Polypyridyl-Based Copper Phenanthrene Complexes: Combining Stability with Enhanced DNA Recognition

We report a series of copper(II) artificial metallo-nucleases (AMNs) and demonstrate their DNA damaging properties and in-vitro cytotoxicity against human-derived pancreatic cancer cells. The compounds combine a tris-chelating polypyridyl ligand, di-(2-pycolyl)amine (DPA), and a DNA intercalating phenanthrene unit. Their general formula is Cu-DPA-N,N' (where N,N'=1,10-phenanthroline (Phen), dipyridoquinoxaline (DPQ) or dipyridophenazine (DPPZ)). Characterisation was achieved by X-ray crystallography and continuous-wave EPR (cw-EPR), hyperfine sublevel correlation (HYSCORE) and Davies electron-nuclear double resonance (ENDOR) spectroscopies. The presence of the DPA ligand enhances solution stability and facilitates enhanced DNA recognition with apparent binding constants (K_app) rising from 10⁵ to 10⁷ m ⁻¹ with increasing extent of planar phenanthrene. Cu-DPA-DPPZ, the complex with greatest DNA binding and intercalation effects, recognises the minor groove of guanine–cytosine (G-C) rich sequences. Oxidative DNA damage also occurs in the minor groove and can be inhibited by superoxide and hydroxyl radical trapping agents. The complexes, particularly Cu-DPA-DPPZ, display promising anticancer activity against human pancreatic tumour cells with in-vitro results surpassing the clinical platinum(II) drug oxaliplatin.     

Switchable Q-switched and laser operating mode-locked erbium-doped fiber in the L-band region

We demonstrate a switchable Q-switched and mode-locked erbium-doped fiber laser （EDFL） operating in the L-band region using the nonlinear polarization rotation effect. The switching operation is achieved by controlling intensity-dependent loss using a polarization controller. In Q-switching mode, the EDFL produces a pulse train with a repetition rate of 21.1 kHz, pulse width of 7.7 #s, and pulse energy of 13.6 nJ. The EDFL also generates a multi-wavelength comb with a very narrow and constant wavelength spacing of 0.045 nm and optical signal-to-noise ratio of at least l0 dB. During mode locking, the EDFL produces stretched pulses with 3-dB bandwidth of 26.2 nm, pulse width of 350 fs, repetition rate of 2.38 MHz, and pulse energy of 48.56 pJ.     

Performance evaluation of polycyclic aromatic hydrocarbons analysis in sediment from proficiency testing with metrological reference values

This paper describes a metrological approach to evaluate the measurement capability of laboratories participating in two proficiency testing (PT) programmes involving the analysis of five polycyclic aromatic hydrocarbons (PAHs) in sediment samples. Reference values of PAHs in the programmes for performance assessment were obtained from an accurate isotope dilution gas chromatography mass spectrometry (ID-GCMS) method which was thoroughly validated and verified. Isotope dilution mass spectrometry (IDMS) technique usually has a well-defined measurement uncertainty budget and a traceability link to an International System of Units. Provision of the metrological reference values in PT enables the establishment of a technical platform to assess the actual competence of the participating laboratories in sediment PAHs analysis. Results of the PT programmes showed that about 80 % of the laboratories employed gas chromatography in their analyses and the remaining used liquid chromatography. Irrespective of the techniques being used, however, the majority of the participating laboratories were observed to underestimate values in which the mean values of the five reported PAHs were less than those of the ID-GCMS-derived reference values by 13–20 %. Only 41–44 % of the participating laboratories were able to achieve satisfactory z-scores. The present study revealed that the reinforcement of the capability for accurate measurement of PAHs in sediment samples in laboratories worldwide should be addressed.     

Effect of synthesis conditions on the mechanism of reversible inhibition in the TEMPO-mediated polymerization of 4-vinylpyridine

The effects of polymerization conditions (the types and concentrations of initiator and solvent, the TEMPO-to-initiator molar ratio, and temperature) on the kinetics and mechanism of pseudoliving radical polymerization of 4-vinylpyridine mediated by the nitroxide TEMPO are studied. The key quantitative parameters of the process are calculated: namely, the rate constant of reinitiation, the rate constant of inhibition, and the product of the propagation-rate constant and the pseudoliving equilibrium constant. The optimum conditions for the controlled synthesis of poly(4-vinylpyridine) mediated by TEMPO are ascertained.     

Inclusion of thymol into cucurbiturils: density functional theory approach with dispersion correction and natural bond orbital analysis

Journal of Inclusion Phenomena and Macrocyclic Chemistry - Stability of inclusion complexes of thymol (a natural flavour) with cucurbit[n]urils was interpreted by using density functional theory...     

A Dynamic Model for Cellulosic Biomass Hydrolysis: a Comprehensive Analysis and Validation of Hydrolysis and Product Inhibition Mechanisms

The objective of this study is to perform a comprehensive enzyme kinetics analysis in view of validating and consolidating a semimechanistic kinetic model consisting of homogeneous and heterogeneous reactions for enzymatic hydrolysis of lignocellulosic biomass proposed by the U.S. National Renewable Energy Laboratory (Kadam et al., Biotechnol Prog 20(3):698–705, 2004) and its variations proposed in this work. A number of dedicated experiments were carried out under a range of initial conditions (Avicel® versus pretreated barley straw as substrate, different enzyme loadings and different product inhibitors such as glucose, cellobiose and xylose) to test the hydrolysis and product inhibition mechanisms of the model. A nonlinear least squares method was used to identify the model and estimate kinetic parameters based on the experimental data. The suitable mathematical model for industrial application was selected among the proposed models based on statistical information (weighted sum of square errors). The analysis showed that transglycosylation plays a key role at high glucose levels. It also showed that the values of parameters depend on the selected experimental data used for parameter estimation. Therefore, the parameter values are not universal and should be used with caution. The model proposed by Kadam et al. (Biotechnol Prog 20(3):698–705, 2004) failed to predict the hydrolysis phenomena at high glucose levels, but when combined with transglycosylation reaction(s), the prediction of cellulose hydrolysis behaviour over a broad range of substrate concentrations (50–150 g/L) and enzyme loadings (15.8–31.6 and 1–5.9 mg protein/g cellulose for Celluclast and Novozyme 188, respectively) was possible. This is the first study introducing transglycosylation into the semimechanistic model. As long as these type of models are used within the boundary of their validity (substrate type, enzyme source and substrate concentration), they can support process design and technology improvement efforts at pilot and full-scale studies.