Base Adduct Formation Research Articles

Mechanism of B‐H Redistribution during Reduction of Polyborazylene by Hydrazine

AbstractDensity functional theory has been used to elucidate the mechanistic underpinnings of the regeneration of ammonia‐borane (H3B−NH3, AB) from polyborazylene (BxNxHx, PBz) in the presence of hydrazine (H2N−NH2, Hz). Herein, borazine (B3N3H6, Bz) is used as the simplest relevant model of PBz for the regeneration process. Digestion of Bz using Hz was found to occur by a string of Lewis acid base adduct (between B atoms of Bz and Hz molecule) formation and Hz assisted proton transfer processes. Later, B−H bonds of HB(NHNH2)2, the Bz digested product, are redistributed to form hydrazine‐borane (H3B−NH2NH2, HzB) and B(NHNH2)3. Redistribution of B−H bonds occurs through hydroboration and concerted proton‐hydride transfer. Another B−H redistributed product, B(NHNH2)3, produces HzB as a result of proton and hydride transfer from cis‐diazene (Dz), the oxidized product of Hz in presence of O2.

Genotoxic Risks to Male Reproductive Health from Radiofrequency Radiation.

During modern era, mobile phones, televisions, microwaves, radio, and wireless devices, etc., have become an integral part of our daily lifestyle. All these technologies employ radiofrequency (RF) waves and everyone is exposed to them, since they are widespread in the environment. The increasing risk of male infertility is a growing concern to the human population. Excessive and long-term exposure to non-ionizing radiation may cause genetic health effects on the male reproductive system which could be a primitive factor to induce cancer risk. With respect to the concerned aspect, many possible RFR induced genotoxic studies have been reported; however, reports are very contradictory and showed the possible effect on humans and animals. Thus, the present review is focusing on the genomic impact of the radiofrequency electromagnetic field (RF-EMF) underlying the male infertility issue. In this review, both in vitro and in vivo studies have been incorporated explaining the role of RFR on the male reproductive system. It includes RFR induced-DNA damage, micronuclei formation, chromosomal aberrations, SCE generation, etc. In addition, attention has also been paid to the ROS generation after radiofrequency radiation exposure showing a rise in oxidative stress, base adduct formation, sperm head DNA damage, or cross-linking problems between DNA & protein.

Enhancing the stability of the polymeric Lewis-base-assisted dual-phase 3D CsPbBr3–Cs4PbBr6 perovskite by molecular engineering and self-passivation

Self-ordered polymeric Lewis acid–base adduct formation for a dual role of passivated CsPbBr3–Cs4PbBr6 perovskite grain morphology modulation and exciton dielectric confinement, thereby exhibiting high performances and stability in PeLEDs.

Functionalization of antimonene and bismuthene with Lewis acids.

Elemental 2D pnictogens (group 15) are an interesting class of materials with tunable band structures and high carrier mobilities. Heavier pnictogens (Sb and Bi) are stable under ambient conditions compared to lighter members (P and As) and are emerging as interesting candidates for various electronic and optoelectronic applications. The reactivity of these materials is due to the presence of a lone pair which can be effectively utilized to tune material properties via different functionalization strategies. In this work, we have synthesized antimonene and bismuthene nanosheets by liquid exfoliation which are emissive in the visible range and functionalized these nanosheets with group 12 and 13 Lewis acids (ZnCl2, CdCl2, BCl3, GaCl3, AlCl3, and InCl3). Interaction of these Lewis acids with the lone pairs on Sb/Bi leads to the formation of Lewis acid-base adducts with the corresponding changes in the bonding environment along with lattice distortion and rehybridization of the band structure. Interestingly, the changes in band structure upon functionalization were realized as a blue shift in the emission of few-layered Sb and Bi. This is the first report on the functionalization of heavier pnictogens by the formation of Lewis acid-base adducts and opens a path for tuning their properties for integration in electronic and optoelectronic devices.

Tris(tetramethylguanidinyl)phosphine: The Simplest Non-ionic Phosphorus Superbase and Strongly Donating Phosphine Ligand.

We report the synthesis and properties of the much sought‐after tris(1,1,3,3‐tetramethylguanidinyl) phosphine P(tmg)3, a crystalline, superbasic phosphine accessible through a short and scalable procedure from the cheap and commercially available bulk chemicals 1,1,3,3‐tetramethylguanidine, tris(dimethylamino)‐phosphine and phosphorus trichloride. The new phosphine exhibits exceptional electron donor properties and readily forms transition metal complexes with gold(I), palladium(II) and rhodium(I) precursors. The formation of zwitterionic Lewis base adducts with carbon dioxide and sulfur dioxide was explored. In addition, the complete series of phosphine chalcogenides was prepared from the reaction of P(tmg)3 with N2O and the elemental chalcogens.

Photoswitchable Nitrogen Superbases: Using Light for Reversible Carbon Dioxide Capture.

Using light as an external stimulus to alter the reactivity of Lewis bases is an intriguing tool for controlling chemical reactions. Reversible photoreactions associated with pronounced reactivity changes are particularly valuable in this regard. We herein report the first photoswitchable nitrogen superbases based on guanidines equipped with a photochromic dithienylethene unit. The resulting N‐heterocyclic imines (NHIs) undergo reversible, near quantitative electrocyclic isomerization upon successive exposure to UV and visible irradiation, as demonstrated over multiple cycles. Switching between the ring‐opened and ring‐closed states is accompanied by substantial pK a shifts of the NHIs by up to 8.7 units. Since only the ring‐closed isomers are sufficiently basic to activate CO2 via the formation of zwitterionic Lewis base adducts, cycling between the two isomeric states enables the light‐controlled capture and release of CO2.

Pyridinylidenaminophosphines: Facile Access to Highly Electron-Rich Phosphines.

Electron‐rich tertiary phosphines are valuable species in chemical synthesis. However, their broad application as ligands in catalysis and reagents in stoichiometric reactions is often limited by their costly synthesis. Herein, we report the synthesis and properties of a series of phosphines with 1‐alkylpyridin‐4‐ylidenamino and 1‐alkylpyridin‐2‐ylidenamino substituents that are accessible in a very short and scalable route starting from commercially available aminopyridines and chlorophosphines. The determination of the Tolman electronic parameter (TEP) value reveals that the electron donor ability can be tuned by the substituent pattern at the aminopyridine backbone and it can exceed that of common alkylphosphines and N‐heterocyclic carbenes. The potential of the new phosphines as strong nucleophiles in phosphine‐mediated transformations is demonstrated by the formation of Lewis base adducts with CO2 and CS2. In addition, the coordination chemistry of the new phosphines towards CuI, AuI, and PdII metal centers has been explored, and a convenient procedure to introduce the most basic phosphine into metal complexes starting from air‐stable phosphonium salt is described.

Model for Metal Extraction from Chloride Media with Basic Extractants: A Coordination Chemistry Approach

The metal extraction mechanism of basic extractants is typically described as an anion exchange process, but this mechanism does not correctly explain all observations. This paper introduces a novel model for the extraction of metals by basic extractants from chloride media supported by experimental data on methyltrioctylammonium chloride and Aliquat 336 chloride systems. This model relies on the hypothesis that the metal species least stabilized in the aqueous phase by hydration (i.e., the metal species with the lowest charge density) is extracted more efficiently than the more water stabilized species (i.e., species with higher charge densities). Once it is transferred to the organic phase, the extracted species can undergo further Lewis acid-base adduct formation reactions with the chloride anions available in the organic phase to form negatively charged chloro complexes, which than associate with the organic cations. Salting-out agents influence the extraction, most likely by decreasing the concentration of free water molecules, which destabilizes the metal complex in the aqueous phase. The evidence provided includes (1) the link between extraction and transition-metal speciation, (2) the trend in extraction efficiency as a function of the concentration of different salting-out agents, and (3) the behavior of HCl in the extraction system. The proposed extraction model better explains the experimental observations in comparison to the anion exchange model and allows the prediction of optimal conditions for metal extractions and separations a priori, by selecting the most suitable salting-out agent and its concentration.

Mass Spectrometric Quantitation of Pyridyloxobutyl DNA Phosphate Adducts in Rats Chronically Treated with N'-Nitrosonornicotine.

The tobacco-specific carcinogens N'-nitrosonornicotine (NNN) and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) require metabolic activation to exert their carcinogenicity. NNN and NNK are metabolized to the same reactive diazonium ions, which alkylate DNA forming pyridyloxobutyl (POB) DNA base and phosphate adducts. We have characterized the formation of both POB DNA base and phosphate adducts in NNK-treated rats and the formation of POB DNA base adducts in NNN-treated rats. However, POB DNA phosphate adducts in NNN-treated rats are still uncharacterized. In this study, we quantified the levels of POB DNA phosphate adducts in tissues of rats chronically treated with ( S)-NNN or ( R)-NNN for 10, 30, 50, and 70 weeks during a carcinogenicity study. The highest amounts of POB DNA phosphate adducts were observed in the esophagus of the ( S)-NNN-treated rats, with a maximum level of 5400 ± 317 fmol/mg DNA at 50 weeks. The abundance of POB DNA phosphate adducts in the esophagus was consistent with the results of the carcinogenicity study showing that the esophagus was the primary site of tumor formation from treatment with ( S)-NNN. Compared to the ( R)-NNN group, the levels of POB DNA phosphate adducts were higher in the oral mucosa, esophagus, and liver, while lower in the nasal mucosa of the ( S)-NNN-treated rats. Among 10 combinations of all isomers of POB DNA phosphate adducts, Ap(POB)C and combinations with thymidine predominated across all the rat tissues examined. In the primary target tissue, esophageal mucosa, Ap(POB)C accounted for ∼20% of total phosphate adducts in the ( S)-NNN treatment group throughout the 70 weeks, with levels ranging from 780 ± 194 to 1010 ± 700 fmol/mg DNA. The results of this study showed that POB DNA phosphate adducts were present in high levels and persisted in target tissues of rats chronically treated with ( S)- or ( R)-NNN. These results improve our understanding of DNA damage during NNN-induced carcinogenesis. The predominant POB DNA phosphate isomers observed, such as Ap(POB)C, may serve as biomarkers for monitoring chronic exposure of tobacco-specific nitrosamines in humans.

Lewis Base Free Oxophosphonium Ions: Tunable, Trigonal‐Planar Lewis Acids

Oxophosphonium ions (R2 P=O)+ are fascinating chemical intermediates related to the well-known acylium cations (RC=O)+ , and comprise a tricoordinate phosphorus(V) center with a phosphorus-oxygen double bond. Here, we report the synthesis of two oxophosphonium ions stabilized by bulky imidazolin-2-imine and imidazolin-2-olefin substituents attached to phosphorus. The novel species were characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis, and the bonding situation was probed by DFT calculations. Determination of the acceptor number and the fluoride ion affinity revealed that the choice of the substituents has a strong influence on the electrophilicity of the phosphorus center. Additionally, the formation of Lewis base adducts with pyridine derivatives and the reactivity with isopropyl alcohol was explored.

YO-1 Synthesis and separation of peptide-oxidized phospholipid adducts, a potential lipoxidation marker

Oxidative stress has been linked to several inflammatory diseases, possibly due to oxidative damage to biomolecules. Recently, oxidized phospholipids have been shown to be related to several pathophysiological pathways through protein modification, creating protein-phospholipid adducts. The literature on protein-phospholipid adducts is sparse, thus the aim of this project is to study the formation of these adducts and to uncover potential biomarkers for disease, using different mass spectrometry techniques. The formation of phospholipid adducts was studied using human serum albumin, firstly reacting the whole protein with pentanal, a saturated aldehyde model of the fragmented chain of an oxidized phospholipid, and then reacting a synthetic HSA peptide, known to be susceptible to pentanal adduct formation, with the oxidized phosphatidylcholine PONPC. The reactions were analysed by LC-MS/MS and LC-MRM. This analysis showed mass shifts consistent with the formation of HSA-pentanal and peptide-PONPC Schiff's base adducts located on the lysine residues. Different separation techniques have also been tested in order to develop an enrichment step. The new diagnostic ions and mass spectrometry approaches developed could be used to detect biomarkers for inflammatory diseases.

First-principles investigation of the Lewis acid-base adduct formation at the methylammonium lead iodide surface.

We have here performed a campaign of ab initio calculations focusing on the anchoring mechanism and adduct formation of some Lewis bases, both aliphatic and aromatic, on a PbI2-rich flat (001) methylammonium lead iodide (MAPI) surface. Our goal is to provide theoretical support to the recently reported experimental techniques of MAPI surface passivation via Lewis acid-base neutralization and similarly of MAI·PbI2·(Lewis base) adduct formation. We tested several X-donor bases (X = :N, :O, :S), paying attention to the thermodynamic stability of the final MAPI·base adducts and to their electronic properties. Factors that impact on the passivation mechanism are the directionality of the Lewis base lone pair and its enhanced/reduced overlap with MAPI Pb p orbitals, the dipole moment of the base and, similarly, the electronegativity of the X donor atom. Also non-covalent interactions, both at the surface side (intra, MAPI) and at the very interface (inter, MAPI·Lewis base), seem to contribute to the stability of the final adducts. Here we show that the thermodynamic stability does not necessarily correspond to the most effective base → acid dative bond formation. Starting from a low coverage (12.5% of the undercoordinated Pb atoms available at the surface are passivated) this paper paves the way towards the study of cooperative and steric effects among Lewis bases at higher coverages representing, to the best of our knowledge, one of the very first studies focusing on the molecular anchoring on the surfaces of this very important class of materials.

P 108 - Identification and localization of protein-pentanal adducts, a potential lipoxidation marker

Oxidative stress has been linked to several inflammatory diseases; this may be due to oxidative damage to biomolecules. Oxidized phospholipids have been shown to be related to several pathophysiological pathways, as antigens or ligands, and more recently through protein modification creating protein-phospholipid adducts. The literature on protein-phospholipid adducts is sparse, although this type of protein modification could be of interest as potential biomarkers for disease. The aim of this project is to study the formation of these adducts, using both intact protein and bottom-up mass spectrometry techniques. For this work, two model proteins were modified with pentanal, a saturated breakdown product of phospholipid oxidation and a model for phospholipid aldehydes, and the adducts stabilized by reduction and analysed by ESI MS. The modified proteins were also subjected to SDS-PAGE, in-gel tryptic digestion, and LC-MSMS analysis. The results of the top-down and bottom-up analysis show the presence of pentanal adducts, and identified the sequence of the modified peptides. The mass shifts observed were consistent with the formation of Schiff's base adducts, and only modifications to lysine were observed. Product ions that might be useful as diagnostic ions for the modification were identified. Future work will investigate adduct formation using oxidized phospholipids.

Vicinal Difunctionalization of Alkenes under Iodine(III) Catalysis involving Lewis Base Adducts

AbstractThe influence of a 2‐pyridinyl substituent on the catalytic performance of aryl iodides as catalyst in iodine(III) chemistry was explored. An efficient Lewis base adduct between the pyridine nitrogen and the electrophilic iodine(III) center was identified and confirmed by X‐ray analysis. This arrangement was shown to generate a kinetically competent superior catalyst structure for the catalytic dioxygenation of alkenes. It introduces the concept of Lewis base adduct formation as a kinetic factor in iodine(I/III) catalysis.magnified image

Evidence for Cation-Controlled Excited-State Localization in a Ruthenium Polypyridyl Compound.

The visible absorption and photoluminescence (PL) properties of the four neutral ruthenium diimine compounds [Ru(bpy)2(dcb)] (B2B), [Ru(dtb)2(dcb)] (D2B), [Ru(bpy)2(dcbq)] (B2Q), and [Ru(dtb)2(dcbq)] (D2Q), where bpy is 2,2'-bipyridine, dcb is 4,4'-(CO2(-))2-bpy, dtb is 4,4'-(tert-butyl)2-bpy, and dcbq is 4,4'-(CO2(-))2-2,2'-biquinoline, are reported in the presence of Lewis acidic cations present in fluid solutions at room temperature. In methanol solutions, the measured spectra were insensitive to the presence of these cations, while in acetonitrile a significant red shift in the PL spectra (≤1400 cm(-1)) was observed consistent with stabilization of the metal-to-ligand charge transfer (MLCT) excited state through Lewis acid-base adduct formation. No significant spectral changes were observed in control experiments with the tetrabutylammonium cation. Titration data with Li(+), Na(+), Mg(2+), Ca(2+), Zn(2+), Al(3+), Y(3+), and La(3+) showed that the extent of stabilization saturated at high cation concentration with magnitudes that scaled roughly with the cation charge-to-size ratio. The visible absorption spectra of D2Q was particularly informative due to the presence of two well-resolved MLCT absorption bands: (1) Ru → bpy, λmax ≈ 450 nm; and (2) Ru → dcbq, λmax ≈ 540 nm. The higher-energy band blue-shifted and the lower-energy band red-shifted upon cation addition. The PL intensity and lifetime of the excited state of B2B first increased with cation addition without significant shifts in the measured spectra, behavior attributed to a cation-induced change in the localization of the emissive excited state from bpy to dcb. The importance of excited-state localization and stabilization for solar energy conversion is discussed.

ChemInform Abstract: Frustrated Lewis Pairs: Design and Reactivity

AbstractReview: 34 refs.

The mycotoxin patulin reacts with DNA bases with and without previous conjugation to GSH: implication for related α,β-unsaturated carbonyl compounds?

The α,β-unsaturated carbonyl group is recognized as alert for mutagenicity, attributed to (1) its direct reaction with DNA, counteractable by glutathione (GSH), and (2) oxidative stress caused indirectly by GSH depletion. Accordingly, the α,β,γ,δ-unsaturated lactone patulin (PAT), a mycotoxin detected in fruits and products derived thereof, is known to induce gene, chromosome, and genome mutations in vitro, its mutagenicity correlating inversely with intracellular GSH levels. Thus, the reactivity of PAT against DNA bases and nucleosides in the absence and presence of GSH and glutathione S-transferases (GSTs) was investigated under cell-free conditions using HPLC mass spectrometry techniques for identification of reaction products. Adduct formation with all four nucleobases as well as with purine base nucleosides occurred even in the presence of GSH, revealing several adducts of PAT, mono- and disubstituted with nucleobases/nucleosides as well as novel GSH-PAT adducts. In addition, novel mixed GSH-PAT-nucleobase adducts were observed. These adducts exhibited a ketohexanoic acid-type structure of the PAT molecule, C6 substituted with GSH and linking C1 of PAT with nitrogens of nucleobases/nucleosides via an amide bond. Formation of GSH-PAT-adenine adducts was not prevented by GSTs, and excess of GSH needed to reduce their formation was higher than for PAT-adenine adducts. The formation of mixed GSH-DNA base adducts has not been described for PAT or any other α,β-unsaturated carbonyl before, although the reaction mechanism seems to be applicable to a variety of α,β-unsaturated carbonyls occurring in food and in the environment.

Photochromic dithienylethene-containing triarylborane derivatives: facile approach to modulate photochromic properties with multi-addressable functions.

A series of dithienylethene-containing triarylboranes has been designed, synthesized, and characterized. The electrochemistry, photophysics, and photochromic behavior have also been studied. The photophysical and photochromic properties could be facilely tuned in this system by varying the thiophene spacers (thiophene, thienothiophene, and bithiophene) between the dithienylethene and the dimesitylboron (BMes2 ) or the position of the BMes2 substitution in the thiophene spacers. The absorption of closed form has been found to be more sensitive towards the structural modification upon incorporation of the BMes2 unit. Moreover, multi-addressable photochromic reactivity is obtained upon addition of Lewis base (F(-) ), which is due to the formation of boron-Lewis base adduct. The dependence of the photophysical and photochromic properties on the thiophene spacers and the position of the BMes2 substitution has been further supported by computational studies.

Evolution of cyclic peptide protease inhibitors

We report a bacterial system for the evolution of cyclic peptides that makes use of an expanded set of amino acid building blocks. Orthogonal aminoacyl-tRNA synthetase/tRNA(CUA) pairs, together with a split intein system were used to biosynthesize a library of ribosomal peptides containing amino acids with unique structures and reactivities. This peptide library was subsequently used to evolve an inhibitor of HIV protease using a selection based on cellular viability. Two of three cyclic peptides isolated after two rounds of selection contained the keto amino acid p-benzoylphenylalanine (pBzF). The most potent peptide (G12: GIXVSL; X=pBzF) inhibited HIV protease through the formation of a covalent Schiff base adduct of the pBzF residue with the ε-amino group of Lys 14 on the protease. This result suggests that an expanded genetic code can confer an evolutionary advantage in response to selective pressure. Moreover, the combination of natural evolutionary processes with chemically biased building blocks provides another strategy for the generation of biologically active peptides using microbial systems.

Thermochemistry of Lewis Adducts of BH3 and Nucleophilic Substitution of Triethylamine on NH3BH3 in Tetrahydrofuran

The thermochemistry of the formation of Lewis base adducts of BH(3) in tetrahydrofuran (THF) solution and the gas phase and the kinetics of substitution on ammonia borane by triethylamine are reported. The dative bond energy of Lewis adducts were predicted using density functional theory at the B3LYP/DZVP2 and B3LYP/6-311+G** levels and correlated ab initio molecular orbital theories, including MP2, G3(MP2), and G3(MP2)B3LYP, and compared with available experimental data and accurate CCSD(T)/CBS theory results. The analysis showed that the G3 methods using either the MP2 or the B3LYP geometries reproduce the benchmark results usually to within ~1 kcal/mol. Energies calculated at the MP2/aug-cc-pVTZ level for geometries optimized at the B3LYP/DZVP2 or B3LYP/6-311+G** levels give dative bond energies 2-4 kcal/mol larger than benchmark values. The enthalpies for forming adducts in THF were determined by calorimetry and compared with the calculated energies for the gas phase reaction: THFBH(3) + L → LBH(3) + THF. The formation of NH(3)BH(3) in THF was observed to yield significantly more heat than gas phase dative bond energies predict, consistent with strong solvation of NH(3)BH(3). Substitution of NEt(3) on NH(3)BH(3) is an equilibrium process in THF solution (K ≈ 0.2 at 25 °C). The reaction obeys a reversible bimolecular kinetic rate law with the Arrhenius parameters: log A = 14.7 ± 1.1 and E(a) = 28.1 ± 1.5 kcal/mol. Simulation of the mechanism using the SM8 continuum solvation model shows the reaction most likely proceeds primarily by a classical S(N)2 mechanism.