Terahertz probe of individual subwavelength objects in a water environment

Terahertz (THz) spectroscopy and imaging have been heralded for some time as potentially revolutionary techniques for biomedical applications. Label‐free detection of molecules and recognition of molecular events are often mentioned as the most exciting possibilities. A crucial practical goal, however, is the ability to perform such measurements on tiny amounts of biological fluids or even on individual organic structures. Living cells, for instance, have diameters at most of some tens of micrometers, i.e. at least λ/10 even for few‐THz radiation. Furthermore, all analyses relevant for a biological perspective must be performed in a water environment, which presents a strong absorption across the whole THz spectral range, severely limiting the penetration of the electromagnetic field. Here, it is shown how both issues can be overcome with a lab‐on‐a‐chip approach based on a microfluidic platform coupled to a plasmonic antenna. Using a quantum cascade laser as THz illumination source, liquid volumes down to the picoliter range are probed, and direct operation on individual 10‐µm diameter microparticles flowing in water is shown. The present demonstration opens the way to the development of THz biosensing of individual living cells and small probe volumes.     

Different methods for β-cyclodextrin/triclosan complexation as antibacterial treatment of cellulose substrates

Two different production ways of antibacterial cotton fabrics by means of triclosan inclusion into a β-cyclodextrin cavity have been compared. On the one hand, triclosan has been dissolved into an aqueous solution of a β-cyclodextrin derivative with the aim of including the antibacterial agent into the cavity before grafting the β-cyclodextrin on a cotton fabric. On the other hand, the same β-cyclodextrin derivative has been grafted onto cotton and, subsequently, the fabric has been immersed into a triclosan water–ethanol solution to allow the inclusion complex formation. The antibacterial properties have been evaluated according to AATCC Test Method 100–1993 before and after two washing cycles at 60 °C. It has been shown that the durability of the antibacterial finishing depends on the production method, obtaining a more durable antibacterial action in case of prior triclosan inclusion followed by grafting. This suggests that the immobilization onto the fiber has affected the cyclodextrin cavity accessibility.     

Synthesis of 1,2-dihydroxyindolizidines from 1-(2-pyridyl)-2-propen-1-ol

1-(2-Pyridyl)-2-propen-1-ol, obtained by vinylation of commercially available picolinaldehyde, resulted a good starting material for the synthesis of the indolizidine skeleton. In particular, a simple process involving bromination, reduction, and nucleophilic substitution (via elimination and addition) allowed an easy conversion of the starting material into (±)-lentiginosine in ~27% overall yield.     

Photodegradation of Brilliant Green Dye by a Zinc bioMOF and Crystallographic Visualization of Resulting CO2

We present a novel bio-friendly water-stable Zn-based MOF (1), derived from the natural amino acid L-serine, which was able to efficiently photodegrade water solutions of brilliant green dye in only 120 min. The total degradation was followed by UV-Vis spectroscopy and further confirmed by single-crystal X-ray crystallography, revealing the presence of CO₂ within its channels. Reusability studies further demonstrate the structural and performance robustness of 1.     

Semiclassical localization and uncertainty principle

Semiclassical localizability problems in phase space constitute a manifestation of the uncertainty principle, one of the cornerstones of our present understanding of Nature. We revisit the subject here within the framework of the celebrated semiclassical Husimi distributions and their associated Wehrl entropy. By recourse to the concept of escort distributions, a well-established statistical concept, we show that it is possible to significantly improve on the current phase-space classical-localization power, thus approaching more closely than before the bounds imposed by Husimi's thermal uncertainty relation.     

The Shapes of Sulfonamides: A Rotational Spectroscopy Study

Benzenesulfonamides are a class of molecules of extreme interest in the biochemical field because many of them are active against a variety of diseases. In this work, the pharmacophoric group benzensulfonamide, its derivatives para-toluensulfonamide and ortho-toluensulfonamide, and the bioactive molecule sulfanilamide, were investigated using rotational spectroscopy to determine their conformations and the influence of different substituents on their structures. For all species, the hyperfine structure due to the ¹⁴N atom was analyzed, and this provided crucial information for the unambiguous identification of the observed conformation of all molecules. In addition, for ortho-toluensulfonamide, the vibration–rotation hyperfine structure related to the methyl torsion was analyzed, and the methyl group rotation barrier was determined. For benzensulfonamide, partial r_S and r₀ structures were established from the experimental rotational constants of the parent and two deuterated isotopic species. In all compounds except ortho-toluensulfonamide, the amino group of the sulfonamide group lies perpendicular to the benzene plane with the aminic hydrogens eclipsing the oxygen atoms. In ortho-toluensulfonamide, where weak attractive interactions occur between the nitrogen lone pair and the methyl hydrogen atoms, the amino group lies in a gauche orientation, retaining the eclipsed configuration with respect to the SO₂ frame. A comparison of the geometrical arrangements found in the PDB database allowed us to understand that the bioactive conformations are different from those found in isolated conditions. The conformations within the receptor are reached with an energy cost, which is balanced by the interactions established in the receptor.     

Effects of Environmental and Electric Perturbations on the pKa of Thioredoxin Cysteine 35: A Computational Study

Here we present a theoretical-computational study dealing with the evaluation of the pKa of the Cysteine residues in Thioredoxin (TRX) and in its complex with the Thioredoxin-interacting protein (TXNIP). The free energy differences between the anionic and neutral form of the Cysteine 32 and 35 have been evaluated by means of the Perturbed Matrix Method with classical perturbations due to both the environment and an exogenous electric field as provided by Molecular Dynamics (MD) simulations. The evaluation of the free energies allowed us to show that the effect of the perturbing terms is to lower the pKa of Cysteine 32 and Cysteine 35 with respect to the free amino-acid. On the other hand, in the complex TRX-TXNIP, our data show an enhanced stabilization of the neutral reduced form of Cys 35. These results suggest that external electric stimuli higher than 0.02 V/nm can modulate the Cysteine pKa, which can be connected to the tight regulation of the TRX acting as an antioxidant agent.