Crystallisation progress in Si-rich ultra-soft nanocomposite alloy fabricated by melt spinning

The crystallisation process and the ultras-soft magnetic properties of amorphous/nanocomposite alloy Fe_73.5Si_17.5B₅Nb₃Cu₁ fabricated by conventional melt-spinning technique are systematically investigated in terms of thermal analysis and in-situ measurement of magnetisation dynamics. The thermal analysis using differential scanning calorimetry showed that crystallisation from Fe-based amorphous state to α-Fe(Si) started at . Further heating the sample leads to a transformation from the α-Fe(Si) to Fe-B phases at . Crystallisation activation energies were determined using two models: Kissinger and John-Mehl-Avrami (JMA), which were consistent to each other with a value of . High resolution transmission electron microscopy investigation revealed an ultrafine structure of α-Fe(Si) nanocrystallite with mean size of 12.5 nm embedded in an amorphous matrix. At a volume fraction of 86% of α-Fe(Si) phase, optimum soft magnetic properties were obtained with very high permeability of 110,000 and a very low coercivity of 0.015 Oe by annealing the amorphous alloy at in 40 min.     

Some imines and azo compounds containing furoxan ring synthesized from methylisoeugenol

Some imines and azo compounds containing furoxan and benzene rings have been prepared starting from methylisoeugenol. The structure of reported compounds has been confirmed by elemental analysis, ms, uv, ir, and nmr spectroscopy. It is shown that, on treatment with Na₂S₂O₄, the nitro group on the benzene ring was reduced to an amino group, but the N←O group of furoxan ring was not. The ¹H‐ and ¹³C nmr signals are assigned based on their spin‐spin splitting patterns, in some cases, NOESY and HMBC spectra are used. The NOESY spectra indicate that the reported imines have E‐configuration. Among 8 tested compounds, there are 5 compounds that exhibit anti‐microbial activity toward Gr+ S. aureus at concentration 12.5μg/mL.     

A dynamic principal-agent problem as a feedback Stackelberg differential game

We consider situations in which a principal tries to induce an agent to spend effort on accumulating a state variable that affects the well-being of both parties. The only incentive mechanism that the principal can use is a state-dependent transfer of her own utility to the agent. Formally, the model is a Stackelberg differential game in which the players use feedback strategies. Whereas in general Stackelberg differential games with feedback strategy spaces the leader’s optimization problem has non-standard features that make it extremely hard to solve, in the present case this problem can be rewritten as a standard optimal control problem. A linear-quadratic example is used to illustrate our approach.     

Highly enantioselective catalytic asymmetric hydrogenation of beta-keto esters in room temperature ionic liquids

Polar phosphonic acid-derived Ru-BINAP systems were used to catalyze asymmetric hydrogenation of beta-keto esters in room temperature ionic liquids (RTILs) with complete conversions and ee values higher than those obtained from homogeneous reactions in MeOH (up to 99.3%), and were recycled by simple extraction and used for four times without the loss of activity and enantioselectivity.     

Posttranslational hydroxylation of human phenylalanine hydroxylase is a novel example of enzyme self-repair within the second coordination sphere of catalytic iron

Phenylalanine hydroxylase, a mononuclear non-heme iron enzyme, catalyzes the hydroxylation of phenylalanine to tyrosine in the presence of oxygen and reduced pterin cofactor. X-ray structural studies have established the coordination around the iron metal center and point to significant interactions within the second coordination sphere. One such interaction involves Tyr325 in human phenylalanine hydroxylase (hPAH), which forms a hydrogen-bonding network with an aqua ligand on iron and the pterin cofactor. The full-length tetramer (1-452) and truncated dimer (117-424) Tyr325Phe hPAH mutant enzymes showed similar kinetics, thermal stabilities, and oligomerization profiles as their corresponding wild-type proteins. The possibility of in vivo posttranslational hydroxylation that would restore the activity of hPAH was examined by mass spectrometry on the trypsin digested full-length (1-452) hPAH Tyr325Phe point mutant. The amino acid tags obtained by ESI-MS/MS confirmed the presence of a Phe325 in the peptide corresponding to the doubly charged precursor ion at m/z 916.4 (L A T I F W F T V E F G L C K), and its hydroxylated counterpart in the peptide corresponding to the m/z 924.4 (L A T I F-OH W F T V E F G L C K) byproduct ion series comprising the fragments y(5)-y(12). Furthermore, the point mutation Tyr325Ala resulted in an enzyme that was totally inactive and did not display any evidence of hydroxylation. These results demonstrate the importance of Tyr325 for proper conformation of the active site, substrate binding, and catalysis. The rescue of the Tyr325Phe mutant in hPAH via self-hydroxylation presents a novel example of oxidative repair on the molecular level.     

Über Schwache Sequenzen

Ohne Zusammenfassung

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Lebbeckoside C,a new triterpenoid saponin from the stem barks of Albizia lebbeck inhibits the growth of human glioblastoma cells

One new acacic acid-type saponin, named lebbeckoside C (1), was isolated from the stem barks of Albizia lebbeck. Its structure was established on the basis of extensive analysis of 1D and 2D NMR (¹H, ¹³C NMR, DEPT, COSY, TOCSY, ROESY, HSQC and HMBC) experiments, HRESIMS studies, and by chemical evidence as 3-O-[β-d-xylopyranosyl-(l→2)-β-d-fucopyranosyl-(1→6)-[β-d-glucopyranosyl(1→2)]-β-d-glucopyranosyl]-21-O-{(2E,6S)-6-O-{4-O-[(2E,6S)-2,6-dimethyl-6-O-(β-d-quinovopyranosyl)octa-2,7-dienoyl]-4-O-[(2E,6S)-2,6-dimethyl-6-O-(β-d-quinovopyranosyl)octa-2,7-dienoyl]-β-d-quinovopyranosyl}-2,6-dimethylocta-2,7-dienoyl}acacic acid 28 O-[β-d-quinovopyranosyl-(l→3)-[α-l-arabinofuranosyl-(l→4)]-α-l-rhamnopyranosyl-(l→2)-β-d-glucopyranosyl] ester. The isolated saponin (1) displayed significant cytotoxic activity against the human glioblastoma cell line U-87 MG and TG1 stem-like glioma cells isolated from a patient tumor with IC₅₀ values of 1.69 and 1.44 μM, respectively.     

Avid AL, a synthetic ligand affinity gel mimicking immobilized bacterial antibody receptor for purification of immunoglobulin G.

Avid AL is an affinity gel designed for the purification of immunoglobulin G (IgG). The gel was prepared by first reacting Sepharose with 3,5-dichloro-2,4,6-trifluoropyridine and 4-dimethylaminopyridine and then with 2-mercaptoethanol. The IgG purified by Avid AL is about 95% pure. The binding parameters of Avid AL for the whole IgG, Fab and Fc fragment and the stability of gel were investigated. The IgG bound to Avid AL can be eluted with an acidic buffer or with a novel neutral buffer containing electron donors. The development of such a mild neutral elution buffer is described. Application of Avid AL in a rapid gram-scale IgG purification was demonstrated. The possible mechanism of IgG binding is discussed.     

Single-molecule fluorescence detection of a tricyclic nucleoside analogue

Fluorescent nucleobase surrogates capable of Watson–Crick hydrogen bonding are essential probes of nucleic acid structure and dynamics, but their limited brightness and short absorption and emission wavelengths have rendered them unsuitable for single-molecule detection. Aiming to improve on these properties, we designed a new tricyclic pyrimidine nucleoside analogue with a push–pull conjugated system and synthesized it in seven sequential steps. The resulting C-linked 8-(diethylamino)benzo[b][1,8]naphthyridin-2(1H)-one nucleoside, which we name ABN, exhibits ε₄₄₂ = 20 000 M⁻¹ cm⁻¹ and Φ_em,540 = 0.39 in water, increasing to Φ_em = 0.50–0.53 when base paired with adenine in duplex DNA oligonucleotides. Single-molecule fluorescence measurements of ABN using both one-photon and two-photon excitation demonstrate its excellent photostability and indicate that the nucleoside is present to > 95% in a bright state with count rates of at least 15 kHz per molecule. This new fluorescent nucleobase analogue, which, in duplex DNA, is the brightest and most red-shifted known, is the first to offer robust and accessible single-molecule fluorescence detection capabilities.

Fluorescent nucleoside analogue ABN is readily detected at the single-molecule level and retains a quantum yield >50% in duplex DNA oligonucleotides.