Effect of sialic acid content on glycoprotein pI analyzed by two‐dimensional electrophoresis

2‐DE is broadly used for quantitative analysis of differential protein expression in complex mixtures such as serum samples or cell lysates. PTMs directly influence the 2‐DE pattern, and knowledge of the rules of protein separation is required in order to understand the protein distribution in a 2‐DE gel. Glycosylation is the most common PTM and can modify both the molecular weight and the pI of a protein. In particular, the effect of charged monosaccharides (mainly sialic acids, SAs) on the 2‐DE pattern of a protein is of major interest since changes in sialylation are regularly observed in comparative studies. Little is known about the pI shift of a glycoprotein induced by the presence of SAs, or whether this shift is the same for all glycoproteins. To address this issue, this study examined the influence of SA on the 2‐DE pattern of three serum glycoproteins (haptoglobin, α1‐antitrypsin and ribonuclease 1), which N‐glycan chains had been previously characterised, and reviewed existing bibliographic data. The SA content of the different glycoforms of a glycoprotein showed a negative linear correlation with the pI, although the slope varied among the studied glycoproteins. We also described a positive correlation between the protein pI and the pI decrease per SA molecule.     

State-dependent Foster–Lyapunov criteria for subgeometric convergence of Markov chains

We consider a form of state-dependent drift condition for a general Markov chain, whereby the chain subsampled at some deterministic time satisfies a geometric Foster–Lyapunov condition. We present sufficient criteria for such a drift condition to exist, and use these to partially answer a question posed in Connor and Kendall (2007) [2] concerning the existence of so-called ‘tame’ Markov chains. Furthermore, we show that our ‘subsampled drift condition’ implies the existence of finite moments for the return time to a small set.     

Subgeometric rates of convergence of f-ergodic strong Markov processes

We provide a condition in terms of a supermartingale property for a functional of the Markov process, which implies (a) f$f$-ergodicity of strong Markov processes at a subgeometric rate, and (b) a moderate deviation principle for an integral (bounded) functional. An equivalent condition in terms of a drift inequality on the extended generator is also given. Results related to (f,r)$(f,r)$-regularity of the process, of some skeleton chains and of the resolvent chain are also derived. Applications to specific processes are considered, including elliptic stochastic differential equations, Langevin diffusions, hypoelliptic stochastic damping Hamiltonian systems and storage models.     

[(C C)Au(N N)]+ Complexes as a New Family of Anticancer Candidates: Synthesis,Characterization and Exploration of the Antiproliferative Properties

A library of eleven cationic gold(III) complexes of the general formula [(C C)Au(N N)]⁺ when C C is either biphenyl or 4,4’-ditertbutyldiphenyl and N N is a bipyridine, phenanthroline or dipyridylamine derivative have been synthesized and characterized. Contrasting effects on the viability of the triple negative breast cancer cells MDA-MB-231 was observed from a preliminary screening. The antiproliferative activity of the seven most active complexes were further assayed on a larger panel of human cancer cells as well as on non-cancerous cells for comparison. Two complexes stood out for being either highly active or highly selective. Eventually, reactivity studies with biologically meaningful amino acids, glutathione, higher order DNA structures and thioredoxin reductase (TrxR) revealed a markedly different behavior from that of the well-known coordinatively isomeric [(C N C)Au(NHC)]⁺ structure. This makes the [(C C)Au(N N)]⁺ complexes a new class of organogold compounds with an original mode of action.     

Size-Controlled Synthesis of β(1→4)-GlcNAc Oligosaccharides Using an Endo-Glycosynthase

Chitin and peptidoglycan fragments are well recognized as pathogen associated molecular patterns (PAMPs). Long-chain oligosaccharides of β(1→4)-linked N-acetyl-D-glucosamine (GlcNAc) units indeed activate plants and mammals innate immune system. However, the mechanisms underlying PAMPs perception by lysine motif (LysM) domain receptors remain largely unknown because of insufficient availability of high-affinity molecular probes. Here, we report a two-enzyme cascade to synthesize long-chain β(1→4)-linked GlcNAc oligomers. Expression of the D52S mutant of hen egg-white lysozyme (HEWL) in Pichia pastoris at 52 mg L⁻¹ provided a new glycosynthase catalyzing efficient polymerization of α-chitintriosyl fluoride. Selective N-deacetylation at the non-reducing unit of the glycosyl fluoride donor by Sinorhizobium meliloti NodB chitin-N-deacetylase abolished its ability to be polymerized by the glycosynthase but not to be transferred onto an acceptor. Using NodB and D52S HEWL in a one-pot cascade reaction allowed the synthesis on a milligram scale of chitin hexa-, hepta- and octasaccharides with yields up to 65 % and a perfect control over their size.     

Near-edge Optical Properties of CuInSe2 Studied by Photoacoustic Spectroscopy

Optical absorption spectra of n-type CuInSe₂ single crystals were evaluated by means of photoacoustic spectroscopy in the photon energy range from 0.94 to 1.02 eV. At photon energies below 0.99 eV the spectra exhibit exponential tails that are ascribed to the presence of shallow impurity states. At higher photon energies the absorption coefficients follow the relation for direct allowed optical transitions between parabolic bands. The parameters of this relation are determined and compared with previous measurements.     

Optical Investigation of Defects in p-type CuInSe2 Single Crystals

Optical absorption spectra in the photon energy range from 0.03 to 1.1 eV and photoreflectance spectra in the range of the fundamental edge are measured on p-type CuInSe₂ single crystals. Besides a dominant contribution to the absorption coefficient due to intervalence band transitions below about 0.75 eV the spectra revealed five additional structures that can be ascribed to defect induced optical transitions with characteristic energies between 0.48 and 0.72 eV. Based on a comparison of the near-edge optical absorption and photoreflectance spectra a shallow defect (donor or acceptor) with an ionisation energy of about 46 meV was identified.