Search results for "Coupling"

Pseudo-solid echoes of proton and deuteron NMR in polyethvlene melts

1981

The solid echo technique is applied to determining residual dipolar and quadrupolar couplings in molten polyethylene (PE) and deuterated PE, respectively. The residual coupling defined by the square root of the second moment is about 1% of the corresponding quantity in the solid. It increases with molecular weight, and decreases with rising temperature. A theoretical treatment of time dependent residual couplings yields a decay time that is found experimentally to be about 0.1 ms in molten PE, and independent of molecular weight and temperature within our limits of accuracy. The residual coupling is discussed in relation with chain entanglement in PE. Measurements of the spin-lattice and sp…

Analysis of amino acids using serially coupled columns.

2017

Single conventional columns in reversed-phase LC are insufficient for analysing the isoindoles of primary amino acids, due to their limited functionality. An interesting possibility for increasing the separation power is the combination of several columns of different nature, where the length is modified by coupling small segments. This approach may require a considerable investment to have multiple lengths for each stationary phase. However, the combination of only two columns of fixed length can be enough to resolve satisfactorily relatively complex mixtures, provided that an optimised gradient program is applied. In this work, a mixture of 19 primary amino acid isoindoles found in protei…

Effective pair potential between charged nanoparticles at high volume fractions

2017

Simulations of charged colloidal dispersions are technically challenging. One possible workaround consists in reducing the system to the colloids only, whose interactions are described through an effective pair potential, wf. Still, the determination of wf is difficult mainly because it depends on the colloidal density, ϕ. Here we propose to calculate wf from simulations of a pair of colloids placed in a cubic box with periodic boundary conditions. The variation in ϕ is mimicked by an appropriate change in the concentration of counterions neutralized by an homogeneous background charge. The method is tested at the level of the primitive model. A good description of the structure of the coll…

Capping α-Cyclodextrin with Cyclotriveratrylene by Triple Disulfide-Bridge Formation

2013

Disulfide-bond formation is an expeditious coupling reaction to make macropolycyclic symmetrical receptors. It is used here for the preparation of unsymmetrical cavitands based on α-cyclodextrin (α-CDX) and cyclotriveratrylene (CTV) analogues. Accordingly, diastereomeric hemicryptophanes 2a and 2b were obtained in 11 % isolated yield by the iodine oxidation of a 1:1 mixture of racemic cyclotrithiophenolene (3) and the C3-symmetric trithiol derivative of permethylated α-cyclodextrin (PM α-CDX) 4. Remarkably, the target hemicryptophanes were obtained in a 5:3 diastereomeric ratio. The reaction produced mainly (34 %) a singly disulfide-bridged PM α-CDX dimer 7, however no traces of triply disu…

Screening of ligands for the Ullmann synthesis of electron-rich diaryl ethers

2012

In the search for new ligands for the Ullmann diaryl ether synthesis, permitting the coupling of electron-rich aryl bromides at relatively low temperatures, 56 structurally diverse multidentate ligands were screened in a model system that uses copper iodide in acetonitrile with potassium phosphate as the base. The ligands differed largely in their performance, but no privileged structural class could be identified.

Heterogeneously catalyzed Suzuki-Miyaura conversion of broad scope

2012

The reaction tolerates a broad range of functional groups in the coupling partners and is usually performed in solution under homogeneous conditions at T ¢ 60 uC using 2–3 mol% catalytic amounts. The catalyst is often a Pd(0) complex with triarylphosphane ligands. 2 The catalytic cycle (Scheme 2) begins with the oxidative addition of an aryl halide to a Pd(0) species formed in situ to form an arylpalladium(II) halide intermediate. 3 Chloroarenes, especially nonactivated aryl chlorides, are notoriously less reactive due to the stability of the C–Cl bond (the relative reactivity of Ar–X is correlated to the respective bond dissociation energy: Ph–Cl: 96 kcal mol 21 ,P h–Br: 81 kcal mol 21 ,P …

Synthesis of Mammalian Gonadoliberin Analogs with the N-terminal glutamine or glutamine or glutamic acid

1991

Synthesis of two mammalian gonadoliberin analogs, [Gln1]GnRH and [Glu1]GnRH, in solution by the peptide segment coupling of the [(2 + 4) + 4] type has been described.

C-Glycosyl amino acids through hydroboration-cross-coupling of exo-glycals and their application in automated solid-phase synthesis.

2013

O-Glycosylation is one of the most important post-translational modifications of proteins. The attachment of carbohydrates to the peptide backbone influences the conformation as well as the solubility of the conjugates and can even be essential for binding to specific ligands in cell-cell interactions or for active transport over membranes. This makes glycopeptides an interesting class of compounds for medical applications. To enhance the long-term availability of these molecules in vivo, the stabilization of the glycosidic bond between the amino acid residue and the carbohydrate is of interest. The described modular approach affords β-linked C-glycosyl amino acids by a sequence of Petasis …

Iron-Catalyzed C(sp2)-C(sp3) Cross-Coupling of Alkyl Grignard Reagents with Polyaromatic Tosylates

2017

Anodic Dehydrogenative Cyanamidation of Thioethers: Simple and Sustainable Synthesis of N‐Cyanosulfilimines

2021

Abstract A novel and very simple to perform electrochemical approach for the synthesis of several N‐cyanosulfilimines in good to excellent yields was established. This method provides access to biologically relevant sulfoximines by consecutive oxidation using electro‐generated periodate. This route can be easily scaled‐up to gram quantities. The S,N coupling is carried out at an inexpensive carbon anode by direct oxidation of sulfide. Therefore, the designed process is atom economic and represents a new “green route” for the synthesis of sulfilimines and sulfoximines.