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The first Lewis acid base adducts of MoF6 and an organic base have been synthesized, i. e., MoF6(NC5H5) and MoF6(NC5H5)2. These adducts are structurally characterized with X‐ray crystallography, showing that both adducts adopt capped trigonal prismatic structures. The MoF6(NC5H5) and MoF6(NC5H5)2 adducts are fluxional on the NMR time scale at room temperature. Two different fluorine environments could be resolved by 19F NMR spectroscopy at −80 °C for the 1 : 2 adduct, MoF6(NC5H5)2, whereas MoF6(NC5H5) remains fluxional at that temperature. Density functional theory (DFT) calculations aide the assignment of the infrared and Raman spectra. Natural Bond Order and Molecular Electrostatic Potential analyses elucidate the structures and properties of the MoF6 pyridine adducts. Regions of significantly higher molecular electrostatic potential, i. e., σ‐holes, in trigonal prismatic compared to octahedral MoF6 rationalize the capped trigonal prismatic geometry of the adducts. Whereas MoF6(NC5H5) is stable at room temperature under exclusion of moisture, MoF6(NC5H5)2 decomposes at 60 °C in pyridine solvent, and the solid slowly decomposes at room temperature after 24 h. [ABSTRACT FROM AUTHOR]

Boronic acids form diester bonds with cis-hydroxyl groups in carbohydrates. The formation of these adducts could impair the physical and chemical properties of precursors, even their biological activity. Two carbohydrate derivatives from d-fructose and d-arabinose and phenylboronic acid were synthesized in a straightforward one-step procedure and chemically characterized via spectroscopy and X-ray diffraction crystallography. Additionally, an acute toxicity test was performed to determine their lethal dose 50 (LD50) values by using Lorke's method. Analytical chemistry assays confirmed the formation of adducts by the generation of diester bonds with the β-d-pyranose of carbohydrates, including signals corresponding to the formation of new bonds, such as the stretching of B–O bonds. NMR spectra yielded information about the stereoselectivity in the synthesis reaction: Just one signal was found in the range for the anomeric carbon in the 13C NMR spectra of both adducts. The acute toxicity tests showed that the LD50 value for both compounds was 1265 mg/kg, while the effective dose 50 (ED50) for sedation was 531 mg/kg. However, differences were found in the onset and lapse of sedation. For example, the arabinose derivative induced sedation for more than 48 h at 600 mg/kg, while the fructose derivative induced sedation for less than 6 h at the same dose without the death of the mice. Thus, we report for the first time two boron-containing carbohydrate derivatives inducing sedation after intraperitoneal administration. They are bioactive and highly safe agents. Further biological evaluation is desirable to explore their medical applications. [ABSTRACT FROM AUTHOR]

During recrystallization from benzene or toluene of the products of interaction of triarylantimony or triarylbismuth with carboxylic acids, phenol, or oxime in the presence of tert-butyl hydroperoxide (molar ratio 1 : 2 : 1, diethyl ether, 24°C, 24 h), minor products, adducts of aryl compounds of antimony or bismuth of the Ar3MX2 type with carboxylic acids, phenol, and oxime are isolated. According to X-ray structural analysis conducted at 293 K using an automatic D8 Quest Bruker four-circle diffractometer (two-coordinate CCD detector, Mo Kα radiation, λ = 0.71073 Å, graphite monochromator), the metal atoms in the crystals of m-Tol3Sb[OC(O)C6H3F2-2,5]2 ⋅ HOC(O)C6H3F2-2,5 (1) [C42H31O6F6Sb, M 867.42; triclinic system, symmetry group P ; cell parameters a = 8.78(5) Å, b = 13.10(6) Å, c = 16.64(8) Å; α = 102.86(19)°, β = 99.3(2)°, γ = 98.0(3)°; V = 1813(16) Å3; Z 2; reflection index intervals –7 ≤ h ≤ 7, –11 ≤ k ≤ 11, –14 ≤ l ≤ 14; total reflections 14 149; independent reflections 2603; Rint 0.0284; GOOF 1.049; R1 = 0.0348, wR2 = 0.0938; residual electron density 0.55/–0.42 e/Å3], p‑Tol3Bi[OC(O)C6HF4-3,4,5,6]2 ⋅ HOC(O)C6HF4-3,4,5,6 (2) [C42H25O6F12Bi, M 1062.60; triclinic system, symmetry group P ; cell parameters a = 12.246(11) Å, b = 12.976(18) Å, c = 14.391(13) Å; α = 68.27(4)°, β = 69.89(3)°, γ = 86.11(5)°; V = 1990(4) Å3; Z 2; reflection index intervals –15 ≤ h ≤ 15, ‒16 ≤ k ≤ 16, –18 ≤ l ≤ 18; total reflections 48 542; independent reflections 9207; Rint 0.0321; GOOF 1.136; R1 = 0.0322, wR2 = 0.0648; residual electron density 1.81/–1.08 e/Å3], [(2-MeO-5-BrC6H3)3SbOC6H4Br-4]2O ⋅ 2HOC6H4Br-4 (3) [C66H54Br10O11Sb2, M 2065.69; monoclinic system, symmetry group C21/c; cell parameters a = 12.017(14) Å, b = 25.54(3) Å, c = 13.181(18) Å; β = 116.71(5)°; V = 3613(8) Å3; Z 2; reflection index intervals –13 ≤ h ≤ 13, –27 ≤ k ≤ 27, –12 ≤ l ≤ 12; total reflections 29 461; independent reflections 4545; Rint 0.0656; GOOF 1.062; R1 = 0.0565, wR2 = 0.1200; residual electron density 1.59/–1.31 e/Å3], and [(2-MeO)C6H4]3Sb[ON=CHC4H2(NO2-2)]2 ∙ 2HON=CHC4H2(NO2-2) ∙ 1/2PhH (4) [C44H38N8O19Sb, M 1104.57; triclinic system, symmetry group P ; cell parameters a = 10.240(5) Å, b = 14.480(8) Å, c = 18.093(11) Å; α = 103.43(3)°, β = 104.50(2)°, γ = 98.876(17)°; V = 2461(2) Å3; Z 2; reflection index intervals –13 ≤ h ≤ 13, –18 ≤ k ≤ 18, –23 ≤ l ≤ 23; total reflections 58 643; independent reflections 10 886; Rint 0.0558; GOOF 1.061; R1 = 0.0429, wR2 = 0.1095; residual electron density 1.91/–0.51 e/Å3] show distorted trigonal-bipyramidal coordination with oxygen atoms in axial positions. Full tables of atom coordinates, bond lengths, and valence angles for the structures are deposited in the Cambridge Structural Database (no. 2050322 for 1, no. 2045173 for 2, no. 2070387 for 3, and no. 2119790 for 4; deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk). [ABSTRACT FROM AUTHOR]

It has been shown that nicotinamide coenzymes (NADPH, NADH, NADP+, and NAD+) are capable of generating superoxide anions () in an alkaline environment. The superoxide-generating activity of the coenzymes is associated with high pH values and is sensitive to SOD. However, nicotinamide itself, being a functional part of coenzyme molecules, does not have this property. Polarographic studies showed that in the presence of coenzymes, molecular oxygen is consumed from the buffer, namely oxygen activation occurs due to the formation of . Based on the obtained results and in accordance with the literature, our observations suggest that the formation of adducts of nicotinamide, which is part of the coenzyme molecule, and hydroxyl anions (OH–) may lead to the formation of . Under mild conditions in the organism, the studied coenzymes, while performing their main functions, are expected to generate superoxide, meaning that they can be signaling molecules. [ABSTRACT FROM AUTHOR]

Acetaminophen (APAP) is a widely used drug, but overdose can cause severe acute liver injury. The first reports of APAP hepatotoxicity in humans were published in 1966, shortly after the development of alanine aminotransferase (ALT) and aspartate aminotransferase (AST) as the first biomarkers of liver injury as opposed to liver function. Thus, the field of liver injury biomarkers has evolved alongside the growth in APAP hepatotoxicity incidence. Numerous biomarkers have been proposed for use in the management of APAP overdose patients in the intervening years. Here, we comprehensively review the development of these markers from the 1960s to the present day and briefly discuss possible future directions. [ABSTRACT FROM AUTHOR]

Acetaminophen (APAP) is a widely used drug, but overdose can cause severe acute liver injury. The first reports of APAP hepatotoxicity in humans were published in 1966, shortly after the development of alanine aminotransferase (ALT) and aspartate aminotransferase (AST) as the first biomarkers of liver injury as opposed to liver function. Thus, the field of liver injury biomarkers has evolved alongside the growth in APAP hepatotoxicity incidence. Numerous biomarkers have been proposed for use in the management of APAP overdose patients in the intervening years. Here, we comprehensively review the development of these markers from the 1960s to the present day and briefly discuss possible future directions.

Boronic acids form diester bonds with cis-hydroxyl groups in carbohydrates. The formation of these adducts could impair the physical and chemical properties of precursors, even their biological activity. Two carbohydrate derivatives from d-fructose and d-arabinose and phenylboronic acid were synthesized in a straightforward one-step procedure and chemically characterized via spectroscopy and X-ray diffraction crystallography. Additionally, an acute toxicity test was performed to determine their lethal dose 50 (LD50) values by using Lorke’s method. Analytical chemistry assays confirmed the formation of adducts by the generation of diester bonds with the β-d-pyranose of carbohydrates, including signals corresponding to the formation of new bonds, such as the stretching of B–O bonds. NMR spectra yielded information about the stereoselectivity in the synthesis reaction: Just one signal was found in the range for the anomeric carbon in the 13C NMR spectra of both adducts. The acute toxicity tests showed that the LD50 value for both compounds was 1265 mg/kg, while the effective dose 50 (ED50) for sedation was 531 mg/kg. However, differences were found in the onset and lapse of sedation. For example, the arabinose derivative induced sedation for more than 48 h at 600 mg/kg, while the fructose derivative induced sedation for less than 6 h at the same dose without the death of the mice. Thus, we report for the first time two boron-containing carbohydrate derivatives inducing sedation after intraperitoneal administration. They are bioactive and highly safe agents. Further biological evaluation is desirable to explore their medical applications.

The performance prerequisites for nonlinear optical (NLO) crystals encompass a substantial second‐harmonic generation (SHG), a considerable laser induced damage threshold, and a moderate degree of birefringence. Nevertheless, the presence of particular anions may result in deficiencies within certain properties. The utilization of mixed anionic groups has emerged as an effective strategy to achieve a balance among numerous performance parameters of NLO crystals, particularly in terms of SHG responses and bandgaps. Compared with other heteroanionic compounds, adduct‐type compounds feature more concise structures with specific properties. Herein, we aim to provide an overview of the recent advancements in adduct‐type NLO crystals, focusing on their structures and properties. Furthermore, we analyze the coordination chemistry and disadvantages involved in adducts, and discuss the current synthesis methods as well as future directions for further exploration. [ABSTRACT FROM AUTHOR]

This study carried out a detailed step‐by‐step PBE/TZVP level analysis of the inclusion of Fe(III)/Fe(II) aqua complexes into the cavity of cucurbit[6]urils (CB[6]). The structural characteristics of all intermediate stable structures formed during the inclusion process from the bulk of aqueous solution to the inclusion compound were obtained. To account for solvation effects, a molecular‐continuum model was used in which six water molecules of the first coordination sphere of aqua complexes and 12 water molecules of the second coordination sphere were taken into account, while the interaction of such a supermolecule with a dielectric medium was accounted within the continuum model (PCM) [Correction added on 9 June 2023, after first online publication. The word molecular continual has been changed to molecular‐continuum in the sentence.]. The process of incorporation of the aqua complex into the cavity was found to be accompanied by a partial desolvation of the second coordination sphere of the aqua complex and a change in the structure of the first coordination sphere. Additionally, the standard electrode potential of the half‐reaction Fe3+(aq) + e = Fe2+(aq) was estimated for all adducts formed in the reaction. [ABSTRACT FROM AUTHOR]

Psoriasis, one of the most frequent immune-mediated skin diseases, is manifested by numerous psoriatic lessons on the skin caused by excessive proliferation and keratinization of epidermal cells. These disorders of keratinocyte metabolism are caused by a pathological interaction with the cells of the immune system, including lymphocytes, which in psoriasis are also responsible for systemic inflammation. This is accompanied by oxidative stress, which promotes the formation of lipid peroxidation products, including reactive aldehydes and isoprostanes, which are additional pro-inflammatory signaling molecules. Therefore, the presented review is focused on highlighting changes that occur during psoriasis development at the level of lipid peroxidation products, including 4-hydroxynonenal, 4-oxononenal, malondialdehyde, and acrolein, and their influence on protein structures. Furthermore, we will examine inducing agents of cellular functioning, as well as intercellular signaling. These lipid peroxidation products can form adducts with a variety of proteins with different functions in the body, including proteins within skin cells and cells of the immune system. This is especially true in autoimmune diseases such as psoriasis. For example, these changes concern proteins involved in maintaining redox homeostasis or pro-inflammatory signaling. Therefore, the formation of such adducts should attract attention, especially during the design of preventive cosmetics or anti-psoriasis therapies.

Herein, we describe the synthesis of coordination compounds starting from carbohydrazide ((H2NHN)2C=O (CHZ)) and the Zn2+ salt of dinitramic acid (HDN), which are high-nitrogen substances that exhibit properties similar to those of a burning-rate inhibitor of pyrotechnic compositions. This study demonstrates that these compounds react with glyoxal to furnish adducts of metal–organic macrocyclic cages bearing the elements of carbohydrazide, complexing metals and the HDN anion, depending on the ratio of the starting reactants. The assembled macrocyclic cage has "host–guest" properties and is a safe container for the storage of HDN salts. X-ray crystallographic analysis of the resultant coordination compound, [Zn(chz)3(N(NO2)2)2]), indicated that the metal–ligand association occurs via the N and O atoms of carbohydrazide. The zinc salt of dinitramic acid, which is enclosed into adducts with a macrocycle, is thermally stable and insensitive to mechanical impacts. The complex zinc salt of dinitramide was shown herein to exhibit inhibitory activity towards the burning rate of pyrotechnic compositions. [ABSTRACT FROM AUTHOR]

Valproic acid (VPA) is a well‐known drug prescribed as anti‐epileptic. It has a narrow therapeutic range and shows great individual differences in pharmacodynamics and pharmacokinetics. Consequently, the therapeutical drug monitoring (TDM) in patient's plasma is of crucial importance. Liquid chromatography coupled to mass spectrometry (LC–MS/MS) has gained importance in TDM applications for its features of sensitivity, selectivity and rapidity. However, in case of VPA, the LC–MS/MS selectivity could be hampered by the lack of a sufficient number of multiple reaction monitoring (MRM) transitions describing the molecule. In fact, the product ion scan of deprotonated molecules of VPA does not produce any ion and thus most LC–MS/MS methods are based on the detection of the unique MRM transition m/z 143➔143. In this way, the advantages of selectivity in LC–MS cannot be effectively exploited. In the present method, stable analyte adducts were exploited for the determination of VPA in blood. An Acquity HSS C18 column and mobile phases consisting of 5‐mM ammonium formate and acetonitrile both added 0.1% formic acid were used. Source worked in negative acquisition mode and parameters were optimized to increase the adduct (m/z 189) and dimer (m/z 287) stability, and their fragmentation were used to increase the selectivity of MRM detection. The method has been validated according to the toxicological forensic guidelines and successfully applied to 10 real blood samples. Finally, the present method showed suitable for the rapid LC–MS/MS detection of VPA in whole blood, demonstrating the possibility to increase specificity by exploiting stable in‐source adducts. This should be considered of utmost importance in the case of forensic applications. [ABSTRACT FROM AUTHOR]

Regulation of Lewis acid‐base adduct intermediate is more critical for the dual metal ions of Sn2+ and Pb2+ than for the single metal ion such as Pb2+ in preparing high quality perovskite films. It has been reported here that the photovoltaic performance of Sn‐Pb alloyed perovskite solar cells is dependent on the interaction between metal ions and Lewis base additives. Urea and thiourea are selected as an O‐ and a S‐donor, respectively, which is used as an additive in the precursor solution including equimolar SnI2 and PbI2 together with organic iodides of formamidinium iodide and methylammonium iodide, forming a nominal composition of FA0.5MA0.5Pb0.5Sn0.5I3. Open‐circuit voltage (Voc) is increased while maintaining short‐circuit photocurrent density (Jsc) after the addition of urea. On the other hand, both Jsc and Voc are simultaneously increased by adding thiourea, leading to a considerable increase in power conversion efficiency from 14.58% (control) to 18.59%. A strong interaction between the relatively soft Sn2+, compared to Sn4+, and the soft sulfur in thiourea, associated with hard and soft acid and base theory, suppresses effectively a disproportionation reaction of 2Sn2+→ Sn4+ + Sn0, which results in a substantial enhancement of carrier lifetime and consequently photovoltaic performance. [ABSTRACT FROM AUTHOR]

Adductomics, an emerging field within the 'omics sciences, focuses on the formation and prevalence of DNA, RNA, and protein adducts induced by endogenous and exogenous agents in biological systems. These modifications often result from exposure to environmental pollutants, dietary components, and xenobiotics, impacting cellular functions and potentially leading to diseases such as cancer. This review highlights advances in mass spectrometry (MS) that enhance the detection of these critical modifications and discusses current and emerging trends in adductomics, including developments in MS instrument use, screening techniques, and the study of various biomolecular modifications from mono-adducts to complex hybrid crosslinks between different types of biomolecules. The review also considers challenges, including the need for specialized MS spectra databases and multi-omics integration, while emphasizing techniques to distinguish between exogenous and endogenous modifications. The future of adductomics possesses significant potential for enhancing our understanding of health in relation to environmental exposures and precision medicine. [Display omitted] • Significance of multi-adductomics analysis for elucidating the exposome. • Current developments for DNA, RNA and protein adductomics. • Advances in HRMS technology facilitating multi-adductomics analysis. • Discussion of challenges and perspectives for multi-adductomics. [ABSTRACT FROM AUTHOR]

Background: Acetaminophen (APAP)-associated transaminase elevation, induced by N-acetyl-p-benzoquinone imine (NAPQI) protein adduction, remains an area of research interest. Distinct from known genetic, physiologic, and dosage associations dictating severity of hepatic injury, no known factors predict an absence of protein adduct formation at therapeutic APAP dosing. Hypothesis: Sex-based physiology is predictive of APAP-induced protein adduct formation and differential metabolite expression at therapeutic doses. Methods: This retrospective study interrogated serum samples collected for a prior study investigating fluctuations of alanine aminotransferase (ALT) over time with 4G daily APAP dosing for ≥ 16 days in subjects from Denver, Colorado. Subjects were grouped by adduct formation (n = 184) vs no adducts (n = 20). Samples were run on ultra-high-performance liquid chromatography mass spectrometry from study days 0, 7, 16, and 31. Significant metabolite expressions were identified using t-tests with false discovery rate correction (FDR), partial least squares discriminant, and ANOVA simultaneous comparison analyses. Demographic and clinical data were explored using t-tests with FDR (age, weight, BMI, ALT) and Chi-square (sex, ethnicity, race) analyses. Results: In pre-treatment samples, relative quantitation caprylic acid was expressed ninefold higher and 6-carboxyhexanoate was expressed threefold lower in subjects who did not develop adducts. Lactate had greater expression in the no adducts group (p = 0.001). Using absolute quantitation, glutathione was expressed 2.6-fold greater among no adduct subjects. Odds of males developing NAPQI protein adducts at therapeutic APAP dosing were 5.91 times lower than females (95% CI = 2.3–14.9; p = 0.0001). Conclusion: Multiple metabolites were differentially expressed based on adduct group and sex. Metabolites were identified unique to adduct development independent of sex. At therapeutic APAP dosing, males were less likely to develop APAP protein adducts. Further research into lipid biosynthesis and metabolism may provide further insight into physiology associated with adduct production. [ABSTRACT FROM AUTHOR]

In this work, we have focused on the synthesis of a copper(II) complex with an imine derived from 4-nitroaniline (4noa) and 2-hydroxy-1-naphthaldehyde (n), as well as its coordinatively saturated adducts. The obtained metal complex is reasonably soluble in pyridine (py) and tetrahydrofuran (thf), resulting in the formation of two adducts. The complex and adducts have been synthesized both by conventional solventbased methods and by liquid-assisted grinding (LAG). All products were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and powder X-ray diffraction (PXRD). Their crystal and molecular structures were determined by single crystal X-ray diffraction (SCXRD). The complex crystallizes in the space group P21/c with a = 11.1022(5), b = 9.4550(5), c = 13.7613(7) Å and ß = 94.035(4)°. Both adducts crystallize in the space group P 1 with the following lattice parameters: py adduct, a = 9.1696(6) Å, b = 9.4808(9) Å, c = 11.6801(8) Å, a = 93.300(7)°, ß = 108.738(6)°, p = 100.650(7)°; and thf adduct, a = 9.1721(13) Å, b = 9.5797(13) Å, c = 11.4448(15) Å, a = 96.138(11)°, ß = 106.466(12)°, p = 101.543(12)°. [ABSTRACT FROM AUTHOR]

The solvent adducts of the tetravalent actinoid chlorides ThCl4 and UCl4 have been isolated with methanol as [ThCl4(MeOH)4] 1 and [UCl4(MeOH)4] 2, and with ethanol as [ThCl4(EtOH)4] 3 and [UCl4(EtOH)4] 4. In hydrochloric acid [ThCl2(H2O)7](Cl)2(H2O)25 forms, which is isotypic to the known [UCl2(H2O)7](Cl)2(H2O)26. The adducts have been analysed using SXRD, IR, CHN, TGA‐MS and PXRD. The material can be isolated from saturated organic (1–4) or acidic aqueous (5–6) solutions, however, drying of the isolated material results in loss of HCl and the formation of oxide species, confirmed by the isolation of U3O8 after complete thermal decomposition. [ABSTRACT FROM AUTHOR]

Summary: In the realm of solar cells, currently, the carbon‐electrode‐based, all‐inorganic perovskite solar cells (C‐IPSCs) based on cesium lead mixed halide perovskites have drawn much attention. Band‐gap tunability and environmental stability of these perovskites (CsPbIBr2) have been gaining attraction as a suitable absorber material for device fabrication. Fabrication of a high‐performing and stable C‐IPSC based on CsPbIBr2 is a challenging process due to high‐temperature fabrication, poor solution deposition of perovskite film, and high recombination at perovskite/carbon interface. In this work, a simple single‐step deposition process was adopted to engineer a good quality perovskite film by replacing conventional precursors with DMSO‐adducts of lead halide (PbX2). Incorporation of the adduct‐based precursor enables crystallization of CsPbIBr2 at a low temperature (~150°C). This enhances the crystallinity of the film, improves the grain size and defects passivation which imparts endurance to the perovskite against phase change and thermal stress. Thereby, enhancing the light absorption and suppressing the non‐radiative recombination in CsPbIBr2 film. As a result, the open‐circuit voltage is enhanced up to 1.18 V and fill factor up to 57%, further improving the power conversion efficiency by 59.4% leading to a champion device efficiency of 5.9%. Adduct‐based C‐IPSC displayed substantial enhancement of ambient stability and the adduct‐based perovskite exhibited excellent thermal stability. [ABSTRACT FROM AUTHOR]

Formaldehyde is a human carcinogen that readily binds to nucleophiles, including proteins and DNA. To investigate whether exogenous formaldehyde produces adducts in extracellular fluids, we characterized modifications to human serum albumin (HSA) following incubation of whole blood, plasma, and saliva with formaldehyde at concentrations of 1, 10 and 100μM. The only HSA locus that showed the presence of formaldehyde modifications was Lys199. A N(6)-Lys adduct with added mass of 12Da, representing a putative intramolecular crosslink, was detected in biological fluids that had been incubated with formaldehyde but not in control fluids. An adduct representing N(6)-Lys formylation was detected in all fluids, but levels did not increase above control values over the tested range of formaldehyde concentrations. An adduct representing N(6)-Lys199 acetylation was also measured in all samples. We then applied the assay to repeated samples of human plasma from 6 nonsmoking volunteer subjects (from Berkeley, CA), and single samples of serum from 15 workers exposed to airborne formaldehyde at about 1.5ppm in a production facility and 15 control workers from Tianjin, China. Although all human plasma/serum samples contained basal levels of the products of N(6)-Lys formylation and acetylation, the putative crosslink product was not detected. Since the putative crosslink was observed in plasma incubated with formaldehyde at 1μM, this suggests that the endogenous concentration of formaldehyde in serum was much lower than reported in the literature. Furthermore, concentrations of the formyl adduct were not higher in workers exposed to formaldehyde at about 1.5ppm than in controls. Follow-up in vitro experiments with gaseous formaldehyde at 1.4ppm detected the putative crosslink in plasma but not whole blood. This combination of results suggests that N(6) formylation occurs within cells with subsequent release of adducted HSA to the systemic circulation. Comparing across human samples, levels of N(6)-Lys199 formyl adducts were present at similar concentrations in subjects from California and China (about 1mmol/mol HSA), but N(6)-Lys199 acetyl adducts were present at higher concentrations in Chinese subjects (0.34 vs. 0.13mmol/mol HSA).

Methylglyoxal (MGO) is a highly reactive precursor which forms advanced glycation end-products (AGEs) in vivo, which lead to metabolic syndrome and chronic diseases. It is also a precursor of various carcinogens, including acrylamide and methylimidazole, in thermally processed foods. Rutin could efficiently scavenge MGO by the formation of various adducts. However, the metabolism and safety concerns of the derived adducts were paid less attention to. In this study, the optical isomers of di-MGO adducts of rutin, namely 6-(1-acetol)-8-(1-acetol)-rutin, were identified in foods and in vivo. After oral administration of rutin (100 mg/kg BW), these compounds reached the maximum level of 15.80 μg/L in plasma at 15 min, and decreased sharply under the quantitative level in 30 min. They were detected only in trace levels in kidney and fecal samples, while their corresponding oxidized adducts with dione structures presented as the predominant adducts in kidney, heart, and brain tissues, as well as in urine and feces. These results indicated that the unoxidized rutin-MGO adducts formed immediately after rutin ingestion might easily underwent oxidation, and finally deposited in tissues and excreted from the body in the oxidized forms. The formation of 6-(1-acetol)-8-(1-acetol)-rutin significantly mitigated the cytotoxicity of MGO against human gastric epithelial (GES-1), human colon carcinoma (Caco-2), and human umbilical vein endothelial (HUVEC) cells, which indicated that rutin has the potential to be applied as a safe and effective MGO scavenger and detoxifier, and AGEs inhibitor.

Plants are widely existing in the environments and have been considered as potential sentinel species of toxic chemicals′ exposure. In this study, the deadly toxic chemicals of three nitrogen mustards (NMs, including NH1, NH2 and NH3) were selected as the investigated targets. First, the reactivities of common endogenous plant components with NMs were examined in vitro. Then, the model plant Nicotiana benthamiana Domin was exposed to NMs. Three γ-aminobutyric acid–nitrogen mustard adducts (GABA–NMs) were identified in the living plant by high resolution mass spectrometry and comparison with the synthesized references. A sensitive detection method with the limits of quantification of 0.0500 ng mL−1 was developed using ultrahigh performance liquid chromatography–triple quadrupole mass spectrometry. The GABA–NMs could be detected after 120 days of the exposure and even in the dead leaves without obvious decrease. Furthermore, 20 different plant species grown in diverse climate zones were exposed to HN1, and the adduct of GABA–HN1 was identified in all the leaves. The results showed the good universality and specificity of GABA–NMs as plant biomarkers for NMs exposure. This work provides a new approach for the pollution investigation of toxic chemicals through analysing biomarkers in plant materials. [Display omitted] • Three novel adducts of nitrogen mustards with GABA were found in exposed plants. • The adducts were unambiguously identified through reference synthesis. • A sensitive LC–MS quantitation method was established for retrospective analyses. • The adducts serve as excellent plant biomarkers for nitrogen mustards exposure. • The biomarkers exhibit long detection windows and universal applicability. [ABSTRACT FROM AUTHOR]

• This study established a method to prepare and detect 8 adducts of organophosphorus pesticides (OPs). • OPs were incubated with BChE or HSA under specific conditions to prepare adducts by in vitro incubation method. • Qualitative and quantitative analysis of adducts was carried out without using the standard synthetic peptides. This study established a method to prepare and detect OPs adducts on butyrylcholinesterase (BChE) and human serum albumin (HSA). OPs (methyl paraoxon, ethyl paraoxon, methyl parathion, parathion) were incubated with BChE or HSA in vitro, and the adducts of OPs-BChE or OPs-HSA were prepared and qualitatively analyzed by ultra-performance liquid chromatography data-dependent high-resolution tandem mass spectrometry (UPLC-ddHRMS/MS). The amounts of BChE and HSA in the incubating systems were varied and the resulting amounts of the adducts were determined using linear regression. OPs-BChE in the blood were isolated by immunomagnetic separation (IMS), and then digested into the OPs-nonapeptide adduct by pepsin. The proteins in the remaining blood plasma were precipitated and digested by pronase to OPs-tyrosines(OPs-Tyr), which were quantified by UPLC-ddHRMS/MS. 4 OPs-nonapeptides and 4 OPs-Tyr adducts were obtained through the process above. The relative mass deviation of incubated adducts between the actual and theoretical exact masses was less than 10 ppm, and further confirmed by fragmentation mass spectra analysis. Calibration curves were linear for all adducts with a coefficient of determination value (R2) ≥0.995. The limits of detection (LOD) and limits of quantification (LOQ) for adducts detected by MS ranged from 0.05 to 1.0 ng/mL, and from 0.1 to 2.0 ng/mL, respectively. The recovery percentages for adducts ranged from 76.1 % to 107.1 %, matrix effects ranged from 83.4 % to 102.1 %. The inter-day and intra-day precision were 6.1–10.1 % and 6.9–12.9 % for adducts. This study provides a new reference method for the detection of organophosphorus pesticide poisoning. In addition, two blood samples with organophosphorus poisoning were tested by the designed method, and the corresponding adducts were detected in both samples. [ABSTRACT FROM AUTHOR]

[Display omitted] Solution crystallization techniques of hybrid lead halides for perovskite photovoltaics, while remaining the most common method for fabricating solar cells, are inevitably complicated by the formation of numerous intermediate solvates that predetermine the morphology and properties of the final perovskite light-harvesting layer. Here, for the first time, a chemical classification of known solvates is proposed based on a comprehensive analysis of their structural features and relationships with possible structural types. [ABSTRACT FROM AUTHOR]

C‐rich graphitic carbonitride materials (CNx) with a large range of compositions have been prepared thanks to the self‐assembly, in different ratios, of melamine (M) and a panel of polycarboxylic acids (A) such as oxalic, tartaric and citric acid. The thermal conversion of the formed adducts (MAy), led to CNx phases, with x ranging from 0.66 to 1.4 (x=1.33 for g‐C3N4 for comparison). The properties of these materials were examined by different techniques (XRD, Raman spectroscopy, TEM, TGA, XPS and DRIFT). It appears that the increase in the C content is associated with the disappearance of the long‐range order of heptazine units and an increase in the sub‐nanometer carbon‐rich cluster size within the graphitic g‐C3N4 structure. This trend is followed by a significant increase in the interlayer spacing and a lower proportion of N=C−N bonds compared to C=C bonds. The thermal stability under an inert atmosphere of these phases and their UV‐Visible absorbance properties were also investigated. [ABSTRACT FROM AUTHOR]

The first Lewis acid base adducts of MoF 6 and an organic base have been synthesized, i. e., MoF 6 (NC 5 H 5 ) and MoF 6 (NC 5 H 5 ) 2 . These adducts are structurally characterized with X-ray crystallography, showing that both adducts adopt capped trigonal prismatic structures. The MoF 6 (NC 5 H 5 ) and MoF 6 (NC 5 H 5 ) 2 adducts are fluxional on the NMR time scale at room temperature. Two different fluorine environments could be resolved by 19 F NMR spectroscopy at -80 °C for the 1 : 2 adduct, MoF 6 (NC 5 H 5 ) 2 , whereas MoF 6 (NC 5 H 5 ) remains fluxional at that temperature. Density functional theory (DFT) calculations aide the assignment of the infrared and Raman spectra. Natural Bond Order and Molecular Electrostatic Potential analyses elucidate the structures and properties of the MoF 6 pyridine adducts. Regions of significantly higher molecular electrostatic potential, i. e., σ-holes, in trigonal prismatic compared to octahedral MoF 6 rationalize the capped trigonal prismatic geometry of the adducts. Whereas MoF 6 (NC 5 H 5 ) is stable at room temperature under exclusion of moisture, MoF 6 (NC 5 H 5 ) 2 decomposes at 60 °C in pyridine solvent, and the solid slowly decomposes at room temperature after 24 h., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

This communication reports experimental and theoretical evidences of σ‐hole interactions in adducts between nitrogen or oxygen nucleophiles and tetroxides of osmium or other group 8 elements. Cocrystals between pyridine or pyridine N‐oxide derivatives and osmium tetroxide are characterized through various techniques and rationalized as σ‐hole interactions using DFT calculations and several other computational tools. We propose the term "osme bond" (OmB, Om=Fe, Ru, Os, (Hs)) for naming the noncovalent interactions wherein group 8 elements have the role of the electrophile. The word osme is the transcription of ὀσμή, the ancient Greek word for smell that was used to name the heaviest group 8 element in relation to the smoky odor of its tetroxide. [ABSTRACT FROM AUTHOR]

Introduction: The migration of chemicals from processing materials into biopharmaceuticals can lead to various problems. Leachables from administration materials, with no possibility of further clearance, are of particular concern. Released chemicals can be toxic or react with formulation components, thereby impacting product safety. Therapeutic proteins, which are susceptible to chemical modifications, have highest risk to be affected. Aim: The aim of this study was to identify a previously unknown leachable compound from clinical administration sets, which was present above the applied generic safety threshold. Methods: Extracts of commonly used clinical administration sets were analyzed using a recently established specific assay allowing the identification and quantification of the α,β-unsaturated aldehyde 4-hydroxynonenal (HNE) in a drug product surrogate solution. HNE was quantified after derivatization with 2,4-dinitrophenylhydrazine (DNPH) and liquid extraction of the formed hydrazone by LC-MRM analysis. Results: Potentially genotoxic HNE was a leachable compound from all tested administration sets, in parts exceeding safety thresholds for genotoxicants. The HNE-releasing polymer was identified as PVC. Conclusion: Clinical administration sets should be, like manufacturing materials and container closure systems, in the focus of routine leachables studies. Manufacturers of clinical administration sets should show responsibility to avoid the presence of safety concerning chemicals, like HNE. [ABSTRACT FROM AUTHOR]

Liquid Chromatography-High Resolution Mass Spectrometry (LC-HRMS) based lipidomics has become the most versatile analytical tool to discover and detect lipids using a non-targeted approach. A way to improve the ionization performance of specific lipid classes in electrospray sources is to modify their electrostatic interactions with both mobile and stationary phases. So far, studies on mobile phases additives, in particular ammonium fluoride, have focused on increasing ionization efficiency and reproducibility of the conditions. However, little attention has been paid to the different rules that apply in adducts formation: type of adducts, their relative intensities, and how this affects the annotation/identification process. In this study, we evaluated the performance of ammonium fluoride as an additive salt in a non-targeted MS-based lipidomic study under both the positive and negative electrospray ionization modes. The new molecular ion adducts observed can lead to wrong identifications if they are not known or considered, while the disappearance of other adducts such as those with sodium can change the traditional identification rules.

Polysorbates (PS) are used in biopharmaceuticals to stabilize therapeutic proteins. Oxidative degradation of (poly)unsaturated fatty acids (PUFAs) contained in PS was shown to lead to α,β-unsaturated carbonyls. The n-6-PUFA linoleic acid accounts for up to 18% of all FAs contained in multi-compendial grade PS80. 4-Hydroxynonenal (HNE) is highly reactive towards nucleophilic amino acids, potentially leading to covalent protein modifications. This study tests whether HNE may be a pharmaceutically relevant PS80 peroxidation product. Since HNE was not directly detectable in the PS80 matrix by UV and MS, a new quantification method was established. After derivatization with 2,4-dinitrophenyl hydrazine (DNPH) and extraction of the formed hydrazone with a salting-out assisted liquid-liquid extraction, the HNE-DNPH adduct was analyzed by multiple reaction monitoring. Kinetic oxidation studies were conducted incubating PS80 in presence and absence of the antioxidant butylhydroxytoluene (BHT). HNE was confirmed as PS80 degradant in oxidatively stressed samples. BHT was shown to prevent its formation. HNE is a detectable PS80 degradation product raising questions about the potential impact on critical quality attributes of biopharmaceuticals formulated with PS80. Addition of BHT prevented HNE formation under oxidative stress. Consequently, BHT might be a valuable additive in PS used in biopharmaceuticals. [ABSTRACT FROM AUTHOR]

[Display omitted] • Orally administration of Morita-Baylis-Hillman adduct (CISACN) inhibits airway eosinophil migration in combined allergic rhinitis and asthma syndrome (CARAS) experimental model. • CISACN reduces the clinical signs of rhinitis through TNF-α inhibition and airway epithelium integrity. • CISACN increases Th1/Th2 ratio. • CISACN inhibits the p38MAPK and p65NF-κB signaling pathway axis in eosinophils. • CISACN ameliorates airway inflammation. Combined allergic rhinitis and asthma syndrome (CARAS) is an airway-type 2 immune response with a profuse inflammatory process widely affecting the world population. Due to the compromise of quality of life and the lack of specific pharmacotherapy, the search for new molecules becomes relevant. This study aimed to evaluate the effectiveness of the Morita-Bailys-Hillman adduct (CISACN) treatment in the CARAS experimental model. Female BALB/c mice were ovalbumin (OVA) -sensitized and -challenged and treated with CISACN. The treatment decreased the eosinophil migration to the nasal and lung cavities and tissues and the goblet cell hyperplasia/hypertrophy, attenuated airway hyperactivity by reducing the hyperplasia/hypertrophy of the smooth muscle and the extracellular matrix's thickness. Also, the treatment reduced the clinical signs of rhinitis as nasal rubbing and sneezing in a histamine-induced nasal hyperreactivity assay. The immunomodulatory effect of CISACN was by reducing OVA-specific IgE serum level, and IL-33, IL-4, IL-13, and TGF-β production, dependent on IFN-γ increase. Furthermore, the effect of CISACN on lung granulocytes was by decreasing the p-p38MAPK/p65NF-κB signaling pathway. Indeed, CISACN reduced the p38MAPK and p65NF-κB activation. These data demonstrated the anti-inflammatory and immunomodulatory effects of the CISACN with scientific support to become a pharmacological tool to treat airway inflammatory diseases. [ABSTRACT FROM AUTHOR]

The consequences of consuming excessive amounts of alcoholic beverages are currently an important problem for many societies, not only in the context of treatment of alcohol dependence, but also the health effects of alcohol abuse. Long-term consumption of alcoholic beverages is associated with increased risk of hypertension, ischemic heart disease, also mouth and throat, stomach, liver or large intestine cancer. Due to almost 90% of consumed alcohol being broken down in the liver by oxidative pathways, this organ is particularly vulnerable to the effects of alcohol metabolism. The consequences of alcohol metabolism in the liver is the formation of byproducts, namely acetaldehyde and interaction between acetaldehyde and proteins, lipoproteins, DNA, also formation of reactive oxygen species and markers of inflammation, which can intensify immunological and inflammatory reactions and oxidative stress, thus contributing to the damage of hepatocytes, and development of alcoholic liver disease. There are three stages of alcoholic liver disease: alcoholic fatty liver disease, alcoholic hepatitis and alcoholic cirrhosis. The more advanced the disease, the worse the prognosis tends to be and the smaller the chance of recovery. Thus, alcoholic liver disease is a significant public health problem.

Me3Si−X (X=CN, N3, OCN, and SCN) was treated with the Lewis acids GaCl3 and B(C6F5)3 in toluene yielding the desired adducts Me3Si−X→GaCl3 and Me3Si−X→B(C6F5)3. All synthesized adducts were isolated and completely characterized including single crystal structure elucidations. The different structures, thermodynamics of formation and charge transfer effects are discussed on the basis of experimental and theoretical data. [ABSTRACT FROM AUTHOR]

Me3Si−X (X=CN, N3, OCN, and SCN) was treated with the Lewis acids GaCl3 and B(C6F5)3 in toluene yielding the desired adducts Me3Si−X→GaCl3 and Me3Si−X→B(C6F5)3. All synthesized adducts were isolated and completely characterized including single crystal structure elucidations. The different structures, thermodynamics of formation and charge transfer effects are discussed on the basis of experimental and theoretical data. [ABSTRACT FROM AUTHOR]

Our understanding of IgE‐mediated drug allergy relies on the hapten concept, which is well established in inducing adaptive reactions of the immune system to small molecules like drugs. The role of hapten‐carrier adducts in re‐challenge reactions leading to mast cell degranulation and anaphylaxis is unclear. Based on clinical observations, the speed of adduct formation, skin and in vitro tests to inert drug molecules, a different explanation of IgE‐mediated reactions to drugs is proposed: These are (a) A natural role of reduced mast cell (MC) reactivity in developing IgE‐mediated reactions to drugs. This MC unresponsiveness is antigen‐specific and covers the serum drug concentrations, but allows reactivity to locally higher concentrations. (b) Some non‐covalent drug‐protein complexes rely on rather affine bindings and have a similar appearance as covalent hapten‐protein adducts. Such drug‐protein complexes represent so‐called "fake antigens," as they are unable to induce immunity, but may react with and cross‐link preformed drug‐specific IgE. As they are formed very rapidly and in high concentrations, they may cause fulminant MC degranulation and anaphylaxis. (c) The generation of covalent hapten‐protein adducts requires hours, either because the formation of covalent bonds requires time or because first a metabolic step for forming a reactive metabolite is required. This slow process of stable adduct formation has the advantage that it may give time to desensitize mast cells, even in already sensitized individuals. The consequences of this new interpretation of IgE‐mediated reactions to drugs are potentially wide‐reaching for IgE‐mediated drug allergy but also allergy in general. [ABSTRACT FROM AUTHOR]

The adducts were synthesized by means of diene condensation reaction of levopimaric acid with acrylic acid, and through carrying out the free radical addition of ethandithiol to levopimaric acid. The composition and structure of these adducts were identified through data of the elemental analysis, IR and PMR spectroscopy. The efficiency of the synthesized diacids as corrosion inhibitors was determined by means of the gravimetric method (on mass losses of a sample of steel plate of mark C-3) in an acidic medium (solutions of 1H and 5H of sulfuric acid). The influence of the medium temperature and concentration of the used compounds on the degree of protection and corrosion inhibition coefficient was analyzed. It found that rise in temperature results in the increase of protective effect of the inhibitor. Note that the increase of the inhibitor concentration, raising the degree of protection though, is not so noticeable. [ABSTRACT FROM AUTHOR]