Design of C2-symmetric pseudopeptides for in vivo detection of Cu(II) through controlled supramolecular nano-assembly.

Pseudopeptides are emerging next-generation soft bioinspired materials for biological applications. Therefore, a new class of C2-symmetric L-valine-derived pseudopeptides has been designed and developed. The newly developed pseudopeptides exhibit intracellular Cu(II) ion detection in live-cell fluorescence studies on RAW264.7 cells. We find that the changes in the amino acid side chain in desired pseudopeptidic moieties lead to a drastic change in their selectivity towards different metal ions. The L-valine-derived pseudopeptides exhibit selectivity towards Cu(II) ions through turn-off fluorescence, and the L-phenylalanine-derived pseudopeptides exhibit selectivity towards Zn(II) ions through turn-on fluorescence. In addition, the L-valine-derived pseudopeptides show an increase in spherical-shaped structures upon incubation with Cu(II) ions during supramolecular nano-assembly formation. In contrast, the L-phenylalanine-derived pseudopeptides show a decrease in spherical-shaped structures upon adding Zn(II) ions. The judiciously designed L-valine-derived and L-phenylalanine-derived bioinspired pseudopeptides are promising for exploring similar effects in various peptidomimetics in advanced biological applications.

L-Phenylalanine-derived pseudopeptidic bioinspired materials: Zn(II) induced fluorescence enhancement and precise tuning of self-assembled nanostructures.

The pseudopeptide, owing to its intriguing, sustainable, and easily accessible multifunctional properties, has attracted significant research interest over the years. C2-symmetric pseudopeptidic chiral bioinspired materials have been developed for their selective sensitivity to Zn(II) ions via a turn-on fluorescence under physiological conditions. Moreover, these are promising soft materials for precisely tuning their self-assembled nanostructures after incubating with Zn(II), opening avenues for exploring similar effects in various peptidomimetics.

Intracellular Zn(II) induced turn-on fluorescence of an L-phenylalanine-derived pseudopeptide.

A C2 symmetric L-phenylalanine-derived pseudopeptide has been synthesized for selective and sensitive recognition of Zn(II) ions in aqueous-organic media. The pseudopeptidic probes exhibit intracellular Zn(II) ion-sensing capabilities as demonstrated via live-cell fluorescence studies on RAW264.7 cells. Hence, we present a bioinspired pseudopeptide for potential biological applications involving intracellular Zn(II) ion detection.

Pyrene Functionalized Luminescent Phenylalanine for Selective Detection of Copper (II) Ions in Aqueous Media.

A novel pyrene-based fluorescent chemosensor 1 (pyren-1-ylmethyl)-L-phenylalanine was designed and synthesized by combining 1-pyrenecarboxyaldehyde and L-phenylalanine. 1 was characterized by several analytical methods and used as a fluorescent chemosensor for the selective and sensitive detection of Cu2+ ions through "turn-off" mechanism with a detection limit of 2 × 10-8 M. 1 can also be used to detect Cu2+ ions in a natural water sample and exhibits gelation properties with high thermal stability.

Synthesis, characterization, and electrocatalytic behaviour of hydrothermally grown nanostructured La2 O3 and La2 O3 /K-complex.

Rare earth metals play a conspicuous role in magnetic resonance imaging (MRI) for detecting cancerous cells. The alkali metal potassium is a neurotransmitter in the sodium-potassium pump in biomedical sciences. This unique property of rare earth metals and potassium drew our attention to carry forward this study. Therefore, in this work, previously synthesized potassium (K) complexes formed by the reflux of 4-N,N-dimethylaminobenzoic acid (DBA) and potassium hydroxide in methanol, and named [(µ2-4-N,N-dimethylaminobenzoate-κO)(µ2-4-N,N-dimethylaminobenzoic acid-κO)(4-N,N-dimethylaminobenzoic acid-κO) potassium(I) coordination polymer)] were treated hydrothermally with La2 O3 nanomaterials to obtain a nanohybrid La2 O3 /K-complex. After that, the K-complex was analyzed using single-crystal X-ray diffraction and 1 H and 13 C NMR spectroscopy. In addition, the structural and morphological properties of the as-prepared nanostructured La2 O3 /K-complex were also characterized, which involved an investigation using X-ray diffraction (XRD)spectroscopy, Fourier transform infrared (FTIR) spectroscopy, atomic force spectroscopy (AFM), transmission electron microscopy (TEM), and energy dispersive X-ray (EDX) analysis. After this, the electrochemical redox behaviour of the synthesized nanohybrid material was studied using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Therefore, the results from these studies revealed that the as-prepared material was a La2 O3 /K-complex that has a promising future role in sensing various analytes, as it showed effective electrocatalytic behaviour.

A zinc (II) complex comprising an aminoethyl-nitropyridine-derived N,N,O-donor Schiff base ligand serves as an efficient ON-OFF probe for Cu(II).

A new fluorescent zinc (II) complex-based probe 1 encompassing a Schiff's base (E)-2-methoxy-6-((2-[5-nitropyridin-2-ylamino]ethylimino)methyl)phenol (HL) was designed, synthesized, and used for the highly selective detection of Cu2+ . Ligand HL and complex 1 were characterized using various spectroscopic techniques such as 1 H, 13 C-NMR, and FTIR spectroscopy, high-resolution mass spectronomy (HRMS), UV/visible light spectroscopy, and fluorescence studies. Ligand HL did not exhibit any considerable change in fluorescence in the presence of various cations. Notably, its Zn(II) complex 1 exhibited highly selective 'TURN-OFF' fluorescence signalling towards Cu2+ that remained uninterrupted with competing analytes. Probe 1 interacted with Cu2+ in 1:2 (1:Cu2+ ) stoichiometry as estimated through a Job's plot. Moreover, the selectivity of 1 was further confirmed through the interaction of the 1 + Cu2+ complex with some possible interfering metal ions inducing an insignificant response. Additionally, the association and quenching constant were determined to be 3.30 × 104 M-1 and 0.21 × 105 M-1 through the Benesi-Hildebrand method and Stern-Volmer plot, respectively.

Development of highly selective fluorescent ferrocenyl-iminopyridine chemosensor for biologically relevant Fe3.

Design, synthesis, characterization, and ion detection studies of two ferrocene-appended Schiff bases namely N-(2-[ferrocenylamino]ethyl)-5-nitropyridin-2-amine (1) and ferrocenylamino-1H-imidazole-4-carboxamide (2) been reported. Both the chemosensors have been thoroughly characterized using Fourier transfer infrared, 1 H and 13 C nuclear magnetic resonance, high resolution mass spectrometry, and ultraviolet/visible (UV/visible) and fluorescence spectral techniques. Probes 1 and 2 were designed with the aim of appending the ferrocenyl group with pyridine ring having an amine substitution (for 1) and imidazole ring with an amide substitution (for 2). Interaction of these probes with a series of cations and anions was examined through UV/vis and fluorescence spectral techniques. Probe 2 exhibited an insignificant response towards anions and loss of selectivity for cations, whereas 1 displayed highly selective detection towards biologically important Fe3+ in 2:1 (probe:cation) stoichiometry. Notably, none of the cations and anions could interfere the selectivity of Fe3+ ensured by 1 in aqueous medium. The limit of detection for Fe3+ detection using 1 was determined to be 0.2 ppm. The results strongly suggest that 1 could find promising future application as a chemosensor for Fe3+ in biological systems for quantification and qualitative analysis.

Investigating the spectral and electrochemical properties of novel flavin-pyrene dyads separated via variable spacer.

The present manuscript describes the synthesis and the photophysical properties of a pair of novel flavin-pyrene dyads where the donor and the acceptor entities are separated via variable spacer. The dyads were well characterized using standard techniques and investigated for their photophysical and electrochemical nature. The observed absorption spectra of the dyads mainly display peaks corresponding to the individual pyrene and flavin units, with some contribution from the flavin entity in the pyrene region. While, strong emission quenching was observed for both the dyads if compared to its individual constituents. However, a careful analysis of the emission spectra and the solvent dependent studies reveals subtle difference between the two dyads. While no significant difference could be observed when excited in the flavin region; excitation at the pyrene region displays a weak and broad emission band in case of closely connected dyad. Further, the electrochemical properties were investigated by cyclic voltammetry and the reduction ability was observed to follow the trend as FlPy2 < FlPy1 < Fl.

A Dual-Signaling Ferrocene-Pyrene Dyad: Triple-Mode Recognition of the Cu(II) Ions in Aqueous Medium.

We report a structure of ferrocene-pyrene conjugate (1) comprising electro and photo-active dual-signaling units. In particular, 1 upon interaction with Cu(II), displays selectively one-photon fluorescence quenching, but it shows two-photon absorption (TPA) cross-section 1230 GM (at 780 nm). Further, 1 displayed two irreversible oxidative waves at 0.39 V and 0.80 V (vs Ag/AgCl), in the electrochemical analysis which upon addition of Cu2+, led to the negative potential shift in both the oxidative waves to appear at 0.25 V and 0.68 V. The triple mode changes in presence of Cu(II) suggesting the possible application of 1 for the detection of Cu(II) in aqueous media. Graphical Abstract.

Zinc-Induced Luminescent l-Valine-Based Pseudopeptidic Soft Bioinspired Materials for Precise Tuning of Nanoassembly.

Pseudopeptide-based bioinspired materials are emerging for selective recognition of biologically significant analytes and are applicable in the modern nanoscience field. Therefore, we have developed novel multifunctional C2-symmetric soft pseudopeptides by amino acid l-valine and salicylaldehyde fragments using a series of aliphatic linkers. They are highly selective and sensitive to Zn (II) ions under physiological conditions and reveal significant fluorescence enhancement with the PET mechanism. The molecular self-assembly shows zinc-induced morphological transformation of the rod-shaped assembly into a chain-like morphology. Such a metal-induced hierarchical nano-assembly may have relevance for specific nanobiotechnology applications.

Efficient removal of chromate from wastewater using a one-pot synthesis of chitosan cross-linked ceria incorporated hydrous copper oxide bio-polymeric composite.

Remediating hexavalent chromium [Cr(VI)] from contaminated water systems is a significant concern due to its harmful effects on human health, aquatic life, and plants. To tackle this issue, scientists have created a chitosan cross-linked hydrous ceria incorporated cupric oxide bio-polymeric composite (CHCCO) by combining chitosan biopolymer with corresponding metal ions using glutaraldehyde as a cross-linker. The composite was characterized using advanced analytical instruments such as FTIR, p-XRD, SEM, XPS, etc. The synthesized composite (CHCCO) was then tested for its efficiency in removing Cr(VI) from synthetic Cr(VI) aqueous samples. The parameters examined included pH, material dose, contact time, concentration, temperature, and co-existing ions. The experimental data showed that the kinetics and equilibrium data fit well with the pseudo-second-order and the Freundlich isotherm models, respectively. Thermodynamic analysis demonstrated that the investigated surface adsorption process is spontaneous and endothermic. Except for the SO42- ion, no other species imparts adverse influence significantly on the reaction. The CHCCO bio-composite surfaces were refreshed using a dilute NaOH (1.0 M) solution and effectively recycled five times for Cr(VI) adsorption, indicating no significant surface activity deterioration. This study highlights the high effectiveness of CHCCO bio-polymeric composites in Cr(VI) remediation and the potential for this technology as an easy-to-use technique for environmental restoration.

L-Tryptophan-based pyrene conjugate for intracellular zinc-guided excimer emission and controlled nano-assembly.

This article describes intracellular zinc-induced excimer emission and tuning of self-assembly from L-tryptophan-pyrene conjugate (1). The zinc-guided excimer formation is due to the interaction of the pyrene moiety in an excited state. AFM studies show the structural modification in the supramolecular nano-assembly of 1 from dome-shaped to porous surface after complexation with zinc ions. Further, the interaction of 1 with Zn(II) ion is also studied using DFT, Job's plot, NMR titration and HRMS. The results of Zn(II) ion determination in natural water samples and RAW 264.7 cells demonstrate the practical utility of 1.

Advancements in the development of fluorescent chemosensors based on CN bond isomerization/modulation mechanistic approaches.

The CN bond isomerization/modulation as a fluorescence signalling mechanism was explored by studying the photophysical properties of conformationally restricted molecules. From the beginning, the CN bond isomerization method has attracted the attention of researchers owing to its simplicity, high selectivity, and sensitivity in fluorescence evaluation. Continuous developments in the field of sensing using CN bond-containing compounds have been achieved via the customization of the isomerization process around the CN bond in numerous ways, and the results were obtained in the form of specific discrete photophysical changes. CN isomerization causes significant fluorescence enhancement in response to detected metal cations and other reactive species (Cys, Hys, ClO-, etc.) straightforwardly and effectively. This review sheds light on the process of CN bond isomerization/modulation as a signalling mechanism depending on fluorescence changes via conformational restriction. In addition, CN bond isomerization-based fluorescent sensors have yet to be well reviewed, although several fluorescent sensors based on this signalling mechanism have been reported. Therefore, CN-based fluorescent sensors are summarized in this review.

Recent advances in AIEgen-based chemosensors for small molecule detection, with a focus on ion sensing.

Since the aggregation-based emission (AIE) phenomenon emerged in 2001, numerous chemical designs have been built around the AIE concept, displaying its utility for diverse applications, including optics, electronics, energy, and biosciences. The present review critically evaluates the broad applicability of AIEgen-based chemical models towards sensing small analytes and the structural design strategies adjusting the mode of action reported since the last decade. Various AIEgen models have been discussed, providing qualitative and quantitative estimation of cationic metal ions and anionic species, as well as biomolecular, cellular, and organelle-specific probes. A systematic overview of the reported structural design and the underlying working mode will pave the way for designing and developing the next generation of AIEgens for specific applications.

Pyrene appendant triazole-based chemosensors for sensing applications.

Over the last two decades, the design and development of fluorescent chemosensors for the targeted detection of heavy transition-metal (HTM) ions, anions, and biological analytes, have drawn much interest. Since the introduction of click chemistry in 2001, triazole moieties have become an increasingly prominent part of chemosensors. Triazoles generated via click reactions are crucial for sensing various ions and biological analytes. Recently, the number of studies in the field of pyrene appendant triazole moieties has risen dramatically, with more sophisticated and reliable triazole-containing chemosensors for various analytes of interest described. This review provides a general overview of pyrene appendant-triazole-based chemosensors that can detect a variety of metal cations, anions, and neutral analytes by using modular click-derived triazoles.

Silver-guided excimer emission in an adenine-pyrene conjugate: fluorescence lifetime and crystal studies.

This Communication describes a novel adenine-pyrene conjugate (1) and its solid-state structure with silver and copper ions. Single-crystal studies of metal complexes of 1 offer insight into molecular interactions and provide a basis to rationalize possible interactions in the solution state, leading to excimer formation. The robust nature of this interaction was further confirmed by deposition of the silver complex on a graphite surface, which exhibited a remarkable resemblance to its solid-state structure. The structural basis of selective excimer formation in the presence of Ag(+) ions presents a viable approach for ratiometric detection of these ions.

Synthesis, structure, and two-photon absorption studies of a phosphorus-based tris hydrazone ligand (S)P[N(Me)N=CH-C6H3-2-OH-4-N(CH2CH3)2]3 and its metal complexes.

A phosphorus-supported multidentate ligand (S)P[N(Me)N=CH-C(6)H(3)-2-OH-4-N(CH (2)CH(3))(2)](3) (1) has been used to prepare mononuclear complexes LM [M = Fe (2) Co (3)] and trinuclear complexes L(2)M(3) [M = Mn (4), Ni (5), Zn (6), Mg (7), Cd (8)]. In both 2 and 3 the ligand binds the metal ion in a facial coordination mode utilizing three imino nitrogen (3N) and three phenolic oxygen (3O) atoms. The molecular structures of L(2)Mn(3), L(2)Ni(3), L(2)Zn(3), L(2)Mg(3), and L(2)Cd(3) (4-8) are similar; two trihydrazone ligands are involved in coordination to hold the three metal ions in a linear fashion. Each of the trishydrazone ligands behaves as a trianionic hexadentate ligand providing three imino and three phenolic oxygen atoms for coordination to the metal ions. The coordination environment around the two terminal metal ions is similar (3N, 3O) while the central metal ion has a 6O coordination environment. Third-order non-linear optical properties of these compounds as measured by their two-photon absorption (TPA) cross section reveals that while 1 does not possess obvious TPA activity, complexes 2 (3213 GM) and 4 (3516 GM) possess a large TPA cross section at 770 nm.

Cyclometalated Ir(III) Complex as a Metalloligand and a Selective Cu(II) Sensor: Synthesis and Structural Characterization of a Heterometallic Tetranuclear Ir(III)/Cu(II) Complex.

A cyclometalated Ir(III) complex, [Ir(ppy)2(LH)] (2) [LH2 = 1,2-bis(pyridine-2-carboxamido)benzene; ppyH = 2-phenylpyridine] was synthesized and structurally characterized. [Ir(ppy)2(LH)] contains free donor sites and functions as a metalloligand. Accordingly, it interacts with a Cu(II) salt to afford the heterometallic tetranuclear complex, [{Ir(ppy)2(L)}2{Cu2Cl2}] (3). In the latter, a Cu2Cl2 dimer bridges the two cyclometalated Ir(III) units, resulting in a IrIII-CuII-CuII-IrIII motif. 2 also functions as a selective and reversible sensor for Cu2+, as revealed by quenching of its emission and subsequent revival of the luminescence signal upon addition of EDTA.

Efficient precipitation of dyes from dilute aqueous solutions of ionic liquids.

The addition of only approximately 1.7 wt% (approximately 0.06 M) ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate to aqueous solutions of six popular cationic dyes resulted in the precipitation of almost all of the dye from the solution.