Complex Formation Research Articles

Unveiling Fluorescence Spectroscopy, Molecular Docking and Dynamic Simulations: Interactions Between Protein and 2, 4-Dinitrophenylhydrazine Schiff Base.

In this study, we aimed to explore the interaction mechanism between bovine serum albumin (BSA) and a Schiff base compound derived from 2,4-dinotrophenyl hydrazine (L) using various spectroscopic techniques. The interaction between BSA and synthesizing molecule can provide insights into binding affinity, conformational changes and potential applications in drug delivery or biochemistry. The interaction between BSA and L was studied by using UV-Vis and fluorescence titration analysis. The fluorescence quenching emission was observed at 343nm, upon addition of L to the buffer solution of BSA. The binding between BSA and ligand is static in nature using fluorescence quenching emission. The thermodynamic parameters were calculated from the temperature-dependent binding constants (i.e., ∆H = -0.318kcal/mol, ∆G = -7.857kcal/mol and ∆S = 0.023kcal/mol), which indicated that the protein-ligand complex formation between L and BSA is mainly due to the electrostatic interactions. The experimental and theoretical results showed excellent agreement with respect to the mechanism of binding and binding constants. The molecular docking and molecular dynamic analysis experiments were performed to establish the interaction between protein and ligand.

Novel, soluble 3-heteroaryl-substituted tanshinone mimics attenuate the inflammatory response in murine macrophages

The RNA binding protein Human Antigen R (HuR) has been identified as a main regulator of the innate immune response and its inhibition can lead to beneficial anti-inflammatory effects. To this aim, we previously synthesized a novel class of small molecules named Tanshinone Mimics (TMs) able to interfere with HuR-RNA binding, and that dampen the LPS-induced immune response. Herein, we present a novel series of TMs, encompassing thiophene 3/TM9 and 4/TM10, furan 5/TM11 and 6/TM12, pyrrole 7b/TM13, and pyrazole 8. The furan-containing 5(TM11) showed the greatest inhibitory effect of the series on HuR-RNA complex formation, as suggested by RNA Electromobility Shift Assay and Time-Resolved FRET. Molecular Dynamics Calculation of HuR − 5/TM11 interaction, quantum mechanics approaches and Surface Plasmon Resonance data, all indicates that, within the novel heteroaryl substituents, the furan ring better recapitulates the chemical features of the RNA bound to HuR. Compound 5/TM11 also showed improved aqueous solubility compared to previously reported TMs. Real-time monitoring of cell growth and flow cytometry analyses showed that 5/TM11 preferentially reduced cell proliferation rather than apoptosis in murine macrophages at immunomodulatory doses. We observed its effects on the innate immune response triggered by lipopolysaccharide (LPS) in macrophages, showing that 5/TM11 significantly reduced the expression of proinflammatory cytokines as Cxcl10 and Il1b.

Rapid method for screening of both calcium and magnesium chelation with comparison of 21 known metal chelators.

Chelation is the rational treatment modality in metal overload conditions, but chelators are often non-selective and can, hence, cause an imbalance in the homeostasis of physiological metals including calcium and magnesium. The aim of this study was to develop an affordable, rapid but sensitive and precise method for determining the degree of chelation of calcium and magnesium ions and to employ this method for comparison on a panel of known metal chelators. Spectrophotometric method using o-cresolphthalein complexone (o-CC) was developed and its biological relevance was confirmed in human platelets by impedance aggregometry. The lowest detectable concentration of calcium and magnesium ions by o-CC was 2.5μM and 2μM, respectively. The indicator was stable for at least 110days. Four and seven out of twenty-one chelators strongly chelated calcium and magnesium ions, respectively. Importantly, the chelation effect of clinically used chelators was not negligible. Structure-activity relationships for eight quinolin-8-ols showed improvements in chelation particularly in the cases of dihalogen substitution, and a negative linear relationship between pKa and magnesium chelation was observed. Calcium chelation led to inhibition of platelet aggregation in concentrations corresponding to the complex formation. A novel method for screening of efficacy and safety of calcium and magnesium ion chelation was developed and validated.

Visible-Light Driven Synthesis of Vinyl Amines without Photocatalyst.

We developed a visible-light-induced vinyl amination of activated alkenes using TMSN3 and CsF through EDA complex formation under an oxygen atmosphere. Without light, the EDA complex forms between activated alkene, CsF, and oxygen. Upon exposure to light, oxygen in the complex gets excited, initiating the HAT process. This method efficiently synthesizes vinyl-amine derivatives via a radical pathway, demonstrating good functional group tolerance and high yields in a short time. Further, the late-stage functionalization enables the synthesis of biologically active heterocycles.

Numerical Simulation of Shock Wave in Gas–Water Interaction Based on Nonlinear Shock Wave Velocity Curve

In a gas–water interaction problem, the nonlinear relationship between shock wave velocity is introduced into a Hugoniot curve, and a Mie–Grüneisen Equation of state (EOS) is established by setting the Hugoiot curve as the reference state. Unlike other simple EOS based on the thermodynamics laws of gas (such as the Tait EOS), the Mie–Grüneisen EOS uses reference states to cover an adiabatic impact relationship and considers the thermodynamics law separately. However, the expression of the EOS becomes complex, and it is not adaptive to many methods. A multicomponent Mie–Grüneisen mixture model is employed in this study to conquer the difficulty of the complex form of an EOS. In this model, some coefficients in the Mie–Grüneisen EOS are regarded as variables and solved using newly constructed equations. The performance of the Mie–Grüneisen mixture model in the gas–water problem is tested by low-compression cases and high-compression cases. According to these two tests, it is found that the numerical solutions of the shock wave under the Mie–Grüneisen EOS agrees with empirical data. When compared to other simple-form EOSs, it is seen that the Mie–Grüneisen EOS has slight advantages in the low-compression case, but it plays an important role in the high-compression case. The comparison results show that the solution of the simple-form EOS clearly disagrees with the empirical data. A further study shows that the gap between the Mie–Grüneisen EOS and other simple-form EOSs becomes larger as the initial pressure and particle velocity increase. The impact effects on the pressure, density and particle velocity are studied. Moreover, the gas–water interaction in a spherical coordinate plane and a two-dimensional coordinate is a significant part of our work.

Role of Organic Fertilizer in the Transfer of Lead to Vegetables Produced in Tropical Mountain Agroecosystems.

Understanding the relationship between the aerobic transformation of organic matter (OM) and the bioavailability of lead to plants may allow the safe application of organic fertilizers (OF) in agriculture. The present study aimed to elucidate the relationship of different OM structures with Pb, revealing the action of OF (poultry litter) on Pb dynamics, presenting the effects of OM transformations on bioavailability and transfer to vegetables produced in tropical mountain agroecosystems (TMA). The association of Pb with hydrophilic structures (CAlk-O and CAlk-di-O) during the aerobic transformation of poultry litter (PL) contributes to the increase in the water-soluble form of this metal (3.17-15.30%). The structural changes promoted by the transformation of OM, in addition to reducing the adsorption capacity of Pb in PL (Kd reduction from 1135.50 to 87.49), favor the formation of outer-sphere complexes. PL that have a more labile structure, i.e., those that are less humified, have greater affinity for Pb. The greater affinity of Pb for labile structures that are preserved in PL during OM transformations contributed to its increase and transport to edible plant parts. Considering the edible parts of vegetables grown in TMA and fertilized with fresh PL, 100% of broccoli, 91.78% of cabbage, 80.00% of tomato, 65.96% of parsley, 49.19% of lettuce, and 32.88% of cauliflower showed Pb contamination that exceeded the permitted level. Therefore, OF contributes to lead contamination of food produced in TMA, representing a risk to human health. Studies are needed to propose additional treatments for this residue before its use.

Synthesis, characterization, and in vitro-in ovo toxicological screening of silibinin fatty acids conjugates as prodrugs with potential biomedical applications.

Silibinin (SIL), the most active phytocompound from Silybum marianum (L.), exerts many biological effects but has low stability and bioavailability. To overcome these drawbacks, the current research proposed the synthesis of silibilin oleate (SIL-O) and silibilin linoleate (SIL-L) derivatives as prodrugs with potentially optimized properties for biomedical applications, and the establishment of their in vitro-in ovo safety profiles. The physicochemical characterization of the obtained compounds using density functional theory (DFT) calculations, and Raman and 1H liquid-state nuclear magnetic resonance (NMR) spectroscopy confirmed the formation of SIL-O and SIL-L complexes. Computational predictions revealed that these lipophilic derivatives present a lower drug-likeness score (-29.96 for SIL-O and -23.55 for SIL-L) compared to SIL, but an overall positive drug score (0.07) and no risk for severe adverse effects. SIL-O and SIL-L showed no cytotoxicity or impairment in cell migration at low concentrations, but at the highest concentration (100 μM), they displayed distinct toxicological profiles. SIL-L was more cytotoxic (on cardiomyoblasts - H9c2(2-1), hepatocytes - HepaRG, and keratinocytes - HaCaT) than SIL-O or SIL, significantly inhibiting cell viability (<60%), altering cellular morphology, reducing cell confluence (<70%), and inducing prominent apoptotic-like nuclear features. At the concentration of 100 μM, SIL-O presented an irritation score (IS) of 0.61, indicating a lack of irritant effect on the chorioallantoic membrane (CAM), while SIL-L was classified as a slight irritant with an IS of 1.99. These findings outline a more favorable in vitro and in ovo biocompatibility for SIL-O compared to SIL L, whose applications are dosage limited due to potential toxicity.

Resistance to linezolid in Staphylococcus aureus by mutation, modification, and acquisition of genes.

Linezolid binds to the 50S subunit of the bacterial ribosome, inhibiting bacterial protein synthesis by preventing the formation of the initiation complex. Oxazolidinone antimicrobial drugs represent the last line of defense in treating Staphylococcus aureus infections; thus, resistance to linezolid in S. aureus warrants high priority. This article examines the major mechanisms of resistance to linezolid in S. aureus, which include: mutations in the domain V of 23S rRNA (primarily G2576); chromosomal mutations in the rplC, rplD, and rplV genes (encoding the ribosomal uL3, uL4, and uL22 proteins, respectively); the exogenous acquisition of the methylase encoded by the chloramphenicol-florfenicol resistance (cfr) gene; the endogenous methylation or demethylation of 23S rRNA; the acquisition of optrA and poxtA resistance genes; and the existence of the LmrS multidrug efflux pump. In conclusion, these mechanisms mediate resistance through mutations or modifications to the bacterial target, thereby reducing the affinity of linezolid for the peptidyl transferase center (PTC) binding site or by preventing the binding of linezolid to the PTC through a ribosomal protective effect. The existence of additional, unexplained resistance mechanisms requires further investigation and verification.

Microglia morphological response to mesenchymal stromal cell extracellular vesicles demonstrates EV therapeutic potential for modulating neuroinflammation

BackgroundMesenchymal stromal cell derived extracellular vesicles (MSC-EVs) are a promising therapeutic for neuroinflammation. MSC-EVs can interact with microglia, the resident immune cells of the brain, to exert their immunomodulatory effects. In response to inflammatory cues, such as cytokines, microglia undergo phenotypic changes indicative of their function e.g. morphology and secretion. However, these changes in response to MSC-EVs are not well understood. Additionally, no disease-relevant screening tools to assess MSC-EV bioactivity exist, which has further impeded clinical translation. Here, we developed a quantitative, high throughput morphological profiling approach to assess the response of microglia to neuroinflammation- relevant signals and whether this morphological response can be used to indicate the bioactivity of MSC-EVs.ResultsUsing an immortalized human microglia cell-line, we observed increased size (perimeter, major axis length) and complexity (form factor) upon stimulation with interferon-gamma (IFN-γ) and tumor necrosis factor-alpha (TNF-α). Upon treatment with MSC-EVs, the overall morphological score (determined using principal component analysis) shifted towards the unstimulated morphology, indicating that MSC-EVs are bioactive and modulate microglia. The morphological effects of MSC-EVs in TNF-α /IFN-γ stimulated cells were concomitant with reduced secretion of 14 chemokines/cytokines (e.g. CXCL6, CXCL9) and increased secretion of 12 chemokines/cytokines (e.g. CXCL8, CXCL10). Proteomic analysis of cell lysates revealed significant increases in 192 proteins (e.g. HIBADH, MEAK7, LAMC1) and decreases in 257 proteins (e.g. PTEN, TOM1, MFF) with MSC-EV treatment. Of note, many of these proteins are involved in regulation of cell morphology and migration. Gene Set Variation Analysis revealed upregulation of pathways associated with immune response, such as regulation of cytokine production, immune cell infiltration (e.g. T cells, NK cells) and morphological changes (e.g. Semaphorin, RHO/Rac signaling). Additionally, changes in microglia mitochondrial morphology were measured suggesting that MSC-EV modulate mitochondrial metabolism.ConclusionThis study comprehensively demonstrates the effects of MSC-EVs on human microglial morphology, cytokine secretion, cellular proteome, and mitochondrial content. Our high-throughput, rapid, low-cost morphometric approach enables screening of MSC-EV batches and manufacturing conditions to enhance EV function and mitigate EV functional heterogeneity in a disease relevant manner. This approach is highly generalizable and can be further adapted and refined based on selection of the disease-relevant signal, target cell, and therapeutic product.

The impact of mineralocorticoid and glucocorticoid receptor interaction on corticosteroid transcriptional outcomes

The mineralocorticoid and glucocorticoid receptors (MR and GR, respectively) are members of the steroid receptor subfamily of nuclear receptors. Their main function is to act as ligand-activated transcription factors, transducing the effects of corticosteroid hormones (aldosterone and glucocorticoids) by modulating gene expression. Corticosteroid signaling is essential for homeostasis and adaptation to different forms of stress. GR responds to glucocorticoids by regulating genes involved in development, metabolism, immunomodulation and brain function. MR is best known for mediating the effects of aldosterone, a key hormone controlling electrolyte and water homeostasis. In addition to aldosterone, MR binds glucocorticoids (cortisol and corticosterone) with equally high affinity. This ligand promiscuity has important repercussions to understand MR function, as well as glucocorticoid signaling. MR and GR share significant sequence and structural similarities, regulate overlapping sets of genes and are able to interact forming heteromeric complexes. However, the precise role of these heteromers in regulating corticosteroid-regulated transcriptional outcomes remains an open question. In this review, we examine the evidence supporting MR-GR heteromerization, the molecular determinants of complex formation and their possible role in differential regulation of transcription in different cellular contexts and ligand availability.

GRASP55 Regulates Sorting and Maturation of the Lysosomal Enzyme β-Hexosaminidase A.

The Golgi apparatus plays a crucial role in the delivery of lysosomal enzymes. Golgi Reassembly Stacking Proteins, GRASP55 and GRASP65, are vital for maintaining Golgi structure and function. GRASP55 depletion results in the missorting and secretion of the lysosomal enzyme Cathepsin D (Xiang et al ., 2013), though the mechanisms remain unclear. In this study, we conducted secretomic analyses of GRASP55 knockout (KO) cells and found a significant increase in lysosome-associated proteins in the extracellular medium. Using the lysosomal beta-hexosaminidase subunit alpha (HEXA) as a model, we found that GRASP55 depletion disrupted normal trafficking and processing of HEXA, resulting in increased secretion of the immature (pro-form) HEXA into the extracellular milieu, along with decreased levels of the mature form and enzymatic activity within the cell. GRASP55 depletion significantly reduced the complex formation between HEXA and mannose-6-phosphate (M6P) receptors (MPR), despite no overall change in MPR expression. And finally, we found there was a notable reduction in the expression of GNPTAB, leading to a reduction in M6P modification of HEXA, hindering its efficient targeting to lysosomes. These findings reveal the role of GRASP55 in regulating lysosomal enzyme dynamics, emphasizing its role in the sorting and trafficking of lysosomal proteins.

Design, Synthesis and Bioactivity Evaluation of Ag(I)-, Au(I)- and Au(III)-Quinoxaline-Wingtip N-Heterocyclic Carbene Complexes Against Antibiotic Resistant Bacterial Pathogens.

Intending to homogenize the biological activities of both quinoxaline and imidazole moieties, the proligand, 1-methyl-3-quinoxaline-imidazolium hexaflurophosphate (1.HPF6), and [Ag(1)2][PF6], (2); [Au(1)2][PF6], (3); and [Au(1)Cl3], (4) NHC complexes were synthesized. All the synthesized compounds were characterized by elemental analysis, NMR, and UV-Vis spectroscopy. Finally, single crystal X-ray structures revealed a linear geometry for complex 2 whereas a square planar geometry for complex 4. The formation of complex 3 was confirmed and supported by its MS spectra. The antibacterial activities of all the synthesized complexes were investigated against gram-positive bacteria and gram-negative bacteria. The Au(III)-NHC complex, 4 showed the highest antibacterial activity with extremely low MIC values against both the bacterial strains (0.24 μg mL-1). Monitoring of zeta potential supports the higher activity of complex 4 compared to 2 and 3. ROS production by complex 4 has also been measured in vitro in the CT26 cancer cell lines, which is directly responsible for targetting and killing the bacterial pathogens. Cell cytotoxicity assay using 293T cell lines has been performed to investigate the biocompatibility nature of complex 4. Also, an excellent hemocompatibility was assigned to it from its hemolytic studies, which provide valuable insights into the design of novel antibacterial agents.

Catalytic Hydrolysis of Paraoxon by Immobilized Copper(II) Complexes of 1,4,7-Triazacyclononane Derivatives.

Organophosphate neuroactive agents represent severe security threats in various scenarios, including military conflicts, terrorist activities and industrial accidents. Addressing these threats necessitates effective protective measures, with a focus on decontamination strategies. Adsorbents such as bentonite have been explored as a preliminary method for chemical warfare agent immobilization, albeit lacking chemical destruction capabilities. Chemical decontamination, on the other hand, involves converting these agents into non-toxic or less toxic forms. In this study, we investigated the hydrolytic activity of a Cu(II) complex, previously studied for phosphate ester hydrolysis, as a potential agent for chemical warfare decontamination. Specifically, we focused on a ligand featuring a thiophene anchor bound through an aliphatic spacer, which exhibited high hydrolytic activity in its Cu(II) complex form in our previous studies. Paraoxon, an efficient insecticide, was selected as a model substrate for hydrolytic studies due to its structural resemblance to specific chemical warfare agents and due to the presence of a chromogenic 4-nitrophenolate moiety. Our findings clearly show the hydrolytic activity of the studied Cu(II) complexes. Additionally, we demonstrate the immobilization of the studied complex onto a solid substrate of Amberlite XAD4 via copolymerization of its thiophene side group with dithiophene. The hydrolytic activity of the resultant material towards paraoxon was studied, indicating its potential utilization in organophosphate neuroactive agent decontamination under mild conditions and the key importance of surface adsorption of paraoxon on the polymer surface.

SYNBIP 2.0: epitopes mapping, sequence expansion and scaffolds discovery for synthetic binding protein innovation.

Synthetic binding proteins (SBPs) represent a pivotal class of artificially engineered proteins, meticulously crafted to exhibit targeted binding properties and specific functions. Here, the SYNBIP database, a comprehensive resource for SBPs, has been significantly updated. These enhancements include (i) featuring 3D structures of 899 SBP-target complexes to illustrate the binding epitopes of SBPs, (ii) using the structures of SBPs in the monomer or complex forms with target proteins, their sequence space has been expanded five times to 12 025 by integrating a structure-based protein generation framework and a protein property prediction tool, (iii) offering detailed information on 78 473 newly identified SBP-like scaffolds from the RCSB Protein Data Bank, and an additional 16401555 ones from the AlphaFold Protein Structure Database, and (iv) the database is regularly updated, incorporating 153 new SBPs. Furthermore, the structural models of all SBPs have been enhanced through the application of the AlphaFold2, with their clinical statuses concurrently refreshed. Additionally, the design methods employed for each SBP are now prominently featured in the database. In sum, SYNBIP 2.0 is designed to provide researchers with essential SBP data, facilitating their innovation in research, diagnosis and therapy. SYNBIP 2.0 is now freely accessible at https://idrblab.org/synbip/.

The Effects of Montmorillonite–Humic Acid Composite Particles on the Photolysis of Tetracycline in Water

Suspended particulate matter (SPM) is an important component of natural water bodies and can significantly influence the photolytic behavior of water pollutants. A comprehensive understanding of the photochemical behavior of water pollutants in natural waters requires consideration of the presence of SPM. In this study, montmorillonite–humic acid (MMT-HA) composite particles were synthesized to simulate SPM in natural waters and their effects on the photolysis of tetracycline (TC) were investigated. The results demonstrated that the presence of MMT-HA composite particles in water significantly enhanced the photolysis of TC, with the photolytic kinetics following a pseudo-first-order model. Electron spin resonance spectra and free radical quenching experiments indicated that the photoactive components (MMT and humic acids) in the composite particles induced the generation of reactive oxygen species under light exposure, further contributing to the enhanced photolysis of TC. Comparative analysis of the free radical signals and adsorption experiments revealed that the accelerated photolysis of TC was also related to the interfacial interaction between the MMT in the composite particles and the TC molecules. The formation of surface complexes between TC molecules and the negatively charged sites on the MMT surface facilitated light absorption and electron transfer, thereby accelerating the photolysis of TC. Photoproduct analysis indicated that the primary degradation pathways of TC in the composite particle systems included the addition of hydroxyl radicals to the aromatic ring, as well as demethylation, deamination and dehydration in the side chains. This study shows that SPM in water bodies can affect the photochemical behavior of pollutants and should be taken into account when assessing the phototransformation of pollutants in natural waters.

Formation and Applications of Typical Basic Protein-Based Heteroprotein Complex Coacervations.

Lactoferrin, lysozyme, and gelatin are three common basic proteins known for their ability to interact with acidic proteins (lactoglobulin, ovalbumin, casein, etc.) and form various supramolecular structures. Their basic nature makes them highly promising for interaction with other acidic proteins to form heteroprotein complex coacervation (HPCC) with a wide range of applications. This review extensively examines the structure, properties, and preparation methods of these basic proteins and delves into the internal and external factors influencing the formation of HPCC, including pH, ionic strength, mixing ratio, total protein concentration, temperature, and inherent protein properties. The applications of different HPCCs based on these three basic proteins are discussed, including the encapsulation of bioactive molecules, emulsion stabilization, protein separation and extraction, nanogel formation, and the development of formulas for infants. Furthermore, the challenges and issues that are encountered in the formation of heteroprotein complexes are addressed and summarized, shedding light on the complexities and considerations involved in utilizing HPCC technology in practical applications. By harnessing the basic proteins to interact with other proteins and to form complex coacervates, new opportunities arise for the development of functional food products with enhanced nutritional profiles and functional attributes.

The EP3-ZNF488 Axis Promotes Self-Renewal of Glioma Stem-like Cells to Induce Resistance to Tumor Treating Fields.

Tumor Treating Fields (TTFields) employ low-intensity, alternating electric fields to exert antitumor activity and have demonstrated efficacy against multiple cancers, including glioblastoma (GBM). Unfortunately, cancer cells inevitably develop resistance to TTFields, highlighting the need to elucidate the underlying mechanisms to develop approaches to induce durable responses. Using a gene network-based machine-learning algorithm, we interrogated TTFields-resistant GBM cells and uncovered a regulatory axis anchored by the prostaglandin E receptor 3 (EP3) and the transcription factor zinc finger 488 (ZNF488). Mechanistically, TTFields induced EP3 upregulation and nuclear envelope localization, where it formed a complex with ZNF488 to induce resistance to TTFields by promoting self-renewal of glioma stem-like cells (GSC). Overexpression of EP3 and/or ZNF488 in TTFields-sensitive GSC conferred resistance and enhanced self-renewal, while expression of non-interacting mutants of these proteins abrogated formation of the nuclear complex and prevented resistance. Inhibition of either partner in this protein complex in resistant GSC, including those freshly isolated from TTFields-resistant GBM tumors, re-sensitized cells to the cytotoxic effects of TTFields, concomitant with reduced self-renewal and in vivo tumorigenicity. Importantly, inhibition of EP3 in TTFields-sensitive GSC preemptively halted the development of resistance. The EP3-ZNF488 axis was significantly upregulated in TTFields-resistant GBM tumors, and co-expression of EP3 and ZNF488 in other cancers correlated with lower survival rates. Collectively, these results indicate that the nuclear EP3-ZNF488 axis is necessary and sufficient to establish TTFields resistance, underscoring the potential to target this axis to prevent or reverse resistance in GBM and possibly other cancers.

The Complexation in Co(NO3)2·6H2O / 2,2'‐bipyridine / Y(NO3)3·6H2O / MeOH System: Still More to Uncover

The formation of novel uncommon heterodinuclear complex was detected in Co(NO3)2·6H2O / 2,2'‐bipyridine / Y(NO3)3·6H2O / MeOH system. The peculiarities of composition and structure of this new compound were found to affect its vibrational and thermal properties compared to those of reported major product formed in the same system.

Naked eye detection of anions: Dihydrazone receptor-based visual sensing

In this study, we designed and synthesized a novel colorimetric sensor for fluoride ions by integrating a thienodicarbohydrazide framework with salicylaldehyde, resulting in a unique bis-hydrazone-phenol receptor. This sensor exhibited exceptional selectivity for fluoride and acetate ions in nonaqueous environments, with detection visible to the naked eye. Upon interaction with fluoride ions, the receptor underwent a significant red shift in its UV–Visible absorption spectrum, moving from an absorption maximum at 332 nm–380 nm, signalling the recognition event. Acetate ions induced a similar shift. The binding interactions were thoroughly investigated, with a Jobs plot revealing a 1:1 receptor-anion complex formation with fluoride ions and a 1:2 complex with acetate ions. Further validation came from 1H NMR titration, which confirmed the presence of hydrogen bonding interactions between the receptor and the ions. The receptor demonstrated remarkable binding constants of 5.2 × 10⁴ M−2 for acetate and 1.6 × 10⁴ M−1 for fluoride ions, highlighting its strong and selective affinity. Fluorescence titrations further confirmed the receptor's potential as a chemo sensor, showing distinct emission changes in the presence of fluoride and acetate ions. This study not only underscores the receptor's capability for visual detection of fluoride ions in non-aqueous systems but also paves the way for its application in diverse analytical and environmental settings.

Structure Elucidation of Pharmaceutically Relevant Compounds Within Pyrene-Based Frameworks.

Single-crystal X-ray diffraction (SCXRD) is the preferred and most accurate technique for determining molecular structures. However, it can present challenges when dealing with specific small molecules and active pharmaceutical ingredients (APIs), as many do not form quality crystals without coformers or can be unstable. In this study, we introduce tetrakis(guanidinium) pyrenetetrasulfonate (G4PYR), a robust guanidinium-organosulfonate (GS) framework that efficiently encapsulates small molecules and APIs rich in functional groups. The hydrogen bonding frameworks formed by G4PYR display well-ordered structures with predictable pyrene-pyrene distances, making them ideally suited for targeting arene-based APIs with pendant groups. Successful encapsulation of various guests, including benzaldehyde, benzamide, and arenes containing multiple hydrogen bond donors and acceptors like uracil and thymine, was achieved. Furthermore, we successfully encapsulated important pharmaceutical and biologically relevant compounds, such as lidocaine, ropinirole, adenosine, thymidine, and others. Notably, we present a workflow for investigating host-guest complex formation using powder X-ray diffraction and high throughput experimentation.