Shedding Novel Photophysical Insights Toward Discriminative Detection of Three Toxic Heavy Metal Ions and a hazard class 1 nitro-explosive By Using a Simple AIEE Active Luminogen.

In this work, we introduced a simple aggregation-induced emission enhancement (AIEE) sensor (PHCS) which can selectively detect and discriminate three environmentally and biologically imperative heavy metal ions (Cu2+, Co2+ and Hg2+) and a hazard class 1 categorized nitro-explosive picric acid (PA) in differential media. By virtue of its weak fluorescence attributes in pure organic medium owing to the synergistic operation of multiple photophysical quenching mechanisms, the molecular probe showcased highly selective 'TURN ON' fluorogenic response towards hazardous Hg2+ with a limit of detection (LOD) as low as 97 nM. Comprehensive investigation of binding mechanism throws light on the cumulative effect of probe-metal complexation induced chelation enhanced fluorescence (CHEF) effect and subsequent AIEE activation within the formed probe-metal adducts. Noteworthily, the probe (PHCS) can be readily used in real water samples for the quantitative determination of Hg2+ in a wide concentration range. In addition, the probe displayed modest colorimetric recognition performances to selectively detect and discriminate two essential heavy metal ions (Cu2+ and Co2+) with a LOD of 96 nM and 65 nM for Cu2+ and Co2+ respectively, in semi-aqueous medium. Intriguingly, based on high photoluminescence efficiency, the AIEE active nano-aggregated PHCS displayed a remarkable propensity to be used as a selective and ultra-sensitive 'TURN-OFF' fluorogenic chemosensor towards PA with LOD of 34.4 ppb in aqueous medium. Finally, we specifically shed light on the interaction of PHCS hydrosol towards PA using some unprecedented techniques, which helped uncover new photophysical insights of probe-explosive molecule interaction. We shed light on novel photophysical insights toward unique multifunctional sensory aptitude of a simple aggregation-induced emission enhancement active organic functional molecule in differential media, enabling ultra-sensitive discriminative detection of toxic heavy metal ions and explosive molecule simultaneously.

Thiophene Appended Dual Fluorescent Sensor for Detection of Hg2+ and Cysteamine.

An efficient and highly selective pyrene-thiophene conjugate has been reported as a dual sensor for Hg2+ and cysteamine (an important drug for genetic disorder). The sensor displays a turn-on fluorescence response towards Hg2+ in a 2:1 stoichiometric ratio via excimer formation with a detection limit as low as of 30.6 nM. The excimer emission upon binding with Hg2+ has been rationalized by experimental as well as theoritical studies. Moreover, the [probe-Hg2+] adduct functions as an efficient sensor for cysteamine. This sensing process happens via the extraction of Hg2+ from the adduct. In this paper, change in emission properties of the receptor with varying pH and water content has also been explained. The sensing abilities of the sensor were examined in real water sample analysis. Therefore, the sensor can be used as an efficient and reusable fluorescent sensor for recognition of Hg2+ in water.

A pyrene-based simple but highly selective fluorescence sensor for Cu(2+) ions via a static excimer mechanism.

A pyrene-based simple fluorosensor has been synthesized by a one step process. It exhibited high selectivity towards Cu(2+) ions via fluorescence enhancement of monomer and excimer emission. The origin of excimer formation was examined and established to be of static in nature from the study of absorption and excitation spectra. The observed monomer and excimer emission in the presence and absence of Cu(2+) ion with varying pH was studied and provided probable justification. The effect of varying portions of water content in solvent on the sensor molecule was also examined. The sensor found its proper application in finding accurate and trace amount of Cu(2+) ions present in drinking water samples from various sources. The detection limit of the current sensor was found to be 4 × 10(-8) M.

Rhodamine-based Cu2+-selective fluorosensor: synthesis, mechanism, and application in living cells.

A rhodamine B-based fluorescence probe (1) for the sensitive and selective detection of Cu(2+) ion has been designed and synthesized using pyridine moiety. The optical properties of this compound have been investigated in acetonitrile-water binary solution (7:3 v/v). Compound 1 is found to be an excellent sensor for a biologically/physiologically very important transition metal ion (Cu(2+)) using only the two very different modes of measurements (absorption and emission); one case displayed intensity enhancement whereas in other case showed intensity depletion (quenching). A mechanistic investigation has been performed to explore the static nature of quenching process. The sensor has been found to be very effective in sensing Cu(2+) ion inside living cells also.

Rotational and vibrational cooling in pulsed high-pressure molecular beam expansions from 3 bar into the supercritical regime.

Experiments employing pulsed high-pressure (< or = 90 bar) supersonic jet expansions into a laser REMPI time-of-flight mass spectrometer are presented. Due to the very short opening time of the high-pressure valve, a compact arrangement with moderate pumping speed requirements is sufficient, which can be used up to 50 Hz repetition frequency, still maintaining an operating pressure in the expansion chamber of ca. 10(-4) mbar. p-Fluorotoluene was used as a rotational and vibrational "molecular thermometer" to characterize the cooling capabilities of high-pressure pulsed argon and CO(2) expansions into vacuum, spanning a wide range of stagnation pressures into the supercritical regime. Rotational and torsional temperatures were deduced from the contour of the S(0) --> S(1)(0-0) transition by an asymmetric-top/free-internal-rotor simulation and compared with the results of a simpler rigid-rotor asymmetric-top fit. The experiments show that average rotational temperatures of ca. 1-2 K in argon and 13-15 K in CO(2) can be reached at the highest pressures studied. The population of higher |m| torsional levels of p-fluorotoluene is clearly demonstrated by the appearance of characteristic features on the blue edge of the contours, which are more pronounced in the warmer CO(2) expansions. While the rotational temperatures in argon expansions compare well with estimated gas dynamical terminal translational temperatures, there are considerable differences in the case of CO(2). Still, the degree of internal cooling reached with CO(2) is sufficiently low, so that a setup of this kind might provide good opportunities for future studies of thermally labile low-volatile molecules to cool them to cryogenic temperatures low enough to achieve a sufficient simplification of their spectra.

The long-range π-conjugation between electron-rich species and multiwall carbon nanotubes influences the fluorescence lifetime and electromagnetic shielding.

The efficient dispersion of carbon nanotubes in a given polymer matrix remains an open challenge. Unless addressed, the full potential of carbon nanotubes towards influencing electronic properties of a composite is far from being well understood. Although several reports are available in an open forum that addresses this challenge using various strategies, a mechanistic insight is still lacking. Herein, we have conjugated different electron-rich species with multi-walled carbon nanotubes. We systematically studied their properties by fluorescence lifetime measurements using time-correlated single-photon counting and by density functional theory. Although such conjugations vary with the electronic structure of the electron-rich species, theoretical and computational modeling sheds more light on the actual orientation of such conjugation. Taken together, the fluorescence lifetime and the type of conjugation allowed us to gain mechanistic insight into this conjugation, which further influenced several key properties of the composites. Herein, we attempted to understand these factors influencing the electrical conductivity, and electromagnetic (EM) shielding efficiency in the composite. With the addition of aminoanthracene, which established a T-shaped conjugation with multiwall carbon nanotubes (2 wt%), a remarkable -25 dB shielding effectiveness was achieved with 87% absorption for a shielding material of just 1 mm thick. The actual shielding mechanism, effect of the electronic structure, and the co-relation with the fluorescence lifetime opens new avenues in designing composite-based EM shielding materials.

Specific and nonspecific interactions in a molecule with flexible side chain: 2-phenylethanol and its 1:1 complex with argon studied by high-resolution UV spectroscopy.

Using high-resolution resonance-enhanced two-photon ionization spectroscopy in combination with genetic-algorithm-based computer-aided rotational fit analysis and ab initio quantum chemistry calculations we determined the conformational structure and transition moment orientation in 2-phenylethanol and its 1:1 clusters with argon. The results clearly demonstrate that the gauche structure of 2-phenylethanol, which is stabilized by the intramolecular pi-hydrogen bond between the folded side chain and the benzene ring, is the most abundant in the cold molecular beam. In this conformer the transition moment is rotated by 18 degrees from the short axis of the aromatic ring. Two distinct 1:1 complexes of 2-phenylethanol with argon in a cis- and trans-configuration with respect to the side chain have been found. Employing the Kraitchman [Am. J. Phys. 21, 17 (1953)] analysis we have found that the structure of the 2-phenylethanol moiety and the orientation of the transition moment do not change after the complexation with argon within the experimental accuracy. From the measured band intensities we conclude that in addition to the dispersion interaction of the argon atom with the aromatic ring a hydrogen-bond-type interaction with the terminal -OH group of the side chain stabilizes the cis-structure of the 1:1 complex of 2-phenylethanol with argon.

Fluorescence spectroscopy of jet-cooled chiral (+/-)-indan-1-ol and its cluster with (+/-)-methyl- and ethyl-lactate.

The laser-induced fluorescence excitation, dispersed fluorescence, and IR-UV double resonance spectra of chiral (+/-)-indan-1-ol have been measured in a supersonic expansion. Three low energy conformers of the molecule have been identified, and the ground state vibrational modes of each conformer are tentatively assigned with the aid of quantum chemistry calculations. The frequencies of the nu(OH) and nu(CH) stretch modes of the two most abundant conformers have been measured by fluorescence dip IR spectroscopy and have been used for their assignment. The dispersed fluorescence spectra clearly indicate the coupling of low-frequency modes, as was seen in other substituted indanes such as 1-aminoindan and 1-amino-2-indanol. (R)- and (S)-indan-1-ol distinctly form different types of clusters with (R)- and (S)- methyl- and ethyl-lactate. Both hetero- and homochiral clusters are characterized by complex spectra which exhibit a progression built on low-frequency intermolecular modes.

Impact of extended pi conjugation on methyl rotor-induced IVR in aromatic molecules.

Laser-induced fluorescence excitation and resolved fluorescence spectra following excitations of the single vibronic levels (SVL) of p-vinyltoluene (p-VT) and p-vinylfluorobenzene (p-VFB) have been measured in a seeded supersonic free-jet expansion. A complete vibronic assignment of the fluorescence spectrum measured following excitation of the 0(0)0-band of p-VT has been presented. Normal vibrational modes in the S0 and S1 states of the molecule have been calculated by CASSCF method, and the correlation between the two set of modes is made by expressing the excited-state normal modes in terms of those of the ground state. The calculations predict that in the excited state methyl and vinyl torsional motions of p-VT are extensively mixed with many of the out-of-plane modes of the aromatic ring. Our resolved fluorescence spectral data measured following SVL excitations essentially agree with such predictions. In the excited state, the molecule exhibits a dramatically low threshold for the rotor-induced IVR in a supersonic jet expansion. Several mechanisms have been discussed to explain the phenomenon.