Red-emitting dyes with photophysical and photochemical properties controlled by pH

New unsymmetrical zinc azaphthalocyanines, bearing one substituted aniline as a peripheral substituent, were prepared by using a statistical condensation approach. Both fluorescence and singlet oxygen quantum yields were extremely low in DMF (Φ(F)<0.01, Φ(Δ)<0.02, respectively), but increased after the addition of sulfuric acid, reaching values comparable to controls without aniline substituents (Φ(F)=0.22-0.29, Φ(Δ)=0.40-0.59, respectively). This behavior was attributed to the deactivation of excited states by intramolecular charge transfer from a donor site (aniline), which was blocked after protonation in acidic media. In the protonated form, all of the compounds efficiently emitted light with λ(em) in the region of 662-675 nm. The investigated compounds were anchored to dioleoylphosphatidylcholine (DOPC) unilamellar vesicles and showed response to buffer pH. They were highly fluorescent at low pH values and almost nonfluorescent in neutral solutions. The pK(a) values were determined in DOPC vesicles and ranged between 2.2 and 4.2.     

Optical Code Generating Device Using 1×N Asymmetric Hollow Waveguide Couplers

An optical code generating device for security access system application is presented. The code generating device constructed using asymmetric hollow optical waveguide coupler design provides a unique series of output light intensities which are successively used as an optical code. The design of the waveguide is made using two major components which are asymmetric Yjunction splitter and a linear taper. Waveguiding is done using a hollow waveguide structure. Construction of higher level 1×N hollow waveguide coupler is done utilizing a basic 1×2 asymmetric waveguide coupler design together with a cascaded design scheme. Nonsequential ray tracing of the asymmetric hollow optical waveguide couplers is performed to predict the optical transmission properties of the waveguide. A representation of the code combination that can be generated from the device is obtained using combinatory number theory.     

Cell surface photoengineering enables modeling of glycocalyx shedding dynamics

The cellular glycocalyx, composed of membrane associated glycoproteins and glycolipids, is a complex and dynamic interface that facilitates interactions between cells and their environment. The glycocalyx composition is continuously changing through biosynthesis of new glycoconjugates and membrane turnover. Various glycocalyx components, such as mucins, can also be rapidly shed from the cell surface in response to acute events, such as pathogenic threat. Mucins, which are large extended glycoproteins, deliver important protective functions against infection by creating a physical barrier at the cell surface and by capturing and clearing pathogens through shedding. Evaluating these mucin functions may provide better understanding of early stages of pathogenesis; however, tools to tailor the composition and dynamics of the glycocalyx with precision are still limited. Here, we report a chemical cell surface engineering strategy to model the shedding behavior of mucins with spatial and temporal control. We generated synthetic mucin mimetic glycopolymers terminated with a photolabile membrane anchor, which could be introduced into the membranes of living cells and, subsequently, released upon exposure to UV light. By tuning the molecular density of the artificial glycocalyx we evaluated lectin crosslinking and its effect on shedding, showing that lectins can stabilize the glycocalyx and limit release of the mucin mimetics from the cell surface. Our findings indicate that endogenous and pathogen-associated lectins, which are known to interact with the host-cell glycocalyx, may alter mucin shedding dynamics and influence the protective properties of the mucosal barrier. More broadly, we present a method which enables photoengineering of the glycocalyx and can be used to facilitate the study of glycocalyx dynamics in other biological contexts.

Engineering cell surfaces with light-responsive mucin mimetic glycopolymers enables modeling of mucosal glycocalyx shedding and its possible roles in mucosal epithelium protection.     

The Development of New Methodology for Determination of Vincristine (VCR) in Human Serum Using LC-MS/MS-Based Method for Medical Diagnostics

In this article, we have presented the development and validation of a rapid and sensitive reversed-phase liquid chromatography with tandem mass spectrometry (LC-MS/MS) method for the determination of vincristine (VCR) in patient serum samples. Chromatographic separation was achieved on a Kinetex^® (Singapore) column using a mobile phase consisting of 25 mM acetic acid and 0.3% formic acid (A) and methanol (B) in a gradient elution mode at a flow rate of 0.3 mL/min. The VCR and internal standard (vinblastine) were monitored using the multiple reaction monitoring mode under positive electrospray ionization. The lower limit of quantification (LLOQ) was 0.67 ng/mL, and the upper limit of quantification (ULOQ) was 250 ng/mL for VCR. The calculated values of LOD and LOQ for VCR were 0.075 and 0.228 ng/mL, respectively. The calibration curve was linear over the VCR concentration range of 1.0–250 ng/mL in serum. The intra- and inter-day precision and precision were within the generally accepted criteria for the bioanalytical method (<15%). The method was successfully applied to the analysis of serum samples in clinical practice.     

Physicochemical Properties and Surface Characteristics of Ground Human Teeth

Enamel, dentin and cementum apatite has a complex composition. The lack of complete reports on the chemical composition of all tooth tissues together and the need to create a modern biomaterial that reproduces the correct ratio of individual tooth mineral components prompted the authors to undertake the research. A detailed evaluation of the micro- and macro-elements of tooth powder, using various methods of chemical analysis was conducted. All four groups of human sound teeth were crushed using the grinder. A fine powder was implemented for the FTIR (Fourier Transform Infrared Spectroscopy), ICP (Inductively Coupled Plasma Optical Emission Spectometry) and for the potentiometric titration, SEM and mercury porosimetry analyses. The obtained studies indicate that there is no significant correlation in chemical composition between the different teeth types. This proves that every removed, crushed tooth free of microorganisms can be a suitable material for alveolar augmentation. It is essential to know the chemical profiles of different elements in teeth to develop a new class of biomaterials for clinical applications.     

Investigations on the Synthesis of Zeolite ZSM-5 (III)

The effect of the chemical composition of the reacting mixture (RM) on the amount of zeolite ZSM-5 and other crystalline phases and the amorphous phase as well in the obtained preparations was investigated. Ethylenediamine (ED) served as a templating agent. The quantitative estimation of the phase composition was made on the ground of X-ray diffraction measurements. Zeolite ZSM-5 of maximum phase purity of 96%, contaminated mainly with quartz and mordenite, was obtained.     

Front Cover: A Highly Sterically Congested Bis-Zinc-Porphyrin Containing a Single Buta-1,3-diyne Linkage: From a Serendipitous Finding to Supramolecular Encapsulation (Eur. J. Org. Chem. 35/2023)

A unique example of a bis-zinc-porphyrin chemical system in which both macrocycles are covalently connected with a single, short buta-1,3-diyne linkage placed at the ortho sites of the meso phenyl rings is presented. This dimeric compound resulted from an homo-coupling side-reaction taking place during a copper-catalyzed click reaction between an alkyne porphyrin and 2-azidopyridine derivatives. Its unexpected formation was rationalized by control experiments and an improved synthesis was achieved under copper-catalyzed Glaser-Hay coupling reaction conditions. This highly sterically congested bis-zinc-porphyrin derivative behaved as a supramolecular host for encapsulating ditopic molecular guests such as 1,4-diazabicyclo[2.2.2]octane (DABCO) with association constant K_1.1 in the order of 10⁶ M⁻¹. This value is comparable to current systems that typically feature several connecting linkages between the two zinc-porphyrin sites resulting in (supra)molecular cages ensuring a high pre-organization. As such, the requirements to take benefit from supramolecular encapsulation can be reduced to a highly rigid, minimal covalent linkage of four atoms between zinc-porphyrins as herein described.     

Synthesis of [60]Fullerene Hybrids Endowed with Steroids and Monosaccharides: Theoretical Underpinning as Promising anti-SARS-CoV-2 Agents

Cyclopropanation reactions between C₆₀ and different malonates decorated with monosaccharides and steroids using the Bingel-Hirsch methodology have allowed the obtention of a new family of hybrid compounds in good yields. A complete set of instrumental techniques has allowed us to fully characterize the hybrid derivatives and to determine the chemical structure of monocycloadducts. Besides, the proposed structures were investigated by cyclic voltammetry, which evidenced the exclusive reductive pattern of fullerene Bingel-type monoadducts. Theoretical calculations at the DFT-D3(BJ)/PBE 6-311G(d,p) level of the synthesized conjugates predict the most stable conformation and determine the factors that control the hybrid molecules′ geometry. Some parameters such as polarity, lipophilicity, polar surface area, hydrophilicity index, and solvent-accessible surface area were also estimated, predicting its potential permeability and capability as cell membrane penetrators. Additionally, a molecular docking simulation has been carried out using the main protease of SARS-CoV-2 (Mpro) as the receptor, thus paving the way to study the potential application of these hybrids in biomedicine.