Cetyltrimethylammonium dichromate: a mild oxidant for coupling amines and thiols

A novel lipopathic oxidizing agent, cetyltrimethylammonium dichromate, was used for coupling aromatic amines and thiols to yield the corresponding diazo compounds and disulfides, respectively.     

A kinetic and mechanistic study of thallium(I) oxidation by quinolinium dichromate (QDC), a new oxidant

Quinolinium dichromate (QDC) oxidation of Tl^I in aqueous AcOH containing large concentrations of HCl is considerably accelerated both by H⁺ and Cl^– ions as well as by increasing the AcOH concentration in the medium; oxidation is made possible by altering the redox potentials. The reaction is first order in oxidant and in reductant but apparently less than unit order in [Cl^–] and nearly second order in [H⁺]. The active species of QDC and Tl^I are ClCrO₃ ^– and TlCl₂ ^– respectively. A possible mechanism is proposed and verified, and the reaction constants involved have been evaluated.     

A density functional study on a biomimetic non-heme iron catalyst: insights into alkane hydroxylation by a formally HO-FeV=O oxidant

The reactivity of [HO-(tpa)Fe(V)=O] (TPA=tris(2-pyridylmethyl)amine), derived from O-O bond heterolysis of its [H(2)O-(tpa)Fe(III)-OOH] precursor, was explored by means of hybrid density functional theory. The mechanism for alkane hydroxylation by the high-valent iron-oxo species invoked as an intermediate in Fe(tpa)/H(2)O(2) catalysis was investigated. Hydroxylation of methane and propane by HO-Fe(V)=O was studied by following the rebound mechanism associated with the heme center of cytochrome P450, and it is demonstrated that this species is capable of stereospecific alkane hydroxylation. The mechanism proposed for alkane hydroxylation by HO-Fe(V)=O accounts for the experimentally observed incorporation of solvent water into the products. An investigation of the possible hydroxylation of acetonitrile (i.e., the solvent used in the experiments) shows that the activation energy for hydrogen-atom abstraction by HO-Fe(V)=O is rather high and, in fact, rather similar to that of methane, despite the similarity of the H-CH(2)CN bond strength to that of the secondary C-H bond in propane. This result indicates that the kinetics of hydrogen-atom abstraction are strongly affected by the cyano group and rationalizes the lack of experimental evidence for solvent hydroxylation in competition with that of substrates such as cyclohexane.     

Catalytic activity tuning of a biomimetic HO-FeV=O oxidant for methane hydroxylation by substituents on aromatic rings: theoretical study

HO-(TPA)FeV=O (TPA = tris(2-pyridylmethyl)amine) has been proposed in the literature as the key high-valent iron-oxo intermediate involved in alkane hydroxylation. Here the structure of this species is investigated theoretically in the framework of density functional theory (DFT). A detailed electronic structure analysis leads to the presumption that the properties of the FeV=O bond can be modified by introducing substituents to the aromatic rings of TPA and thus the reactivity of HO-(TPA)FeV=O for the hydrogen atom abstraction of methane hydroxylation can be tuned on the quartet potential energy surface. The validity of our presumption is verified by DFT calculations. According to the rebound mechanism, the H-abstraction step is examined by using five complexes with TPA and TPA-derivative ligands and the corresponding reaction energies and energy barriers are obtained and compared with each other. The results are fully in agreement with our qualitative model, showing that electron-withdrawing groups are able to lower the barrier and facilitate the reaction, whereas the electron-donating groups increase the barrier and reduce the reactivity.     

Radiochemical microdetermination of catecholamines. II. Oxidation with labelled potassium dichromate

Summary A radiochemical method of determination of microquantities of catecholamines by means of oxidation with labelled potassium dichromate is described. A sensitivity of better than one picomole is obtained and with addition of copper ions the determination is rapid and the precision better than 10%.

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Zusammenfassung Eine radiochemische Methode zur Bestimmung von Mikromengen Catecholamin durch Oxydation mit markiertem Kaliumbichromat wurde beschrieben. Die Empfindlichkeit übertrifft ein Picomol. Bei Zusatz von Kupferionen verläuft die Bestimmung rasch. Die Genauigkeit ist besser als 10%.

     

The intercalation of cetyltrimethylammonium cations into muscovite by a two-step process: II. The intercalation of cetyltrimethylammonium cations into Li-muscovite

The alkylammonium cations were successively intercalated into the interlayer of muscovite. It was achieved by inorganic-organic ion exchange in the hydrothermal reaction of the LiNO₃-treated muscovite with cetyltrimethylammonium bromide solution. One-dimensional Patterson plots and electron density calculations show that hydrated Li⁺ and CTA⁺ cations entered the interlayer of muscovite successively. The CTA⁺-intercalated muscovite was characterized by powder X-ray diffraction and elemental analysis, in conjunction with FTIR, nuclear magnetic resonance, X-ray photoelectron spectra, high-resolution transmission electron microscopy, etc. The experiments show that organo-muscovite composite with ordered structure has been obtained. The CTA⁺ headgroups are distributed in the interlayer uniformly. However, the arrangement and conformation of CTA⁺ chains are strongly dependent upon the reaction temperature. At lower reaction temperature, the chains of CTA⁺ ions adopt a little more disordered arrangement and have higher gauche/trans conformer ratio, resulting in the disturbance to the interlayer symmetry. Whereas at higher reaction temperature, the sample with paraffin-like arrangement of CTA⁺ chains could be obtained, in which the methylene chains of CTA⁺ adopt a fully stretched, all-trans conformation.     

Membrane assembly driven by a biomimetic coupling reaction

One of the major goals of synthetic biology is the development of non-natural cellular systems. In this work, we describe a catalytic biomimetic coupling reaction capable of driving the de novo self-assembly of phospholipid membranes. Our system features a coppercatalyzed azide-alkyne cycloaddition that results in the formation of a triazole-containing phospholipid analogue. Concomitant assembly of membranes occurs spontaneously, not requiring preexisting membranes to house catalysts or precursors. The substitution of efficient synthetic reactions for key biochemical processes may offer a general route toward synthetic biological systems.     

Fabrication of nanoaggregates of a triple hydrophilic block copolymer by cetyltrimethylammonium chloride binding

A triple hydrophilic block copolymer composed of poly(ethylene oxide), poly(sodium 2-acrylamido-2-methylpropanesulfonate), and poly(methacrylic acid) (PEO-PAMPS-PMAA) does not form a micelle by itself when it is dissolved in water. However, if the anionic PAMPS and/or PMAA blocks are electrically neutralized with a cationic surfactant, such as cetyltrimethylammonium chloride (CTAC), micelle-like nanoaggregates are obtained, where the core is formed by the insolubilized PAMPS and/or PMAA blocks. Formation of the nanoaggregates was confirmed by dynamic light scattering (DLS) measurements and scanning electron microscopy (SEM), while the binding of CTAC to PEO-PAMPS-PMAA was monitored by electrophoresis measurements. The aggregates were characterized by fluorescence spectroscopy as well as DLS and SEM. It was found that the nanoaggregates have a spherical structure, and the hydrodynamic diameter ranges from 125 to 193 nm depending on the concentrations of the PEO-PAMPS-PMAA and CTAC. The critical aggregate concentration is on the order of 10-4 g L-1 when the ionic blocks of PEO-PAMPS-PMAA are fully neutralized with CTAC.     

Oxidation of isoniazid by quinolinium dichromate in an aqueous acid medium and kinetic determination of isoniazid in pure and pharmaceutical formulations.

The kinetics of oxidation of isoniazid in acidic medium was studied spectrophotometrically. The reaction between QDC and isoniazid in acid medium exhibits (4:1) stoichiometry (QDC:isoniazid). The reaction showed first order kinetics in quinolinium dichromate (QDC) concentration and an order of less than unity in isoniazid (INH) and acid concentrations. The oxidation reaction proceeds via a protonated QDC species, which forms a complex with isoniazid. The latter decomposes in a slow step to give a free radical derived from isoniazid and an intermediate chromium(V), which is followed, by subsequent fast steps to give the products. The reaction constants involved in the mechanism are evaluated. Isoniazid was analyzed by kinetic methods in pure and pharmaceutical formulations.     

Potentiometric determination of plutonium by argentic oxidation, ferrous reduction and dichromate titration

A simple and rapid method is described for the routine determination of plutonium with a coefficient of variation of better than 0.2%. It is directly applicable to nitrate solutions containing a large amount of uranium; moderate amounts of iron, molybdenum, fluoride and phosphate do not interfere. Chromium, cerium and manganese interfere quantitatively, and the procedure may also prove convenient for the determination of these elements. The plutonium is oxidised to the sexivalent state with argentic oxide in nitric acid solution, and the excess of oxidant is destroyed by reaction with sulphamic acid. A weighed small excess of iron(II) solution is then added, and the excess is titrated potentiometrically with standard potassium dichromate solution using polarised gold indicator electrodes. The whole determination is performed in one vessel at room temperature, and takes about 20 min.     

Total synthesis of angelone enabled by a remarkable biomimetic sequence

The natural product angelone was readily accessed with a remarkable biomimetic journey that sequentially features carbonyl formation–elimination, 6π-electrocyclization, visible light-promoted singlet O₂ Diels–Alder reaction, Kornblum–DeLaMare-type peroxide rearrangement, 6π-electrocyclic ring-opening, and conjugative addition–elimination as the key steps. With key intermediates isolated and characterized, this study stands to reveal a rare system in which bio-inspired synthetic strategies were found to mirror experimental realities.     

Improvement of a biomimetic porphyrin catalytic system by addition of acids

The conditions of the use of the manganese/porphyrin/imidazole system needed to be improved in order to obtain larger amounts of models of metabolites. An increase of the oxidation yields and a better preservation of this catalytic system have been obtained on the examples of various alkanes, by an acid addition in the reaction mixture. Three manganoporphyrins were checked for evaluation of the reaction. These results were extended to molecules of therapeutical interest such as ibuprofen and phenylbutazone.     

Design, synthesis, and evaluation of a biomimetic artificial photolyase model

Two new artificial photolyase models that recognize pyrimidine dimers in protic and aprotic organic solvents as well as in water through a combination of charge and hydrogen-bonding interactions and use a mimic of the flavine to achieve repair through reductive photoinduced electron transfer are presented. Fluorescence and NMR titration studies show that it forms a 1:1 complex with pyrimidine dimers with binding constants of approximately 10(3) M(-1) in acetonitrile or methanol, while binding constants in water at pH 7.2 are slightly lower. Excitation of the complex with visible light leads to clean and rapid cycloreversion of the pyrimidine dimer through photoinduced electron transfer catalysis. The reaction in water is significantly faster than in organic solvents. The reaction slows down at higher conversions due to product inhibition.     

Synthesis of (+)-sch 642305 by a biomimetic transannular Michael reaction

[reaction: see text] The synthesis of (+)-Sch 642305 (1) has been completed in 17 steps in 1.6% overall yield. Transannular Michael reaction of 2b with NaH in THF provided cyclohexenone 23 stereospecifically. Heating 23 in TFA/CDCl(3) provided a 3:1 equilibrium mixture of 23 and 25, which was hydrolyzed to give (+)-6-epi-Sch 642305 (24) and (+)-Sch 642305 (1), respectively.     

Optimization of a biomimetic transamination reaction

For a range of protein substrates, N-terminal transamination offers a convenient way to install a reactive ketone or aldehyde functional group at a single location. We report herein the effects of the identity of N-terminal residues on the product distribution generated upon reaction with pyridoxal 5'-phosphate (PLP). This study was accomplished through the combination of solid-phase peptide synthesis with detailed liquid chromatography-mass spectrometry analysis. Many N-terminal amino acids provided high yields of the desired transaminated products, but some residues (His, Trp, Lys, and Pro) generated adducts with PLP itself. N-terminal Cys and Ser residues were observed to undergo beta-elimination in addition to transamination, and the transamination product of N-terminal Gln was resistant to subsequent oxime formation attempts. The information generated through the screening of peptide substrates was successfully applied to a protein target, changing an initially unreactive terminus into one that could be modified in high (70%) yield. Thus, these studies have increased our predictive power for the reaction, both in terms of improving conversion and suppressing reaction byproducts. An initial set of guidelines that may be used to increase the applicability of this reaction to specific proteins of interest is provided.