Tetra-benzimidazoles flanking divinyl-phenothiazine: AIEgens as aza-Michael acceptors in concentration-tuned responses to biogenic amine vapors.

Tetra-benzimidazole rotors flanking a divinyl-phenothiazine stator are realized as red AIEgens and newly identified as efficient aza-Michael acceptors for the identification of biogenic amine vapors. Weakly red-emissive solids display a blue-shifted turn-on emission by rapid aza-Michael addition and simultaneous reverse Knoevenagel reactions. Concentration variation imposes better crystallinity and facilitates radiative decay, offering distinct emissions.

Unveiling the Long-Awaited Aldehyde Intermediate in Oxidative Dephosphorylation: A Unique Approach to Access Useful Carboxaldehydes.

Oxidative dephosphorylation reactions usually generate symmetrically substituted alkenes from organophosphonates. Even the ubiquitous presence of oxygen can produce such alkenes inadvertently as a side product in small amounts from Wittig/Horner-Wadsworth-Emmons (HWE) reactions. So far, aldehydes have been expected to be the on-pathway intermediate since their discovery, but there was no substantial experimental evidence to support this.

Access to Diverse Glutamic Acid Dendrons and a Janus Peptide Dendrimer Using an Atypical Solid Phase Synthesis.

The negligible cytotoxicity of anion surface-linked dendrons makes glutamic acid-based dendrons a potential candidate for materials and biological applications. Despite the inherent drawbacks of the conventional solution phase synthesis of glutamic acid-based dendrons, there have been no advancements in these protocols. Herein, we demonstrate the first-ever convergent solid phase synthesis of dendrons, up to fourth generation, having glutamic acid branching points produced by preactivation of dicarboxylic acid groups with -hydroxysuccinimide and simultaneous coupling with amine groups of two growing peptide chains, with excellent yields (30-70%).

Targeting hexokinase 2 for oral cancer therapy: structure-based design and validation of lead compounds.

The pursuit of small molecule inhibitors targeting hexokinase 2 (HK2) has significantly captivated the field of cancer drug discovery. Nevertheless, the creation of selective inhibitors aimed at specific isoforms of hexokinase (HK) remains a formidable challenge. Here, we present a multiple-pharmacophore modeling approach for designing ligands against HK2 with a marked anti-proliferative effect on FaDu and Cal27 oral cancer cell lines.

Isomeric Benzenediol-Linked Organophosphonates as a Handy Reusable Emitting Platform: Diversity in Polyamine Vapor Detection.

This work introduces metal/column-free facile quantitative access to conformationally twisted catechol-linked organophosphonate () as a blue-emitting solid that could reversibly detect only 1,3-diaminopropane (DAP) and 1,2-ethylenediamine (EDA) vapors, belonging to industrially and pharmaceutically abundant crucial diamines. In , two adjacent hydroxy groups in a benzene ring facilitate selective diamine-dihydroxy (amine-phenol type) interactions in the solid phase, leading to a quenched emission with selectively smaller aliphatic PAs, that is, DAP and EDA. The disparity was noticed with an isomeric resorcinol-linked emitter (), detecting various polyamine vapors with superior sensitivity.

Concentration-tuned diverse response to selective biogenic amines using a reusable fluorophore: monitoring protein-rich food spoilage.

Maintaining the freshness of food is essential for a healthy and quality life. Nevertheless, it remains a global challenge. Hence, an easy detection and monitoring protocol would be highly desirable.

Concentration-Guided Visual Detection of Multiphase Aliphatic Biogenic Amines through Amine-Phenol Recognition Using a Dual-State Emitter.

Intermolecular amine-phenol interactions are largely recognized as unique models with diverse supramolecular interactions. However, fluorescence (FL) variations originating from such interactions are rare. Herein, FL changes are well realized from amine-phenol interactions to identify an important biomarker, biogenic amines (BAs).

Solid-state emitting twisted π-conjugate as AIE-active DSE-gen: anticancer properties against FaDu and 4T1 with biocompatibility and bioimaging.

Dual-state emissive fluorogens (DSE-gens) are currently defining their importance as a transpiring tool in biological and biomedical applications. This work focuses on designing and synthesizing indole-anthracene-based solid-state emitting twisted π-conjugates using a metal-free protocol to achieve AIE-active DSE-gens, expanding their scope in biological applications. Special effort has been made to introduce proficient and photo/thermostable DSE-gens that inhibit cancer but not normal cells.

Naked-Eye Optical Recognition of Ammonia Vapor and Melamine in Water Using a Fluorophore Appended Polymer Matrix.

The generation of solid-state emitters is a challenge due to the intrinsic aggregation-caused quenching feature of the fluorophores. A conformationally twisted pyridyl π-conjugate as a solid-state emitter is appended with well-known and inexpensive poly(methylmethacrylate) [PMMA] to afford a handy, portable, and reusable solid-state emitting polymer matrix. Entrapment of the probe is noticed through non-covalent interactions, resulting in a green-emitting platform.

A -symmetric twisted organic salt as an efficient mechano-/thermo-responsive molecule: a reusable and sensitive fluorescent thermometer.

-Symmetric triaminoguanidinium chloride is condensed with -pentylphenothiazine carboxaldehyde to realise a thermally stable twisted organic salt on a gram scale. It appears as a nonmetallic economic salt having an integrated propeller shape with three tub-like cores and displays efficient reversible mechano- and thermo-fluorochromic behaviour. Unlike previous reports, the designed fluorescent, colorimetric thermometer works over a higher temperature range of 130-170 °C with five distinct colour variations.

An unprecedented pyridine-based dinuclear mixed-valent Re oxo-bridged complex: a solvatochromic and AIE-active probe for nanomolar detection of picric acid and trinitrotoluene.

This paper describes the synthesis of an unprecedented oxo-bridged rheniumI/VII (Re) complex by treating Re2(CO)10 with a pyridyl-linked anthracene-based twisted π-conjugated ligand. The molecular structures of both the ligand and the complex are determined by analyzing IR, NMR, and HR-MS spectra and unequivocally determined using single-crystal X-ray diffraction studies. Unlike previous observations, the complexation occurs uniquely to yield an unprecedented oxo-bridged ReI/VII complex.

Binding interactions and FRET between bovine serum albumin and various phenothiazine-/anthracene-based dyes: a structure-property relationship.

The present study demonstrates binding interactions and Förster resonance energy transfer (FRET) between bovine serum albumin (BSA) and a series of structurally and electronically diverse phenothiazine (PTZ) and anthracene (ANT) dyes. Upon selective excitation of tryptophan (Trp) residues of BSA, radiationless energy transfer to a dye takes place, resulting in fluorescence quenching of the former. Fluorescence quenching mechanisms, FRET parameters, possible locations, and binding constants of dyes with the BSA have been examined to deduce a structure-property relationship.

Mechanofluorochromic Anthryl Phosphonate/Benzoic Acid Cocrystals with a Large Blue Shift: The Role of P=O⋅⋅⋅H Interactions.

Organophosphonates have a rich and diverse chemistry, but their mechanofluorochromic features have rarely been documented. Herein, we report on cocrystals of anthranylphosphonate with (E)-4-(2-(anthracen-9-yl)vinyl)benzoic acid that exhibit reversible mechanofluorochromic properties with large blue shifts. Anisotropic grinding (or pressure of just 25 kPa) maintains the co-crystals emission features but leads to a pronounced 59 nm (2087 cm ) blue-shift.

An electron-rich small AIEgen as a solid platform for the selective and ultrasensitive on-site visual detection of TNT in the solid, solution and vapor states.

Promising research on AIEgen (aggregation-induced emission active fluorogens)-based sensors for the detection of explosives (mostly picric acid) is primarily dominated by polymeric molecules. However, herein, we report the ability of a recently developed anthracene-based electron-rich π-conjugate as a small and suitable AIEgen for the selective and sensitive detection of 2,4,6-trinitrotoluene (TNT) through fluorescence (PL) quenching. This fluorophore consists of trimethoxybenzene-linked anthranyl-π-phenothiazine, which is recognized as a significantly electron-rich AIEgen suitable for the selective detection of TNT detection.

Carbazole-Anthranyl π-Conjugates as Small and Stable Aggregation-Induced Emission-Active Fluorogens: Serving as a Reusable and Efficient Platform for Anticounterfeiting Applications with an Acid Key and Multicolor Ink for a Quill Pen.

Being a unique, simple, and inexpensive approach, continuous development on the fluorescence-based technologies remains active in fluorescent anticounterfeiting. A number of polymeric, nano-, carbon dot, and rare-earth oxide materials were preferably explored for such applications, but the complex synthesis, purity, and high cost are the major concerns to make these materials accessible for commercial applications. To address these difficulties, we herein report simple mono-carbazole-linked anthranyl π-conjugates that are synthesized in a gram scale via an inexpensive and convenient route.

Positional Variation of Monopyridyl-N in Unsymmetrical Anthracenyl π-Conjugates: Difference between Solution- and Aggregate-State Emission Behavior.

Fluorescence enhancement on aggregation for π-conjugates linked with pyridyl ring has been established as a part of widely studied smart organic functional materials. Therefore, the photophysical features in the solution and aggregate states for such compounds remain impressive. In this work, we synthesized three series of photostable unsymmetrical aryl-substituted anthracenyl π-conjugates linked to pyridyl ring with a variation of the position of a pyridyl-N atom and examined the difference in the photophysical properties preferably in the aggregate state.

Weak Donor-/Strong Acceptor-Linked Anthracenyl π-Conjugates as Solvato(fluoro)chromophore and AEEgens: Contrast between Nitro and Cyano Functionality.

Steady development on photophysical behaviors for a variety of organic fluorophores inspired us to generate anthracene-based fluorescent molecules with a strong acceptor and a significantly weak donor through a π-spacer. Such molecules are found to have substantial twisted conformational orientations in the solid state and enhanced apolar character because of the attachment of tolyl or mesityl group with an anthracenyl core. Upon exposure to a variety of solvents, strong solvatochromism was noticed for 4-nitro compound (84 nm red shift) in contrast to the cyano analogue (18 nm red shift).

Haloarene-Linked Unsymmetrically Substituted Triarylethenes: Small AIEgens To Detect Nitroaromatics and Volatile Organic Compounds.

Unsymmetrically substituted triarylalkenes as aggregation-induced emission-active fluorogens (AIEgens) are sporadically explored by different researchers. In this Article, naphthalene, biphenyl, and haloarene-linked new triarylethenes are conveniently synthesized and presented as unsymmetrically substituted extensive π-conjugates to continue the discovery of small molecules as new AIEgens. Moreover, fluorophores attached to haloarenes are noteworthy, but such compounds are barely investigated as AIEgens.

An easy access to α-aryl substituted γ-ketophosphonates: Lewis acid mediated reactions of 1,3-diketones with α-hydroxyphosphonates and tandem regioselective C-C bond cleavage.

A range of α-aryl substituted γ-ketophosphonates is synthesised by Lewis acid mediated reactions of 1,3-diketones and easily accessible, inexpensive benzylic α-hydroxyphosphonates in an operationally simple method under solvent-free conditions without exclusion of air/moisture. A regioselective C-C bond cleavage for 1,3-diketones in a tandem fashion has also been demonstrated. Synthesis of a γ-ketophosphonate with phenol functionality at the α-position (structural analogue of raspberry ketone, a natural product) has also been presented.

Cycloaddition reactions of allenylphosphonates and related allenes with dialkyl acetylenedicarboxylates, 1,3-diphenylisobenzofuran, and anthracene.

Cycloaddition reactions of allenylphosphonates [(RO)(2)P(O)[(R(1))C═C═CR(2)(2)] with dialkyl acetylenedicarboxylates, 1,3-diphenylisobenzofuran, and anthracene have been investigated and compared with those of allenoates [(EtO(2)C)RC═C═CH(2)] and allenylphosphine oxides [Ph(2)P(O)(R(1))C═C═CR(2)(2)] in selected cases. Allenylphosphonates (RO)(2)P(O)(Ar)C═C═CH(2) with an α-aryl group preferentially undergo [4 + 2] cycloaddition with DMAD/DEAD under thermal activation, but in addition to the expected 1:1 (allene: DMAD) product, the reaction also leads to 1:2 as well as 2:1 products that were not reported before. When an extra vinyl group is present at the γ-carbon of allenylphosphonate [e.

Molecularly nonstoichiometric crystals in phosphorus compounds.

Molecularly nonstoichiometric crystals obtained as a result of differential occupation of sites with oxygen atom/phosphorus lone pair of electrons or with sulfur/selenium in three sets of phosphorus compounds are described. These are formed by a combination of (a) [CH2(6-t-Bu-4-MeC6H2O)2]PNMe2 (11) and [CH2(6-t-Bu-4-MeC6H2O)2]P(O)NMe2 (13), (b) [CH2(6-t-Bu-4-MeC6H2O)2]P(S)NMe2 (14) and [CH2(6-t-Bu-4-MeC6H2O)2]P(Se)NMe2 (15), and (c) [(2,6-Me2C6H3O)(O)P-micro-N-t-Bu]2 (16) and (2,6-Me2C6H3O)(O)P(micro-N-t-Bu)2P(O-2,6-Me2C6H3) (17). In the case of c, three different types of crystals with varying stoichiometry of 16 and 17 (1:9, 1:1.

Palladium-catalyzed coupling of allenylphosphonates, phenylallenes, and allenyl esters: remarkable salt effect and routes to novel benzofurans and isocoumarins.

Coupling reactions of allenylphosphonates (OCH(2)CMe(2)CH(2)O)P(O)CH=C=CRR' [R, R' = H (1a), R = H, R' = Me (1b), R = R' = Me (1c)] with aryl iodides, iodophenol, and iodobenzoic acid in the presence of palladium(II) acetate are investigated and compared with those of phenylallenes PhCH=C=CR2 [R = H (2a), Me (2b)] and allenyl esters EtO(2)CCH=C=CR(2) [R = H (2c), Me (2d)]. While 1b and 1c couple with different stereochemical outcomes using PhI in the presence of Pd(OAc)(2)/PPh(3)/K(2)CO(3) to give phenyl-substituted 1,3-butadienes, 1a does not undergo coupling but isomerizes to the acetylene (OCH(2)CMe(2)CH(2)O)P(O)CCMe (7). In the reaction of 1c with PhI, use of K(2)CO(3) affords the butadiene (Z)-(OCH(2)CMe(2)CH(2)O)P(O)CH=C(Ph)-C(Me)=CH(2) (12); in contrast, the use of Ag(2)CO(3) leads to the allene (OCH(2)CMe(2)CH(2)O)P(O)C(Ph)=C=CMe(2) (20), showing that these bases differ very significantly in their roles.

Non-stoichiometry induced by differential oxygen/lone pair occupation in chiral bicyclic 1,1'-binaphthoxy cyclodiphosphazanes.

Non-stoichiometry and isostructurality in a set of chiral phosphorus compounds as a result of lone pair/oxygen exchange, substantiated by the combined use of 31P NMR spectroscopy and X-ray crystallography, is described.