7-amino-4-azaheptyl grafted onto a silica gel as a sorbent for the on-line preconcentration and determination of iron(III) in water samples.

A new sorbent was synthesized by anchoring 7-amino-4-azaheptyltrimetoxisilane, freshly prepared, to silica gel, producing 7-amino-4-azaheptyl anchored silica gel (AAHSG). This material was characterized by infrared spectroscopy (IR), elemental analysis (CHN), and nitrogen adsorption-desorption isotherms. Isotherms of the adsorption of Fe3+, Fe2+ and Cu2+ on AAHSG were recorded, which indicated that Fe3+ presents a higher affinity by the sorbent. Therefore, AAHSG was successfully employed as a sorbent in a simple flow system for the preconcentration of Fe3+ in natural water samples, such as, river water, lagoonwater, springwater, stream water, well water and two water reference materials (NIST-SRM 1640, NIST-SRM 1643d). The obtained preconcentration factor was 82.2, and the detection limit achieved was 5.9 ng ml(-1). The recovery of spiked water samples ranged from 95.0 - 103.1%.     

On the resilience of nitrogen assimilation by intact roots under starvation,as revealed by isotopic and metabolomic techniques

The response of root metabolism to variations in carbon source availability is critical for whole‐plant nitrogen (N) assimilation and growth. However, the effect of changes in the carbohydrate input to intact roots is currently not well understood and, for example, both smaller and larger values of root:shoot ratios or root N uptake have been observed so far under elevated CO₂. In addition, previous studies on sugar starvation mainly focused on senescent or excised organs while an increasing body of data suggests that intact roots may behave differently with, for example, little protein remobilization. Here, we investigated the carbon and nitrogen primary metabolism in intact roots of French bean (Phaseolus vulgaris L.) plants maintained under continuous darkness for 4 days. We combined natural isotopic ¹⁵N/¹⁴N measurements, metabolomic and ¹³C‐labeling data and show that intact roots continued nitrate assimilation to glutamate for at least 3 days while the respiration rate decreased. The activity of the tricarboxylic acid cycle diminished so that glutamate synthesis was sustained by the anaplerotic phosphoenolpyruvate carboxylase fixation. Presumably, the pentose phosphate pathway contributed to provide reducing power for nitrate reduction. All the biosynthetic metabolic fluxes were nevertheless down‐regulated and, consequently, the concentration of all amino acids decreased. This is the case of asparagine, strongly suggesting that, as opposed to excised root tips, protein remobilization in intact roots remained very low for 3 days in spite of the restriction of respiratory substrates. Copyright © 2009 John Wiley & Sons, Ltd.     

Photothermal deflection microscopy for imaging sub-micronic defects in optical materials

Photothermal deflection is widely used to study defects in optical coatings and role of these defects in laser damage. Because defects responsible for laser damage are assumed to be nanometer-sized and lowly absorbing, both high spatial resolution and high sensitivity are required to detect them. In this work we theoretically and experimentally explore the capability of collinear photothermal deflection to give micronic resolution by reduction of the pump beam diameter. Thanks to a model describing temperature distribution and photothermal deflection, we have studied the effects of pump beam focusing on photothermal deflection. Then, we have developed a high resolution, high sensitivity microscope based on the photothermal deflection of a transmitted probe beam. The setup is characterized and the theoretical predictions are checked. We present a test of lateral spatial resolution obtained on specially prepared absorbing resolution targets and show that a lateral spatial resolution of 1 μm is reached on non-isolated defects. In case of single defects, we expect that 10 nm sized defects could be detected.     

Design of the First‐in‐Class,Highly Potent Irreversible Inhibitor Targeting the Menin‐MLL Protein–Protein Interaction

The structure‐based design of M‐525 as the first‐in‐class, highly potent, irreversible small‐molecule inhibitor of the menin‐MLL interaction is presented. M‐525 targets cellular menin protein at sub‐nanomolar concentrations and achieves low nanomolar potencies in cell growth inhibition and in the suppression of MLL‐regulated gene expression in MLL leukemia cells. M‐525 demonstrates high cellular specificity over non‐MLL leukemia cells and is more than 30 times more potent than its corresponding reversible inhibitors. Mass spectrometric analysis and co‐crystal structure of M‐525 in complex with menin firmly establish its mode of action. A single administration of M‐525 effectively suppresses MLL‐regulated gene expression in tumor tissue. An efficient procedure was developed to synthesize M‐525. This study demonstrates that irreversible inhibition of menin may be a promising therapeutic strategy for MLL leukemia.     

Terminal Alkyne Coupling Reactions through a Ring: Mechanistic Insights and Regiochemical Switching

The mechanism and selectivity of terminal alkyne coupling reactions promoted by rhodium(I) complexes of NHC‐based CNC pincer ligands have been investigated. Synthetic and kinetic experiments support E‐ and gem‐enyne formation through a common reaction sequence involving hydrometallation and rate‐determining C?C bond reductive elimination. The latter is significantly affected by the ligand topology: Employment of a macrocyclic variant enforced exclusive head‐to‐head coupling, contrasting the high selectivity for head‐to‐tail coupling observed for the corresponding acyclic pincer ligand.     

Chemical analysis and antiviral activity evaluation of Baccharis anomala

The chemical composition and antiviral activity of aqueous extract from Baccharis anomala was studied by bioactivity-guided fractionation. Ethanol precipitation and fractionation by molecular permeation allowed the separation of the anti-herpes simplex virus 1 (HSV-1) active fraction from aqueous extract (Fraction B). Natural Product Reagent A, FeCl₃ and thin-layer chromatography indicated the presence of phenolic compounds in the aqueous extract. Fraction B showed pronounced antiviral activity when tested with HSV-1 strains VR733/ATCC and Acyclovir-resistant 29-R, displaying virucidal but not virustatic activity.     

Recent Updates on the Barrier Properties of Ethylene Vinyl Alcohol Copolymer (EVOH): A Review

The gas barrier properties of ethylene vinyl alcohol copolymer (EVOH) against oxygen, carbon dioxide and water vapor have been widely investigated in relation to different material characteristics, environmental conditions and new processing technologies. Recently, EVOH is gaining more attention as a barrier material against other gases and organic substances such as aromas, flavors, fuels, chemicals (e.g., BTEX), and as a functional barrier, e.g., to avoid mineral oil migration. This review contains an update on permeability data of EVOH emphasizing its potential as a barrier material for new and versatile applications in food and pharmaceutical packaging, agriculture, construction, automotive, etc.     

Active Esters as Pseudostoppers for Slippage Synthesis of [2]Pseudorotaxane Building Blocks: A Straightforward Route to Multi‐Interlocked Molecular Machines

The efficient synthesis and very easy isolation of dibenzo[24]crown‐8‐based [2]pseudorotaxane building blocks that contain an active ester motif at the extremity of the encircled molecular axle and an ammonium moiety as a template for the dibenzo[24]crown‐8 is reported. The active ester acts both as a semistopper for the [2]pseudorotaxane species and as an extensible extremity. Among the various investigated active ester moieties, those that allow for the slippage process are given particular focus because this strategy produces fewer side products. Extension of the selected N‐hydroxysuccinimide ester based pseudorotaxane building block by using either a mono‐ or a diamino compound, both containing a triazolium moiety, is also described. These provide a pH‐dependent two‐station [2]rotaxane molecular machine and a palindromic [3]rotaxane molecular machine, respectively. Molecular machinery on both interlocked compounds through variation of pH was studied and characterized by means of NMR spectroscopy.     

A TPA-caged precursor of (imino)coumarin for “turn-on” fluorogenic detection of Cu

We strategize to utilize the precursors of (imino)coumarin fluorophores to deliver novel reactive Cu⁺ probes, where tris[(2-pyridyl)-methyl] amine (TPA) works as a reactive receptor towards Cu⁺. To verify this strategy, CP1, a representative probe and relevant sensing behaviors towards Cu⁺ are presented here. CP1 features good solubility and fast response for monitoring labile copper in aqueous solution and live cells. The sensing mechanism of CP1 is determined by HPLC titration and mass spectrometric analysis. The probe CP1 exhibits a 60-fold fluorescence enhancement and a detection limitation of 10.8 nM upon the detection of Cu⁺. CP1 is further applied for imaging labile copper in live cells. This work provides a starting point for future development of Cu⁺ probes, based on in situ formation of (imino)coumarin scaffolds, as well as their further investigations of copper signaling and biological events.