Photonic Patterns Printed in Chiral Nematic Mesoporous Resins

Chiral nematic mesoporous phenol‐formaldehyde resins, which were prepared using cellulose nanocrystals as a template, can be used as a substrate to produce latent photonic images. These resins undergo swelling, which changes their reflected color. By writing on the films with chemical inks, the density of methylol groups in the resin changes, subsequently affecting their degree of swelling and, consequently, their color. Writing on the films gives latent images that are revealed only upon swelling of the films. Using inkjet printing, it is possible to make higher resolution photonic patterns both as text and images that can be visualized by swelling and erased by drying. This novel approach to printing photonic patterns in resin films may be applied to anti‐counterfeit tags, signage, and decorative applications.     

Instabilités de l'écoulement produisant le bruit de fenteFlow instabilities producing the slot-tone

The nature of the instability governing the self-sustained tones produced by a low Mach number plane jet impinging on a slotted plate, known as slot-tone, is identified experimentally. For a given Reynolds number, the natural shear-layer and the jet column mode frequencies of the free jet delimit the values of the measured slot-tone operating frequencies. The oscillations at lower frequencies are the result of the amplification of the jet column mode, and those at higher frequencies correspond to the shear layer instabilities. To cite this article: A. Billon et al., C. R. Mecanique 332 (2004).     

Tandem mass spectrometric analysis of novel diquaternary ammonium gemini surfactants and their bromide adducts in electrospray-positive ion mode ionization

Gemini surfactants are cationic lipids which are utilized for both in vitro and in vivo gene delivery. Structurally, they are comprised of two hydrophobic tail regions with polar head termini that are attached to one another through a spacer region. Structural elucidation and characterization of 29 novel diquaternary ammonium gemini surfactant molecules were achieved using a quadrupole time-of-flight mass spectrometer (QqToF-MS) and a quadrupole-hexapole-quadrupole mass spectrometer (QhQ-MS). The tested compounds were categorized into four distinct structural families based upon the composition of the spacer region. Single stage (MS), tandem stage (MS/MS) and quasimulti-stage (quasi MS(3)) mass spectrometric analysis allowed for confirmation of each gemini surfactant's molecular composition and structure through the identification of common and unique product ions. Identification of similarities in the gemini surfactants' fragmentation behaviour resulted in the production of a universal fragmentation pathway that can assist in the future MS/MS analysis of novel quaternary ammonium gemini surfactants, with unique product ions being indicative of specific structural elements. Furthermore, evidence for the association of agemini surfactant with bromine counter ion was confirmed during MS analysis of tested gemini surfactants regardless of their chemical composition; previously, evidence for bromine and gemini surfactant association was only observed with compounds bearing short alkyl spacer regions. MS/MS analysis of the bromine adducts was also confirmatory to the molecular structure.Understanding the ionization and fragmentation behaviour of gemini surfactants, including bromine adducts, will allow for future qualitative and quantitative identification of these novel drug delivery agents within biological samples.     

Quantum nature of the sign preference in ion-induced nucleation

Observed first in Wilson's pioneering experiments in the cloud chamber, the sign preference has remained a mystery for more than a century. We investigate the sign preference using a quantum approach and show that this puzzling phenomenon is essentially quantum in nature. It is shown that the effect of the chemical identity of the core ion is controlled by the electronic structure of the core ion through the influence on the intermolecular bonding energies during the initial steps of cluster formation. Our results demonstrate the superiority of the quantum approach and indicate fundamental problems of conventional ion-induced nucleation theories, in which the electronic structure of the core ion is either ignored or not treated rigorously.     

Mass Spectrometry,Review of the Basics: Electrospray,MALDI, and Commonly Used Mass Analyzers

Abstract

Mass spectrometry (MS) has progressed to become a powerful analytical tool for both quantitative and qualitative applications. The first mass spectrometer was constructed in 1912 and since then it has developed from only analyzing small inorganic molecules to biological macromolecules, practically with no mass limitations. Proteomics research, in particular, increasingly depends on MS technologies. The ability of mass spectrometry analyzing proteins and other biological extracts is due to the advances gained through the development of soft ionization techniques such as electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI) that can transform biomolecules into ions. ESI can efficiently be interfaced with separation techniques enhancing its role in the life and health sciences. MALDI, however, has the advantage of producing singly charges ions of peptides and proteins, minimizing spectral complexity. Regardless of the ionization source, the sensitivity of a mass spectrometer is related to the mass analyzer where ion separation occurs. Both quadrupole and time of flight (ToF) mass analyzers are commonly used and they can be configured together as QToF tandem mass spectrometric instruments. Tandem mass spectrometry (MS/MS), as the name indicates, is the result of performing two or more sequential separations of ions usually coupling two or more mass analyzers. Coupling a quadrupole and time of flight resulted in the production of high-resolution mass spectrometers (i.e., Q-ToF). This article will historically introduce mass spectrometry and summarizes the advantages and disadvantages of ESI and MALDI along with quadrupole and ToF mass analyzers, including the technical marriage between the two analyzers. This article is educational in nature and intended for graduate students and senior biochemistry students as well as chemists and biochemists who are not familiar with mass spectrometry and would like to learn the basics; it is not intended for mass spectrometry experts.     

Rotating polarizer,compensator, and analyzer ellipsometry

In this paper we propose theoretically a set of ellipsometric configurations using a rotating polarizer, compensator, and analyzer at a speed ratio of N1ω：N2ω：N3ω. Different ellipsometric configurations can be obtained by giving different integral values to N1, N2, and N3. All configurations are applied to bulk c-Si and GaAs to calculate the real and imaginary parts of the refractive index of the samples. The accuracies of all ellipsometric configurations are investigated in the presence of a hypothetical noise and with small misalignments of the optical elements. Moreover, the uncertainties in the ellipsometric parameters as functions of the uncertainties of the Fourier coefficients are studied. The comparison among different configurations reveals that the rotating compensator–analyzer configuration corresponds to the minimum error in the calculated optical parameters.     

Modeling the sound transmission between rooms coupled through partition walls by using a diffusion model

In this paper, a modification of the diffusion model for room acoustics is proposed to account for sound transmission between two rooms, a source room and an adjacent room, which are coupled through a partition wall. A system of two diffusion equations, one for each room, together with a set of two boundary conditions, one for the partition wall and one for the other walls of a room, is obtained and numerically solved. The modified diffusion model is validated by numerical comparisons with the statistical theory for several coupled-room configurations by varying the coupling area surface, the absorption coefficient of each room, and the volume of the adjacent room. An experimental comparison is also carried out for two coupled classrooms. The modified diffusion model results agree very well with both the statistical theory and the experimental data. The diffusion model can then be used as an alternative to the statistical theory, especially when the statistical theory is not applicable, that is, when the reverberant sound field is not diffuse. Moreover, the diffusion model allows the prediction of the spatial distribution of sound energy within each coupled room, while the statistical theory gives only one sound level for each room.     

Photosensitized breakage and damage of DNA by CdSe-ZnS quantum dots

Strand breakages and nucleobase damages in plasmid DNA (pDNA) by CdSe-ZnS quantum dots (QDs) are investigated under different conditions of photoactivation. Here, streptavidin functionalized CdSe-ZnS QDs are conjugated to biotinylated pDNA, and photosensitized strand breakages and nucleobase damages in the conjugates are investigated using atomic force microscopy (AFM) imaging, gel electrophoreses analyses, and assay of reactive oxygen intermediates (ROI). Also, reactions of photoactivated pDNA-QD conjugates with base excision repair enzymes such as formamidopyrimidine glycosylase (Fpg) and endonuclease III (Endo III) show damages of purine and pyrimidine bases. The base excision repair enzymes recognize and remove the damaged bases. The base excision reactions of photoactivated pDNA-QD conjugates resulted in pDNA strand breakages, which appeared as sheared bands in agarose gel images. On the basis of AFM imaging, reactions of Fpg and Endo III with damaged pDNA, ROI assay, and literature reports, we attribute the breakage and damage of pDNA to its reactions with ROI. The production of ROI by photoactivated QDs is confirmed by nitroblue tetrazolium (NBT) assay. The current work shows that photoactivation of QD-conjugated nucleic acids for an extended period of time is not favorable for their stability. On the other hand, photoinduced production of ROI by QDs is an emerging research area with potential applications in the photodynamic therapy of cancer. In this regard, photosensitized damage of pDNA observed in the current work shows possibilities of QDs in nucleus-targeted photodynamic therapy.     

Cover Picture: Nanomaterials for Fluorescence and Multimodal Bioimaging (Chem. Rec. 3/2023)

Bioconjugated nanomaterials replace molecular probes in bioanalysis and bioimaging in vitro and in vivo. Nanoparticles of silica, metals, semiconductors, polymers, and supramolecular systems, conjugated with contrast agents and drugs for image-guided (MRI, fluorescence, PET, Raman, SPECT, photodynamic, photothermal, and photoacoustic) therapy infiltrate into preclinical and clinical settings. Small bioactive molecules like peptides, proteins, or DNA conjugated to the surfaces of drugs or probes help us to interface them with cells and tissues. Nevertheless, the toxicity and pharmacokinetics of nanodrugs, nanoprobes, and their components become the clinical barriers, underscoring the significance of developing biocompatible next-generation drugs and contrast agents. This account provides state-of-the-art advancements in the preparation and biological applications of bioconjugated nanomaterials and their molecular, cell, and in vivo applications. It focuses on the preparation, bioimaging, and bioanalytical applications of monomodal and multimodal nanoprobes composed of quantum dots, quantum clusters, iron oxide nanoparticles, and a few rare earth metal ion complexes.     

Iodine assisted palladium catalyzed ring opening of bicyclic hydrazines with organoboronic acids: stereoselective synthesis of functionalized cyclopentenes and alkylidene cyclopentenes

A novel reactivity of organoboronic acids with bicyclic hydrazines leading to the stereoselective formation of trans-vicinal disubstituted cyclopentenes in good to excellent yield is discussed. The reaction of cyclopentadiene and fulvene derived azabicyclic alkenes with organoboronic acids afforded the trans-3,4-disubstituted cyclopentenes and alkylidene cyclopentenes in good to excellent yields. The products, having a broad range of substituents, are important intermediates in the synthesis of a number of pharmaceutically important molecules.