Mandapati V. Ramakrishnam Raju

Novel pyrene- and anthracene-based Schiff base derivatives as Cu2+ and Fe3+ fluorescence turn-on sensors and for aggregation induced emissions

Novel pyrene- and anthracene-based Schiff base derivatives P1 and A1 were synthesized via a one-pot reaction and utilized as fluorescence turn-on sensors towards Cu2+ and Fe3+ ions, respectively, and for aggregation induced emissions (AIEs). P1 in CH3CN and A1 in THF illustrated the fluorescence turn-on sensing towards Cu2+ and Fe3+ ions, respectively, via chelation enhanced fluorescence (CHEF) through excimer (P1–P1* and A1–A1*) formation. The 2 : 1 stoichiometry of the sensor complexes (P1 + Cu2+ and A1 + Fe3+) were calculated from Job plots based on UV-Vis absorption titrations. In addition, the binding sites of sensor complexes (P1 + Cu2+ and A1 + Fe3+) were well established from the 1H NMR titrations and supported by the fluorescence reversibility by adding metal ions and PMDTA sequentially. The detection limits (LODs) and the association constant (Ka) values of P1 + Cu2+ and A1 + Fe3+ sensor responses were calculated by standard deviations, linear fittings and from their fluorescence binding isotherms. More importantly, P1 + Cu2+ and A1 + Fe3+ sensors were found to be active in wide ranges of pHs (1–14 and 2–14, respectively). Moreover, the time effect along with the enhancements of quantum yield (Φ) and time resolved photoluminescence (TRPL) decay constant (τ) towards sensor responses were investigated. Similarly, P1 in CH3CN and A1 in THF showed AIEs by increasing the aqueous media concentration from 0% to 90%, with altered fluorescence peak shifts (red and blue shifts, respectively). As well as τ value enhancements, the Φ values of 0.506 and 0.567 (with 630- and 101-fold enhancements) were acquired for P1 in CH3CN : H2O (20 : 80) and A1 in THF : H2O (40 : 60), respectively.

A Novel Diketopyrrolopyrrole (DPP)-Based [2]Rotaxane for Highly Selective Optical Sensing of Fluoride

A novel [2]rotaxane based on an orthogonal H-bonded motif and 3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP) with controlled topicity was successfully constructed, displaying excellent stimulated responses toward anion and solvent polarity. The preorganized host selectively recognized F(-) with high optical sensitivity and reversibility via enhanced positive cooperativity and noncovalent interaction by evidence of a shorter fluorescence lifetime.

Aldehyde Detection in Electronic Cigarette Aerosols

Acetaldehyde, acrolein, and formaldehyde are the principal toxic aldehydes present in cigarette smoke and contribute to the risk of cardiovascular disease and noncancerous pulmonary disease. The rapid growth of the use of electronic cigarettes (e-cigarettes) has raised concerns over emissions of these harmful aldehydes. This work determines emissions of these aldehydes in both free and bound (aldehyde–hemiacetal) forms and other carbonyls from the use of e-cigarettes. A novel silicon microreactor with a coating phase of 4-(2-aminooxyethyl)-morpholin-4-ium chloride (AMAH) was used to trap carbonyl compounds in the aerosols of e-cigarettes via oximation reactions. AMAH–aldehyde adducts were measured using gas chromatography–mass spectrometry. 1H nuclear magnetic resonance spectroscopy was used to analyze hemiacetals in the aerosols. These aldehydes were detected in the aerosols of all e-cigarettes. Newer-generation e-cigarette devices generated more aldehydes than the first-generation e-cigarettes because of higher battery power output. Formaldehyde–hemiacetal was detected in the aerosols generated from some e-liquids using the newer e-cigarette devices at a battery power output of 11.7 W and above. The emission of these aldehydes from all e-cigarettes, especially higher levels of aldehydes from the newer-generation e-cigarette devices, indicates the risk of using e-cigarettes.

Self-Assembly of Tetraphenylethene-Based [2]Catenane Driven by Acid Base-Controllable Molecular Switching and Its Enabled Aggregation-Induced Emission

A novel [2]catenane 2-C based on the tetraphenylethene (TPE) and orthogonal H-bonded cleft was successfully constructed. VT-NMR and TEM measurements demonstrate that 2-C could be self-assembled to induce an enabled aggregation-induced emission (AIE) in aqueous solution and solid state owing to its TPE unit as well as present unique acid-base controllable and reversible supramolecular self-assembled nanosuperstructures by interplay of a wide range of noncovalent interactions.

Acid/Base and H2PO4- Controllable High-Contrast Optical Molecular Switches with a Novel BODIPY Functionalized [2]Rotaxane

A novel multifunctional mechanically interlocked switchable [2]rotaxane R4 containing two molecular stations and rotaxane arms terminated with boron-dipyrromethene (BODIPY) fluorophores and its derivatives were synthesized for the first time by CuAAC click reaction. The shuttling motion of macrocycle between the dibenzylammonium and triazolium recognition sites and the distance dependent photoinduced electron transfer process of R4 is demonstrated by utilizing external chemical stimuli (acid/base). Interestingly, the reversible self-assembly process of R4 was recognized by the acid-base molecular switch strategy. Notably, two symmetrical triazolium groups acted as molecular stations, H2PO4(-) receptors, and H-bonded donors. Both [2]rotaxane R4 and thread R2 demonstrated excellent optical responses and high selectivity toward H2PO4(-) ion. The specific motion and guest-host interactions of mechanically interlocked machines (MIMs) were also further explored by quantum mechanical calculations. The thread R2 also demonstrated to enable the detection of H2PO4(-) in RAW 264.7 cells successfully.

Release-Modulated Antioxidant Activity of a Composite Curcumin-Chitosan Polymer.

Curcumin is known to have immense therapeutic potential but is hindered by poor solubility and rapid degradation in solution. To overcome these shortcomings, curcumin has been conjugated to chitosan through a pendant glutaric anhydride linker using amide bond coupling chemistry. The hybrid polymer has been characterized by UV-visible, fluorescence, and infrared spectroscopies as well as zeta potential measurements and SEM imaging. The conjugation reactivity was confirmed through gel permeation chromatography and quantification of unconjugated curcumin. An analogous reaction of curcumin with glucosamine, a small molecule analogue for chitosan, was performed and the purified product characterized by mass spectrometry, UV-visible, fluorescence, and infrared spectroscopies. Conjugation of curcumin to chitosan has greatly improved curcumin aqueous solubility and stability, with no significant curcumin degradation detected after one month in solution. The absorbance and fluorescence properties of curcumin are minimally perturbed (λmax shifts of 2 and 5 nm, respectively) by the conjugation reaction. This conjugation strategy required use of one out of two curcumin phenols (one of the main antioxidant functional groups) for covalent linkage to chitosan, thus temporarily attenuating its antioxidant capacity. Hydrolysis-based release of curcumin from the polymer, however, is accompanied by full restoration of curcumins antioxidant potential. Antioxidant assays show that curcumin radical scavenging potential is reduced by 40% after conjugation, but that full antioxidant potential is restored upon hydrolytic release from chitosan. Release studies show that curcumin is released over 19 days from the polymer and maintains a concentration of 0.23 ± 0.12 μM curcumin/mg polymer/mL solution based on 1% curcumin loading on the polymer. Release studies in the presence of carbonic anhydrase, an enzyme with known phenolic esterase activity, show no significant difference from nonenzymatic release studies, implying that simple ester hydrolysis is the dominant release mechanism. Conjugation of curcumin to chitosan through a phenol ester modification provides improved stability and solubility to curcumin, with ester hydrolysis restoring the full antioxidant potential of curcumin.

Synthesis of novel platinum complex core as a selective Ag+ sensor and its H-bonded tetrads self-assembled with triarylamine dendrimers for electron/energy transfers

A novel platinum complex PtC with a tri-armed uracil hydrogen-bonded (H-bonded) unit was synthesized via a modular synthetic approach and characterized by 1H, 13C NMR and MALDI-TOF mass spectroscopies. Two H-bonded tetrads, PtC–(TPAD1)3 and PtC–(TPAD2)3, based on a metal core PtC complexed with two generations of triarylamine dendrimers, TPAD1 and TPAD2 (with electron-donating nature), were successfully constructed with improved organic solubility via a classical H-bonded self-assembly approach. Supramolecular H-bonding in solution and solid state was elucidated by 1H NMR titrations, IR spectral studies and time resolved photoluminescence (TRPL) measurements. The electron/energy transfers, as well as the self-assemblies of supramolecular tetrads, were established by UV-Vis and PL titrations and AFM morphological studies. Furthermore, metal complex core PtC showed selective sensitivity towards Ag+ ions through fluorescence turn-off responses without any interference from other common metal ions. The 1 : 1 binding stoichiometry and complexation mechanism between the probe and Ag+ ion was established by 1H NMR titration. Moreover, PL reversibility of PtC + Ag+ could be achieved on addition of PMDTA.

A cyanide-responsive supramolecular nanovalve based on Pd(II)-templated pseudo-rotaxane

We report here the design and synthesis of a nanovalve system consisting of a carrier based on mesoporous silica nanoparticles and mechanized with a square planar Pd(II)-templated pseudo-rotaxane. This nanovalve was responsive to demetalation by cyanide anions, followed by the concomitant release of both the macrocycles and the contents of the pores, in this instance dye indicators. Gate-keeping of the mesopores was achieved by the formation of an intact coordination between the monodentate pyridine axles soluble in aqueous solution and the tridentate macrocycle Pd complex via a square planar metal template approach. A facile nanovalve system responsive to an anionic stimulus was therefore developed. Luminescence spectrometry was successfully used to demonstrate that the anion-stimulated dye release from the nanovalves gated by the Pd(II) metal template was independent of pH.

Electronic nose for detection of toxic volatile organic compounds in air

We demonstrate a general approach using novel thiols to functionalize gold nanoparticles for fabricating gas sensors to detect toxic volatile organic compounds (VOCs) in air. Poor selectivity and low sensitivity are common challenges for chemiresistor-based gas sensors. Gold nanoparticle-based gas sensors have the advantage of accommodating thiols for surface modification. The designed thiols with a molecular recognition motif for interaction with target analytes dramatically increase both selectivity and sensitivity of the sensors. The sensors showed a linear response relationship in a broad vapor concentration range from 0.1 ppb to 1000 ppm for various VOCs. A sensor array of the thiol functionalized gold nanoparticles enables analysis of target VOCs.