yield of regenerated cello-oligomers (mean Viscosimetric Degree of Polymerization value of 81) obtained after 40 min. The depolymerization of cellulose fibers at 80 °C appeared to proceed via a second-order kinetic reaction with respect to the catalyst concentration of 0.23 mmol H3O(+). As such, the cellulose depolymerization process could afford some degree of control on the degree of polymerization or chain lengths of cello-oligomers formed., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Rapid qualitative and quantitative analysis of 4-methylimidazole (4-MEI) in caramel and beverage samples is demonstrated using the paper spray form of ambient ionization mass spectrometry. The minimum level of pure 4-MEI detectable using multiple reaction monitoring (MRM) in a triple quadrupole instrument was 3 pg μL⁻¹ in neat solvent and 5 pg μL⁻¹ in a matrix containing caramel. This method was used to analyze 11 caramel samples for 4-MEI. After implementing effective quality control protocols, average relative standard deviations for paper spray triple quadrupole MS were less than 15% and the linear dynamic range was three orders of magnitude. Results obtained on three different days by two different analyst groups agreed closely. An ion trap tandem MS method of approximate quantitative analysis is also described and it gave similar precision to the triple quadrupole experiment when fluctuations in ion currents were cancelled by simultaneously isolating the analyte and internal standard and fragmenting both in an ion trap simultaneous MRM experiment. As another alternative, a rapid qualitative screening method based on the use of high-resolution measurements instead of tandem mass spectrometry using an Orbitrap was also tested and found to give a detection limit of 100 pg μL⁻¹.

Iron gall inks have been known since Roman times, were widely used in the Medieval Age, and became the most used ink in the Renaissance period. They were still officially used by the German Government as recently as 1973. The two main constituents of the ink are tannic acid and ferrous sulfate (vitriol). The vitriol normally used was not very pure and likely contained a mixture of iron sulfate with traces of other metals, in particular, copper. Certain transition-metal ions contained in iron gall inks and their acidity are known to deteriorate paper. Therefore, stabilization treatments consist of deacidification and the addition of antioxidants. To this end, the use of tetraalkylammonium bromides was recently proposed. Here, it is shown that 1-butyl-2,3-dimethylimidazolium bromide both in aqueous and in alcoholic solution can prevent the oxidative deterioration of cellulose. Furthermore, it does not lead to the yellowing of paper nor does it significantly affect the colour of the ink.

• Two Fe3+ fluorescent probes based D-A type imidazole derivatives have been developed, which possessed a relatively great selectivity and sensitivity. • The probe molecules showed a relatively rare fluorescence color change response to Fe3+, its fluorescence changed from deep-blue to green. • The fluorescence sensing behavior of the probe molecules to Fe3+ was also applied to realize the rewritable paper in a very simple way. D-A type fluorescent probe usually shows a fluorescence quenching response to Fe3+, and relatively few probes can exhibit the fluorescence color change response. Herein, two high-luminescence D-A type imidazole derivatives TPABM and TPAFM were synthesized and used as Fe3+ fluorescent probes with an obvious fluorescence color change and remarkable sensing performance. Upon the addition of Fe3+, the original emission of TPABM and TPAFM was quenched, while a new emission peak emerged in the red-shifted direction, resulting in the fluorescence color changing from deep blue to green. This phenomenon may be caused by the coordination between the molecular imidazole ring and Fe3+ with a 1:1 ratio, which efficiently decreased the LUMO energy level of the probe molecules and formed a new CT emission with a lower energy gap. Furthermore, the probe molecules exhibited the potential for detecting Fe3+ in actual water samples and could be appropriated for the preparation of rewritable paper using a simple method. By using filter paper soaked with probe molecules as writing paper, Fe3+ aqueous solution as ink, and NaF aqueous solution as an eraser, the cycle of fluorescence writing and erasing was realized under UV irradiation. [Display omitted] [ABSTRACT FROM AUTHOR]

A simple approach to the mass production of nanoporous gold electrode arrays on cellulose membranes for electrochemical sensing of oxygen using ionic liquid (IL) electrolytes was established. The approach, combining the inkjet printing of gold nanoparticle (GNP) patterns with the self-catalytic growth of these patterns into conducting layers, can fabricate hundreds of self-designed gold arrays on cellulose membranes within several hours using an inexpensive inkjet printer. The resulting paper-based gold electrode arrays (PGEAs) had several unique properties as thin-film sensor platforms, including good conductivity, excellent flexibility, high integration, and low cost. The porous nature of PGEAs also allowed the addition of electrolytes from the back cellulose membrane side and controllably produced large three-phase electrolyte/electrode/gas interfaces at the front electrode side. A novel paper-based solid-state electrochemical oxygen (O(2)) sensor was therefore developed using an IL electrolyte, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF(6)). The sensor looked like a piece of paper but possessed high sensitivity for O(2) in a linear range from 0.054 to 0.177 v/v %, along with a low detection limit of 0.0075% and a short response time of less than 10 s, foreseeing its promising applications in developing cost-effective and environment-friendly paper-based electrochemical gas sensors.

Cellulose-based aerogel (CBA) was prepared from waste newspaper (WNP) without any pretreatment using 1-allyl-3-methyimidazolium chloride (AmImCl) as a solvent via regeneration and an environmentally friendly freeze-drying method. After being treated with trimethylchlorosilane (TMCS) via a simple thermal chemical vapor deposition process, the resulting CBAs were rendered both hydrophobic and oleophilic. Successful silanization on the surface of the porous CBA was verified by a variety of techniques including scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), and water contact angle (WCA) measurements. As a result, the silane-coated, interconnected CBAs not only exhibited good absorption performance for oils (e.g., waste engine oil), but also showed absorption capacity for organic solvents such as chloroform (with a representative weight gain ranging from 11 to 22 times of their own dry weight), making them diversified absorbents for potential applications including sewage purification., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Waste newspapers, composed of cellulose (>60wt%), lignin (∼15wt%), hemicellulose (∼10wt%) and other additives, are one kind of low-cost, easily collected and abundant resources. In order to get value-added products from this waste, in this work an attempt was made to directly convert waste newspapers into cellulose-based films by employing an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as a solvent. Most of the organic substances in this waste were dissolved quickly in AmimCl under mild conditions, and then coagulated and dried. Although containing lignin, hemicellulose and inorganic additives, the regenerated cellulose-based films were smooth, compact and semi-transparent, and exhibited good mechanical properties. If the newspaper/AmimCl solution was filtered to remove undissolved inorganic substances, the regenerated films became transparent and had a tensile strength of 80MPa. Thus, this work provides a new, simple and highly efficient way to achieve a high-valued utilization of waste newspapers for packaging and wrapping., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Simple paper chromatography of urine obtained in the Figlu test has been found satisfactory for determining excess excretion of the imidazole metabolites of histidine. It has been confirmed that examination for these in addition to formiminoglutamic acid is necessary for a full assessment of this test. When excretion of the latter is not abnormal in folic-acid and/or vitamin B(12) deficiency, that of urocanic acid, a glycine conjugate of urocanic acid and/or imidazole propionic acid, is usually raised. An abnormally high excretion of hydantoin-5-propionic acid after histidine has also been found in these deficiencies, and its estimation may be of additional use in the evaluation of the Figlu test.

Microwave irradiation can facilitate the dissolution and delignification of lignocelluloses in ionic liquids compared to simple oil bath heating as demonstrated here where 92.5% of 0.5 g ground southern yellow pine was dissolved in 10 g 1-ethyl-3-methylimidazolium acetate using microwave irradiation in only 4 min. Cellulose-rich material (pulp) regenerated from the wood/ionic liquid solution had a lignin content of ~10%; significantly lower than the lignin content of the original wood (31.9%) or that of pulp obtained from the same experiment but using 16 h of oil bath heating (16-24%). The 10% lignin content obtained with the microwave method was close to that of pulp obtained from the oil bath heating method when polyoxometalate catalysts were used (5-9%)., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

First pass metabolism by phase I and phase II enzymes in the intestines and liver is a major determinant of the oral bioavailability of many drugs. Several studies analyzed expressions of major drug-metabolizing enzymes (DMEs), such as CYP3A4 and UGT1A1 in the human gut and liver. However, there is still a lack of knowledge regarding other DMEs (i.e., "minor" DMEs), although several clinically relevant drugs are affected by those enzymes. Moreover, there is very limited intra-subject data on hepatic and intestinal expression levels of minor DMEs. To fill this gap of knowledge, we analyzed gene expression (quantitative real-time polymerase chain reaction) and protein abundance (targeted proteomics) of 24 clinically relevant DMEs, that is, carboxylesterases (CES), UDP-glucuronosyltransferases (UGT), and cytochrome P450 (CYP)-enzymes. We performed our analysis using jejunum and liver tissue specimens from the same 11 healthy organ donors (8 men and 3 women, aged 19-60 years). Protein amounts of all investigated DMEs, with the exception of CYP4A11, were detected in human liver samples. CES2, CYP2C18, CYP3A4, and UGT2B17 protein abundance was similar or even higher in the jejunum, and all other DMEs were found in higher amounts in the liver. Significant correlations between gene expression and protein levels were observed only for 2 of 15 jejunal, but 13 of 23 hepatic DMEs. Intestinal and hepatic protein amounts only significantly correlated for CYP3A4 and UGT1A3. Our results demonstrated a notable variability between the individuals, which was even higher in the intestines than in the liver. Our intrasubject analysis of DMEs in the jejunum and liver from healthy donors, may be useful for physiologically-based pharmacokinetic-based modeling and prediction in order to improve efficacy and safety of oral drug therapy., (© 2023 The Authors. Clinical Pharmacology & Therapeutics published by Wiley Periodicals LLC on behalf of American Society for Clinical Pharmacology and Therapeutics.)

Vegetable waste, including mixed cabbage residue (MCR), is considered a promising raw material for bioenergy production because of its high lignocellulosic component. In this study, the pretreatment of MCR by ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) was optimized based on response surface methodology. The optimal condition for MCR pretreatment was determined at 55.8 °C, with a reaction of 2.65 h and liquid-solid ratio of 4.60:1 v/w. Hydrolysis of pretreated MCR from optimal pretreatment conditions generated a maximum glucose yield of 156.65 ± 7.66 mg/g MCR. Untreated and pretreated MCRs were successfully characterized by scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. The pretreated MCR exhibited increased clear pores and incomplete structure. Moreover, compared with untreated biomass, decreased lignin, decreased hemicellulose, increased surface area, and cellulose crystallinity were observed. Thus, [Emim][OAc] pretreatment is a promising alternative approach for higher glucose production from MCR., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Gizzerosine [2-amino-9-(4-imidazolyl)-7-azanonanoic acid] is a toxic amino acid formed from histamine and lysine at high temperatures, and may be present in foodstuffs (e.g., fishmeal and meat-bone meal) for animals including cats and dogs. Here we developed a simple, rapid, sensitive, specific, and automated method for the analysis of gizzerosine in foodstuffs by high-performance liquid chromatography (HPLC) involving pre-column derivatization with o-phthaldialdehyde (OPA) in the presence of N-acetylcysteine (instead of the usual 2-mercaptoethanol or ethanethiol reagent). OPA reacted immediately (within 1 min) with gizzerosine in an autosampler at room temperatures (e.g., 20-25 °C), and their derivative was directly injected into the HPLC column. The highly fluorescent gizzerosine-OPA derivative was well separated from the OPA derivatives of all natural amino acids known to be present in physiological fluids (e.g., plasma), proteins and foodstuffs, and was detected at an excitation wavelength of 340 nm and an emission wavelength of 450 nm. The total time for chromatographic separation (including column regeneration) was 20 min per sample rather than 40 min and longer in previous HPLC methods. The detection limit for gizzerosine was at least 6 pmol/ml in an assay solution (HPLC vial) or at least 0.09 pmol per injection into the HPLC column. The analysis of gizzerosine was linear between 1 and 100 pmol per injection. When gizzerosine was extracted from foodstuffs, its detection limit was at least 875 pmol/g foodstuff or at least 0.21 mg/kg foodstuff. Our routine HPLC technique does not require any cleanup of samples or the OPA derivatization products (including the OPA-gizzerosine adduct), and is applicable for the analysis of gizzerosine in both foodstuffs and animal tissues., (© 2024. The Author(s), under exclusive license to Springer Nature Switzerland AG.)

Background: Based on the new data from the primary analysis of the OPTIC (Optimizing Ponatinib Treatment in CP-CML) trial on dose optimization of ponatinib in patients with chronic phase (CP)-CML, the German consensus paper on ponatinib published in 2020 (Saussele S et al., Acta Haematol. 2020) has been updated in this addendum., Summary: Focus is on the update of efficacy and safety of ponatinib, reflecting the new data set, as well as the update of the benefit-risk assessment and recommendations for ponatinib starting dose in CP-CML - provided that the decision to use ponatinib has already been made. Furthermore, based on OPTIC and additional empirical data, the expert panel collaborated to develop a decision tree for ponatinib dosing, specifically for intolerant and resistant patients. The recommendations on cardiovascular management have also been updated based on the most recent 2021 guidelines of the European Society of Cardiology (ESC) on cardiovascular disease prevention in clinical practice., Key Messages: The OPTIC data confirm the high efficacy of ponatinib in patients with CP-CML and provide the basis for individualized dose adjustment during the course of treatment., (© 2023 The Author(s). Published by S. Karger AG, Basel.)

[Display omitted] • Oxidative photocyclization of 4,5-diphenyl-substituted imidazoles led to 9,10-phenanthroimidazoles. • The intermediate 4a,4b-dihydrophenanthrene derivatives are very unstable species. • The revised structures of photoproducts, reported in [ J. Photochem. Photobiolog. A 2024 , 454 , 115750]. In the recent paper of S. Pu and coworkers (J. Photochem. Photobiolog. A 2024 , 454 , 115750), three novel 4,5-diphenylimidazole derivatives were studied. The fluorescent properties of these compounds changed drastically upon UV irradiation, as a result of irreversible phototransformation. As products of this reaction, the authors proposed questionable 7a,7b-dihydrophenanthro[9,10-d]imidazoles with completely non-aromatic core. Based on the literature data as well as author's results, we suggest more believable structures of photoproducts, formed via well-known oxidative photocyclization (Mallory reaction) or photocyclization / H-migration. [ABSTRACT FROM AUTHOR]

Lignocellulosic biomass offers economic and environmental advantages over corn starch for biofuels production. However, its fractionation currently requires energy-intensive pretreatments, due to the lignin chemical resistance and complex cell wall structure. Recently, ionic liquids have been used to dissolve biomass at high temperatures. In this study, thin sections of poplar wood were swollen by ionic liquid (1-ethyl-3-methylimidazolium acetate) pretreatment at room temperature. The samples contract when rinsed with deionized water. The controlled expansion and contraction of the wood structure can be used to incorporate enzymes and catalysts deep into the wood structure for improved pretreatments and accelerated cellulose hydrolysis. As a proof of concept, silver and gold nanoparticles of diameters ranging from 20 to 100 nm were incorporated at depths up to 4 mum. Confocal surface-enhanced Raman images at different depths show that a significant number of nanoparticles were incorporated into the pretreated sample, and they remained on the samples after rinsing. Quantitative X-ray fluorescence microanalyses indicate that the majority of nanoparticle incorporation occurs after an ionic liquid pretreatment of less than 1 h. In addition to improved pretreatments, the incorporation of materials and chemicals into wood and paper products enables isotope tracing, development of new sensing, and imaging capabilities.

Chemiluminescence (CL) reagent luminol was loaded into the porous structure of cobalt-imidazole metal-organic framework (MOF) ZIF-67 to obtain luminol-functionalized ZIF-67 (luminol@ZIF-67) with CL property. The morphology, composition, CL property, and CL mechanism of luminol@ZIF-67 were carefully investigated. The obtained luminol@ZIF-67 exhibited strong, stable, and visible CL emission that reacted with H2O2, attributed to the strong catalytic effect of ZIF-67 combined with the shortened diffusion distance between luminol and the catalytic center. The CL intensity of luminol@ZIF-67 was more than 550 times higher than that of luminol. Catechol can effectively quench the CL emission of luminol@ZIF-67 that reacted with H2O2. Then, a simple paper-based CL imaging detection method was developed for the detection of catechol by using a smartphone as a portable detector. The linear calibration curve of the developed CL assay for catechol ranged from 5 to 100 mg/L with detection limit of 1.1 mg/L (S/N = 3δ). The strong CL emission of luminol@ZIF-67 combined with the effective quench ability of catechol guaranteed high sensitivity of the detection method. The practical application ability of the developed CL assay was tested by the determination of catechol in tea and tap water samples, resulting in acceptable results. This work provides an effective paper-based CL detection method for catechol and enriches the species of the chemiluminescent MOF material. [ABSTRACT FROM AUTHOR]

A new method for simultaneous determination of two diastereomers in each of S-[2-carboxy-1-(1H-imidazol-4-yl)ethyl]-L-cysteine (I) and N-¿S-[2-carboxy-1-(1H-imidazol-4-yl)ethyl]-L-cysteinyl¿glycine (II) was developed by electrophoresis using a neutral coated capillary with a separation buffer, pH 6.00, containing 80 mM hydroxypropyl-beta-cyclodextrin at a field strength of 500 V cm-1 at 20 degrees C. This method was applied to establishment of a catabolic pathway from S-[2-carboxy-1-(1H-imidazol-4-yl)ethyl]glutathione (III) to compound I. Incubation of either of compound II diastereomers as an enzyme substrate with rat kidney homogenate in a phosphate buffer, pH 7.4, resulted in a formation of compound I only having correspondent configurations on asymmetric carbon atoms of its molecule with those of the substrate, i.e., no occurrence of isomerization in the catabolism. Additionally, little difference in action as the substrate between two diastereomers of compound II was found. When an equimolar mixture of two diastereomers of compound III was allowed to react with the homogenate in the presence of glycylglycine, two diastereomers of compound II were formed in the same yield with each other and then these were catabolized gradually to both isomers of compound I. These results suggest that compound II is a metabolic intermediate for the formation of compound I from compound III, and that little variation in reactivities of two diastereomers of compound III as well as compound II with enzymes is given by the difference in stereoisomerism of asymmetric carbon atoms on their molecules.

In anaerobic bacteria, glycine, formate, and the amide-N of glutamine are building blocks for the biosynthesis of the imidazole moiety of the vitamin B12-base 5,6-dimethylbenzimidazole. These building blocks are also used for the biosynthesis of the imidazole moiety of purine bases. Therefore we tested 4(5)-aminoimidazole, the base moiety of the purine nucleotide precursor 5-aminoimidazole ribonucleotide, for its putative function as precursor of 5,6-dimethylbenzimidazole. The anaerobic vitamin B12-producer Eubacterium limosum, grown in the presence of [2-13C]4(5)-aminoimidazole, synthesized nonlabeled vitamin B12, but also [2-13C]7-azabenzimidazolylcobamide and [2-13C]5,6-dimethyl-7-azabenzimidazolylcobamide. [2-13C]limidazole was used by E. limosum to form [2-13C]imidazolylcobamide. Simultaneously nonlabeled vitamin B12 was synthesized. This shows that 4(5)-aminoimidazole and imidazole are not intermediates in the biosynthesis of 5,6-dimethylbenzimidazole. However, 4(5)-aminoimidazole has obviously a structure similar to the structure of an as yet unknown precursor of the vitamin B12-base, and is therefore transformed into the aza analogs. In order to prepare a reference compound 4(5)-azabenzimidazole was added to a culture of Propionibacterium shermanii and to a culture of E. limosum, P. shermanil transformed this base mainly to 4-azabenzimidazolylcobamide, as determined by 1H NMR-spectroscopy (NOE experiment). In contrast E. limosum produced mainly 7-azabenzimidazolylcobamide. The reason for this difference is discussed.

Formation of 3-[(carboxymethyl)thio]-3-(1H-imidazol-4-yl)propanoic acid (I) and S-[2-carboxy-1-(1H-imidazol-4-yl)ethyl]cysteine (II), compounds found in human urine, has been demonstrated by enzymatic degradation of S-[2-carboxy-1-(1H-imidazol-4-yl)ethyl]glutathione (III). Compound (III) was chemically synthesized in 72% yield by incubating the reaction mixture of trans-urocanic acid and 3-fold excess GSH at 65 degrees C for 1 wk, which was accompanied by formation of N-(S-[2-carboxy-1-(1H-imidazol-4-yl)ethyl]cysteinyl)glycine (IV) in 15% yield. S-[2-Carboxy-1-(1H-imidazol-4-yl)ethyl]-N-gamma-glutamylcysteine (V) was produced by partial hydrolysis of compound (III) in HCl. The synthesized compounds were characterized mainly by fast-atom bombardment mass spectrometry and high-voltage paper electrophoresis as well as chemical degradation. Incubation of compound (III) with rat kidney homogenate in a Tris buffer (pH 8), formed compound (II) in 80% yield possibly via compound (IV). Yield of compound (II) was increased by adding glycylglycine to the reaction mixture. However, little degradation of compound (III) occurred in the use of rat liver, brain, heart or spleen homogenate as the enzyme source. Compound (II) was further metabolized to compound (I) by incubation with rat kidney homogenate in a phosphate buffer of pH 7.4. From these results, we suggest that the urinary compounds are products of enzymatic degradation of compound (III) and that GSH may participate in the metabolism of urocanic acid, the first catabolite of L-histidine.

The described analytical method for histamine determination in fish and seafood consists of sample extraction, adsorption onto a paper disc, application of the paper disc onto electrophoresis paper, electrophoresis for only 10 min, drying, and color developing by Pauly’s reagent. Histamine can be satisfactorily detected and completely separated from histidine, carnosine and other Pauly reagent-positive compounds. This method does not require expensive instrumentation and any tedious pretreatment to eliminate potential interference by other imidazole compounds, such as histidine or carnosine. This method can be used to detect histamine in multiple fish and seafood samples simultaneously that contain as little as 15 p.p.m. histamine (1.5 mg/100 g). [ABSTRACT FROM AUTHOR]

• A new strategy was proposed to produce multi-colored solid-state carbon dots. • The product exhibited photo-triggering, reversible and dynamic-optical properties. • Photo-rewritable paper and dynamic anti-counterfeit patterns were fabricated. Dynamic optical materials can respond to external stimuli to give intriguing and chameleon-like visual effect and carry more information, they hence have attracted considerable attention. In this work, we propose a simple and efficient strategy to construct multi-color solid-state carbon dots (CDs) materials with photo-switchable and reversible dynamic-optical properties. A photochromic and positively-charged cellulose derivative C-Im+-SP with an imidazole salt (Im+) group and a spiropyran (SP) group is designed and synthesized. Subsequently, C-Im+-SP is spontaneously coated on the surface of negatively-charged CDs (NCDs) via electrostatic attraction to form a physical protective shell, which not only inhibits aggregation-caused quenching (ACQ) in NCDs but also promotes effective fluorescence resonance energy transfer (FRET). The resultant NCDs@C-Im+-SP exhibits a photo-triggering reversible dynamic-optical property. The NCDs to C-Im+-SP ratio can be used to effectively regulate fluorescence emission and fluorescence kinetics. The polymeric C-Im+-SP shell layer endows NCDs with excellent processability and formability, whereby NCDs@C-Im+-SP materials can be utilized as functional coatings and inks to fabricate photo-rewritable paper and dynamic anti-counterfeit patterns that have considerable potential applications for special coatings, complex anti-counterfeiting, and information encryption. [ABSTRACT FROM AUTHOR]

Due to the fast dynamics and re-equilibration of supramolecular self-assembly, bottom-up molecular strategies to fabricate well-defined and controllable multiblock structures are rare. Herein, we propose a new concept for fabrication of fluorescent multiblock microcolumns containing 1 to 7 blocks via hierarchical supramolecular self-assembly based on cucurbit[8]uril (CB[8]), NaBr and an AIEgen guest. Through the complexation between CB[8] and different numbers of AIEgen guests (2, 1, 0), the competitive displacement caused by the binding of the sodium cation to the CB[8] portal, and the reversible assembly of positively charged guests in salt solutions, one-pot hierarchical supramolecular self-assembly is realized. The molecular structure of each block is analyzed by single-crystal X-ray diffraction. The AIEgen enables the self-assembly of multiblocks to be visualized, understood, and regulated., (© 2022 Wiley-VCH GmbH.)

1. Imidazol-5-ylpropionate and imidazol-5-yl-lactate are degraded by Pseudomonas testosteroni via inducible pathways. 2. Growth on either compound as the sole source of carbon results in the induction of the enzymes for histidine catabolism. 3. The pathway of histidine degradation in this organism, a non-fluorescent Pseudomonad, is shown to be the same as that operating in Pseudomonas fluorescens and Pseudomonas putida. It consists of the successive formation of urocanate, imidazol-4-on-5-ylpropionate, N-formimino-l-glutamate, N-formyl-l-glutamate and glutamate. 4. Whole cells of P. testosteroni accumulate urocanate in the reaction mixture when incubated with imidazolylpropionate, but only after an adaptive lag period which is removed by previous growth on imidazolylpropionate as the source of carbon. 5. Imidazolyl-lactate is oxidized to imidazolylpyruvate, which then gives rise to histidine by specific transamination with l-glutamate. 6. Cells grown on histidine, urocanate or imidazolylpropionate are also able to degrade imidazolyllactate. 7. Mutants lacking urocanase are unable to grow on imidazolylpropionate, imidazolyl-lactate, histidine or urocanate. One with impaired histidase activity cannot utilize histidine or imidazolyl-lactate, but grows normally on imidazolylpropionate or urocanate. A mutant unable to grow on imidazolylpropionate is indistinguishable from the wild-type with respect to growth on histidine, imidazolyl-lactate or urocanate. 8. Thus it is established that imidazolyl-lactate is metabolized via histidine whereas imidazolylpropionate enters the histidine degradation pathway after conversion into urocanate.

To develop an efficient method for the production of urocanic acid, optimal conditions for the production of microbial L-histidine ammonia lyase and for the conversion of L-histidine to urocanic acid by this enzyme were studied. A number of microorganisms were screened to test their ability to form and accumulate urocanic acid from L-histidine. Achromobacter liquidum was selected as the best organism. With this organism, enzyme activity as high as 2.0 units/ml could be produced by a shaking culture at 30 C in a medium containing glucose, urea, potassium phosphate, L-histidine, yeast extract, peptone, and inorganic salts. Appropriate addition of a surface-active agent to the reaction mixture shortened the time required for the conversion. A large amount of L-histidine was converted stoichiometrically to urocanic acid in 48 h at 40 C. Accumulated urocanic acid was readily isolated in pure form by ordinary procedures with isoelectric precipitation. Yields of isolated urocanic acid of over 92% from L-histidine were easily attainable. When the culture of Achromobacter liquidum was added to DL-histidine, D-histidine and urocanic acid were simultaneously obtained in high yields.

Reaction of 0.20M orthophosphate with 0.20M N,S-diacetylcysteamine in 0.40M imidazole at pH 7.0 or 8.0 under drying conditions at 50 degree C for 6 days yields pyrophosphate and tripolyphosphate in the presence and absence of 0.10M divalent metal ion. The efficiency of utilization of N,S-diacetylcysteamine in the formation of pyrophosphate linkages ranges from 3 - 8% under the above conditions. The thioester, N,S-diacetylcysteamine, and imidazole are required for phosphoanhydride formation. Reaction of 0.40M orthophosphate with 0.20M N,S-diacetylcysteamine in 0.40M orthophosphate with 0.20M N,S-diacetylcysteamine in 0.40M imidazole at ambient temperature for 6 days yields phosphorylimidazole in the absence or presence of 0.50M MgCl2. Phosphorylimidazole and pyrophosphate are formed in the presence of 0.05M CaCl2; pyrophosphate and tripolyphosphate are formed with 0.15M CaCl2. The efficiency of utilization of N,S-diacetylcysteamine in the formation of pyrophosphate linkages is roughly 7% at 6 days of reaction with 0.15M CaCl2. The thioester, N,S-diacetylcysteamine and imidazole are required for the formation of phosphoanhydrides. The significance of these reactions to molecular evolution is discussed.

1. Serine reacts with N,N'-carbonyldiimidazole in aqueous solution at 0 degrees C to yield Nalpha-[imidazolyl-(1)-carbonyl]-L-serine. This compound slowly transforms to L-2-oxo-oxazolidine-5-carboxylic acid. We found that L-2-oxo-oxazolidine-5-carboxylic acid was stable to hydrolysis under a variety of conditions and did not oligomerize to yield peptides. Threonine was found to react in an analogous manner with N,N'-carbonyldiimidazole, yielding Nalpha-[imidazolyl-(1)-carbonyl]-L-threonine and L-(+)-trans-5-methyl-2-oxo-oxazolidine-5-carboxylic acid. 2. Histidine reacts with N,N'-carbonyldimidazole in aqueous solution at 0 degrees C to yield a variety of histidine-containing intermidiates. These slowly transform to give 7-carboxy-imidazole-[1,5cotetrahydropyrimidin-5-one in up to 90% yield. 3. The polymerization of 7-carboxy-imidazo-[1,5c]-tetrahydropyrimidin-5-one in imidazole buffer at 30 degrees gives excellent yields of oligohistidines.