New Methods for β-Lactam Formation from β-Amino Acids Using (C6H5)3P/CC14 and (C6H5)3P/NBS

Triphenylphosphine/carbon tetrachloride and triphenyl-phosphine/N-bromosuccinimide were found to be very effective for β-lactam formation from β-amino acids in acetonitrile.     

Switchable peptide-equipped protein/cucurbit[7]uril supramolecular assembly for targeted drug delivery

ABSTRACT

Herein, we develop a switchable peptide-equipped protein/cucurbit[7]uril (CB[7]) supramolecular assembly as novel targeted drug vector. Specifically, bovine serum albumin (BSA) is used to interact with CB[7], serving as the core of drug vector. Then, a peptide shield layer is formed on the surface of BSA/CB[7], yielding peptide-equipped supramolecular assembly (Pep@BSA@CB[7]). The equipped peptide shield layer is composed of switchable peptide probes consisting of a polycationic cell-penetrating peptide (CPP) motif, a polyanionic motif and a linking motif, and therefore provides a variety of desirable properties. First, the CPP motif displays excellent cell penetration ability and can facilitate internalisation of the drug vector. Secondly, the polyanionic motif performs intramolecular electrostatic interaction with CPP motif and thereby can reduce non-targeted delivery towards normal cells. Thirdly, the linking motif can be specifically cleaved by matrix metalloproteinases 2 that is up-regulated in tumour microenvironment, thus enabling precise cancer-targeting. As a consequent, Pep@BSA@CB[7] can serve as a promising drug vector that exhibits superior targeting ability and high uptake efficiency towards cancer cells, which may be of great potential in cancer-targeted treatment.     

Potent Anticancer Efficacy of First-In-Class CuII and AuIII Metaled Phosphorus Dendrons with Distinct Cell Death Pathways

First-in-class Cu^II and Au^III metaled phosphorus dendrons were synthesized and showed significant antiproliferative activity against several aggressive breast cancer cell lines. The data suggest that the cytotoxicity increases with reducing length of the alkyl chains, whereas the replacement of Cu^II with Au^III considerably increases the antiproliferative activity of metaled phosphorus dendrons. Very interestingly, we found that the cell death pathway is related to the nature of the metal complexed by the plain dendrons. Cu^II metaled dendrons showed a potent caspase-independent cell death pathway, whereas Au^III metaled dendrons displayed a caspase-dependent apoptotic pathway. The complexation of plain dendrons with Au^III increased the cellular lethality versus dendrons with Cu^II and promoted the translocation of Bax into the mitochondria and the release of Cytochrome C (Cyto C).     

Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3− and SO32− in Aqueous Solution

The kinetics and mechanism of the reaction of S^IV (SO₃^2?+HSO₃^?) with a ruthenium(VI) nitrido complex, [(L)Ru^VI(N)(OH₂)]⁺ (Ru^VIN, L=N,N′‐bis(salicylidene)‐o‐cyclohexyldiamine dianion), in aqueous acidic solutions are reported. The kinetic results are consistent with parallel pathways involving oxidation of HSO₃^? and SO₃^2? by Ru^VIN. A deuterium isotope effect of 4.7 is observed in the HSO₃^? pathway. Based on experimental results and DFT calculations the proposed mechanism involves concerted N?S bond formation (partial N‐atom transfer) between Ru^VIN and HSO₃^? and H⁺ transfer from HSO₃^? to a H₂O molecule.     

Goniodilactone and gomoheptenolactone,two novel cytotoxic styryllactones from the leaves of Goniothalamus cheliensis

Two novel styryllactones,goniodilactone（1） and gonioheptenolactone（2）,were isolated from the leaves of Goniothalamus cheliensis Hu.Their structures were determined on the basis of spectroscopic data as well as X-ray crystallography analysis. Compounds 1 and 2 exhibited significant cytotoxicities in a panel of human cancer cells,including DU-145,PC-3,MCF-7,A-549, KB and KBvin,with GI₅₀S in the range of 1.29-4.56μg/mL.     

New approach to development of phenolic thermopolymerization inhibitors for processing of pyrolysis products (by example of pyrocatechol)

New approach to processing of phenols to enable their use as thermopolymerization inhibitors of unsaturated components of pyrocondensates is suggested. The method consists in a mild thermal treatment of a mixture of phenol, solvent, and kraft terpentine. A treatment of this kind results in that any (un)substituted phenol acquires inhibiting properties that compare well with those of the best phenolic inhibitors.     

Experimental Evidence for Ion Accumulation Time Affecting Qualitative and Quantitative Analysis of Ophiopogons in Ophiopogon Extract by Hybrid Ion Trap Time-of-Flight Mass Spectrometry

The qualitative and quantitative capability of the ion trap mass analyzer could be greatly affected by the accumulation time. However, the importance of the accumulation time has not so far been thoroughly explored. Here, the influence of ion accumulation time on qualitative and quantitative analysis of complicated components was systematically investigated based on the case study of 40 ophiopogonins in Ophiopogon extract by hybrid ion trap time-of-flight mass spectrometry (LCMS-IT-TOF). In this process, the accumulation time was set at 10, 25, 50, 100, and 200 ms, respectively. The effect of accumulation time on qualitative analysis of ophiopogonins was studied by comparing the total ion current (TIC) of MS¹, TIC of MS², and the number and signal of fragmental ions. The results demonstrated that the signal could be greatly influenced by varying the accumulation time. The number and signal of the fragmental ions were increased significantly with a longer accumulation time in the range of 10–100 ms. Also, the effect of accumulation time on quantitative analysis of ophiopogonins was investigated by comparing the linearity, accuracy, and precision measured on LCMS-IT-TOF. Importantly, quantitative parameters could all be significantly improved by choosing an appropriate accumulation time.

     

Euphorbiane: A Novel Triterpenoid with an Unprecedented Skeleton from Euphorbia tirucalli

Euphorbiane ( 1 ), a novel triterpenoid exhibiting a unique skeleton, together with seven known compounds were isolated from the 95% EtOH extract of the fresh stems of Euphorbia tirucalli. The structure of 1 and relative stereochemistry were elucidated by extensive NMR and a single‐crystal X‐ray crystallographic analysis.