A Highly Selective Pyrene Appended Oxacalixarene Receptor for MNA and 4-NP Detection: an Experimental and Computational Study.

A novel pyrene-substituted oxacalixarene was designed and synthesized as a selective probe for the simultaneous detection of MNA and 4-NP. Utilizing 1H-NMR, 13C-NMR, and FT-IR analysis techniques, its structure was characterized. The binding property of BPOC to a variety of NACs, including 1,3-DNB, 2,3-DNT, 2,4-DNT, 2,6-DNT, 4-NP, 4-NT, and PA, revealed that the sensor binds to MNA and 4-NP with remarkable selectivity. Binding constant reveals lower detection limits of MNA is 0.2 µM and 0.3 µM for 4-NP. Using docking and density functional theory (DFT), computational insights were provided for investigating the stability and spectroscopic analysis of the inclusion complex. From molecular docking study, we observed the best docking score of BPOC with 4-NT and MNA complex. The calculations supplement the findings significantly and clarify the structural geometry and mode of interactions in supramolecular complexation. In an MTT experiment on human PBMC to check for cytotoxicity, this chemical was found to influence 1 × 105 cell viability dose-dependently.

Fluorescence Quenching and the Chamber of Nitroaromatics: A Dinaphthoylated Oxacalix[4]arene's (DNOC) Adventure Captured through Computational and Experimental Study.

This research presents the application of Dinaphthoylated Oxacalix[4]arene (DNOC) as a novel fluorescent receptor for the purpose of selectively detecting nitroaromatic compounds (NACs). The characterization of DNOC was conducted through the utilization of spectroscopic methods, including 1H-NMR, 13C-NMR, and ESI-MS. The receptor demonstrated significant selectivity in acetonitrile towards several nitroaromatic analytes, such as MNA, 2,4-DNT, 2,3-DNT, 1,3-DNB, 2,6-DNT, and 4-NT. This selectivity was validated by the measurement of emission spectra. The present study focuses on the examination of binding constants, employing Stern-Volmer analysis, as well as the determination of the lowest detection limit (3σ/Slope) and fluorescence quenching. These investigations aim to provide insights into the inclusion behavior of DNOC with each of the six analytes under fluorescence spectra investigation. Furthermore, the selectivity trend of the ligand DNOC for NAC detection is elucidated using Density Functional Theory (DFT) calculations conducted using the Gaussian 09 software. The examination of energy gaps existing between molecular orbitals, namely the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), provides a valuable understanding of electron-transfer processes and electronic interactions. Smaller energy gaps are indicative of heightened selectivity resulting from favorable electron-transfer processes, whereas bigger gaps suggest less selectivity attributable to weaker electronic contacts. This work integrates experimental and computational methodologies to provide a full understanding of the selective binding behavior of DNOC. As a result, DNOC emerges as a viable chemical sensor for detecting nitroaromatic explosives.

Pyrene functionalized oxacalix[4]arene architecture as dual readout sensor for expeditious recognition of cyanide anion.

A pyrene functionalized oxacalix[4]arene architecture (DPOC) was utilized as a fluorescence probe for selective recognition of cyanide ions. The receptor DPOC shows excellent selectivity towards cyanide ion with a red shift of 108 nm in absorption band along with a significant change in colour from light yellow to pink. The fluorescence titration experiments further confirm the lower limit of detection as 1.7µM with no significant influences of competing anions. 1 H-NMR titration experiments support the deprotonation phenomena, as the -NH proton disappears upon successive addition of cyanide ions. The DFT calculation also indicates a certain increment of -NH bond length upon interaction with cyanide ions. The spectral properties as well as colour of DPOC-CN- system may be reversed upon the addition of Ag+/ Cu2+ ions up to 5 consecutive cycles. Moreover, DPOC coated "test strips" were prepared for visual detection of cyanide ions.

Development of tBu-phenyl Acetamide Appended Thiacalix[4]arene as "Turn-ON" Fluorescent Probe for Selective Recognition of Hg(II) Ions.

Herein, a novel N-(4-(tert-butyl)-phenyl)-2-chloroacetamide functionalized thiacalix[4]arene architecture, viz TCAN2PA has been synthesized and the sensing behaviour towards metal ions were explored. The probe, TCAN2PA displayed "turn-on" fluorescence response towards Hg(II) ions in acetonitrile over a series of competing common metal ions. A bathochromic shift in absorption band along with a significant "Turn-On" fluorescence behaviour of TCAN2PA was observed upon interaction with Hg(II) ions. The lower rim modification of thiacalixarene with N-(4-(tert-butyl)-phenyl)-2-chloroacetamide actively contributes toward the fluorescence property due to the presence of strong electron-donating aryl amido substituent. Fluorescence titration experiments were conducted to find out the limit of detection and to understand binding stoichiometry as well. The electron transfer interactions between the electron rich TCAN2PA host with Hg(II) ions have been postulated which is also supported by computational modelling insights.

Recent Advancements for the Recognization of Nitroaromatic Explosives Using Calixarene Based Fluorescent Probes.

In this era, explosives are easily available compared to the early days. Thus, more effective detection of explosives has become the main concern of homeland security. In the past decades, a large number of sensing materials have been developed for the detection of explosives in solid, vapor, and solution states through fluorescence methods. In recent years, great efforts have been devoted to developing new fluorescent materials with various sensing mechanisms for detecting explosives in order to achieve super-sensitivity, ultra-selectivity, as well as fast response time. Modified calixarenes have high potentials to detect nitroaromatic compounds (NACs) due to their favorable structural properties. It summarizes the detection of NACs by the modified calixarene system formed by the complex. Various methodologies responsible for complex formation and binding mechanisms (PET, FRET, EE, etc.) are the centerpiece of this review. Finally, conclusions and future outlook are presented and discussed.

A switch-off fluorescence probe towards Pb(II) and cu(II) ions based on a calix[4]pyrrole bearing amino-quinoline group.

A new fluorescence receptor calix[4]pyrrole-N-(quinoline-8-yl) acetamide (CAMQ) containing a pyrrolic ring connected via the meso-position was synthesized, purified and characterized by elemental analysis, NMR and mass spectroscopy. This compound was examined for its fluorescence properties towards different metal ions e.g. Ag(I), Hg(II), Co(II), Ca(II), Ni(II), Zn(II), Cr(II), Ba(II), Fe(II), Cu(II), Pb(II)and Mg(II) ions by spectrophotometry and spectrofluorometry. It was concluded that the compound (CAMQ) possessed significantly enhanced selectivity for Pb(II) and Cu(II) ions in dimethyl sulfoxide (DMSO) even at very low concentrations (1 µM). It exhibit 'turn-on' fluorescence when exposed to Pb(II) and Cu(II) and did so in preference to other metal ions. The binding constants, stoichiometry and quantum yields have been determined. The quenching mechanism was assessed using the Stern-Volmer equation and was also discussed.

Calix-Based Nanoparticles: A Review.

Calixarenes are considered as third generation supramolecules with hollow cavity-like architecture whereas nanoparticles are small entities with dimensions in the nanoscale. Many exciting achievements are seen when the calix system merges with nanoparticles which produces many fascinating facets in all fields of contemporary chemistry. The properties of nanoparticles which are tuned by calixarenes find applications in sensing, catalysis, molecular recognition, etc. Here, we have reviewed the chemistry of calix-based nanoparticles, and emphasis is laid on the modified, reducing, templated and stabilizing roles of calixarenes. This review covers the research being carried out in the domain of calix protected metal nanoparticles during last 18 years under the canopy of important 109 references. This article contains 58 figures which include 81 easy to understand structures. Calix-protected nanoparticles have enthralled researchers in the field of nanoscience with a tremendous growth in its applications, which heralds much promise to become in future a separate area of research.

Efficiently functionalized oxacalix[4]arenes: Synthesis, characterization and exploration of their biological profile as novel HDAC inhibitors.

A series of novel substituted oxacalix[4]arene has been synthesized and explored for their biological profile by evaluating anticancer, antifungal and antibacterial properties. The derivatives have been characterized by various spectroscopic techniques such as IR, (1)H NMR, (13)C NMR and Mass spectrometry. Many compounds showed strong inhibition (MIC) in the range of ∼0-50 µM with interesting cytotoxic activities against Hela cells in particular. The compounds were theoretically evaluated by docking studies as potential histone deacetylase inhibitors (HDACi). The study indicates that compounds bound adequately with HDAC, and hence complemented the experimental findings.