Improved deprotection in solid phase peptide synthesis: quantitative reduction of methionine sulfoxide to methionine during HF cleavage

The reduction of methionine sulfoxide residues in peptides was found to be quantitative by treatment with a low concentration of HF in dimethylsulfide (HF:dimethylsulfide, 1:3, v/v). The reduction was dependent on the acidity function of HF and was optimal with an HF concentration between 25% and 40%. The low HF concentration cleavage reagent also deprotected most of the benzyl alcohol-derived protecting groups.     

Determination of aflatoxins B1, B2, G1 and G2 by high-performance liquid chromatography with electrochemical detection

A new approach to the determination of afiatoxins B₁, B₂, G₁ and G₂ is given; the method involves high-performance liquid chromatography with amperometric detection in the differential-pulse mode at the dropping mercury electrode with 1-s drop time. These aflatoxins can be determined simultaneously with good resolution but with some compromise in sensitivity. The detection limit of underivatized aflatoxin standards is around 5 ng. Average recoveries of aflatoxins from peanut butter by the Beebe method were G₂ 81%, G₁ 87%, B₂ 77% and B₁ 76%.     

2:1:1 Resonance in the Quasi-Periodic Mathieu Equation

We present a small $ \ddot x + (\delta + \epsilon \cos t + \epsilon \cos \omega t) x=0 $ \ddot x + (\delta + \epsilon \cos t + \epsilon \cos \omega t) x=0      

A combined measurement of thermal and mechanical relaxation

In order to describe relaxation the thermodynamic coefficient can be generalized into a complex frequency-dependent cross response function. We explore theoretically the possibility of measuring for a supercooled liquid near the glass transition. This is done by placing a thermistor in the middle of the liquid which itself is contained in a spherical piezoelectric shell. The piezoelectric voltage response to a thermal power generated in the thermistor is found to be proportional to but factors pertaining to heat diffusion and adiabatic compressibility κ_S(ω) do also intervene. We estimate a measurable piezoelectric voltage of 1 mV to be generated at 1 Hz for a heating power of 0.3 mW. Together with κ_S(ω) and the longitudinal specific heat c_l(ω) which may also be found in the same setup a complete triple of thermoviscoelastic response functions may be determined when supplemented with shear modulus data.     

Spectroscopy and rectification of three donor-sigma-acceptor compounds, consisting of a one-electron donor (pyrene or ferrocene), a one-electron acceptor (perylenebisimide), and a C19 swallowtail

We report spectroscopic characterization and unimolecular rectification (asymmetric electrical conduction) measurements of three donor-sigma-acceptor (D-sigma-A) compounds N-(10-nonadecyl)-N-(1-pyrenylmethyl)perylene-3,4,9,10-bis(dicarboximide) (1), N-(10-nonadecyl)-N-(4-[1-pyrenyl]butyl)perylene-3,4,9,10-bis(dicarboximide) (2), and N-(10-nonadecyl)-N-(2-ferrocenylethyl)perylene-3,4,9,10-bis(dicarboximide) (3). These molecules were arranged as one-molecule thick Langmuir-Blodgett monolayers between Au electrodes. In such an "Au | D-sigma-A | Au" sandwich, molecule 1 is a unimolecular rectifier, with rather small rectification ratios (between 2 and 3 at +/-1 V) that decrease upon cycling. Molecule 2 does not rectify. Molecule 3 rectifies, with a rectification ratio of between 14 and 28 at +/-1 V; the through-film rectification and currents persist, even with scans of +/-2 V, for up to 40 cycles of measurement. Qualitative arguments, based on a two-level rectification mechanism, are consistent with the current asymmetries observed in the monolayers of 1 and 3.     

Biocatalytic deuterium- and hydrogen-transfer using over-expressed ADH-'A': enhanced stereoselectivity and 2H-labeled chiral alcohols

Employing the over-expressed highly organic solvent tolerant alcohol dehydrogenase ADH-'A' from Rhodococcus ruber DSM 44541, versatile building blocks, which were not accessible by the wild type catalyst, were obtained in > 99% e.e.; furthermore, employing d8-2-propanol as deuterium source, stereoselective biocatalytic deuterium transfer was made feasible to furnish enantiopure deuterium labeled sec-alcohols on a preparative scale employing a single enzyme.     

Ethynylphosphonamidates for the Rapid and Cysteine‐Selective Generation of Efficacious Antibody–Drug Conjugates

Requirements for novel bioconjugation reactions for the synthesis of antibody–drug conjugates (ADCs) are exceptionally high, since conjugation selectivity as well as the stability and hydrophobicity of linkers and payloads drastically influence the performance and safety profile of the final product. We report Cys‐selective ethynylphosphonamidates as new reagents for the rapid generation of efficacious ADCs from native non‐engineered monoclonal antibodies through a simple one‐pot reduction and alkylation. Ethynylphosphonamidates can be easily substituted with hydrophilic residues, giving rise to electrophilic labeling reagents with tunable solubility properties. We demonstrate that ethynylphosphonamidate‐linked ADCs have excellent properties for next‐generation antibody therapeutics in terms of serum stability and in vivo antitumor activity.