14 research outputs found
Structure and Properties of Double-Sandwich Complexes at the Graphene Surface:A Theoretical Study
Interaction between Small Gold Clusters and Nucleobases: A Density Functional Reactivity Theory Based Study
Rhinosporidiosis of Conjunctiva: A Rare Presentation
Abstract Rhinosporidiosis is a chronic and localized infection of the mucous membrane of nose and paranasal sinuses caused by Rhinosporidium seeberi which is endemic in several parts of India particularly south India but it is rare in north eastern part of India. Ocular rhinosporidiosis is rare with less than 15 % of total cases. It usually presents as polypoidial mass and may mimic clinically as papilloma therefore histopathological diagnosis is crucial for correct diagnosis and treatment. We present a rare case of ocular rhinosporidiosis presenting as a polypoid conjunctival mass from Silchar, Barak valley region of north eastern India
Spintronics on Demand: Optically Tunable Kondo-Type Phenomena in Germanene-Azobenzene Single-Molecule Junctions
This study delves into the exploration of AZB–germanene
composite systems, which are known for their intriguing characteristics,
including the emergence of Kondo features and the precise manipulation
of electronic spin induced by light exposure. The spin-polarized signature
within trans-AZB exerts a significant influence on
the band structure near the Fermi level, highlighting the critical
role of conformational changes within the AZB component in regulating
the magnetoelectronic coupling within the composite system. The research
systematically analyzed the intricate interplay of electronic states
within these systems with a specific focus on the potential observation
of Kondo-like resonance in the trans-AZB–Ge
system, resulting in the development of a spin-polarized electronic
current within the junction. Theoretical insights suggest that the
presence of a Kondo-like effect has the potential to significantly
impact the electronic and magnetic properties of the system, making
it a promising avenue for precise electronic control within the field
of molecular electronics
An Iminosemiquinone-Coordinated Oxidovanadium(V) Complex: A Combined Experimental and Computational Study
Ligand
H<sub>4</sub>Sar<sup>(AP/AP)</sup> contained two terminal amidophenolate
units that were connected by a disulfane bridge. The ligand reacted
with VOSO<sub>4</sub>·5H<sub>2</sub>O in the presence of Et<sub>3</sub>N under air and provided a mononuclear octahedral oxidovanadium
complex (<b>1</b>). X-ray crystal structure analysis of complex <b>1</b> revealed that the oxidation state of the V ion was V and
the VO<sup>3+</sup> unit was coordinated to an iminosemiquinone radical
anion. An isotopic signal at <i>g</i> = 1.998 in the X-band
electron paramagnetic resonance (EPR) spectrum and the solution magnetic
moment μ<sub>eff</sub> = 1.98 μ<sub>B</sub> at 298 K also
supported the composition. The formation of complex <b>1</b> preceded through the initial generation of a diamagnetic VO<sup>2+</sup>–iminoisemiquinone species, as established by time-dependent
UV–vis–near-IR (NIR), X-band EPR, and density functional
theory studies. The UV–vis–NIR spectrum of complex <b>1</b> consisted of four ligand-to-metal charge-transfer transitions
in the visible region, while an intervalence ligand-to-ligand charge
transfer appeared at 1162 nm. The cyclic voltammogram of the complex
showed four oxidation waves and one reduction wave. Spectroelectrochemical
studies at fixed potentials revealed that the oxidation and reduction
processes were ligand-based
Highly Selective Detection of H<sup>+</sup> and OH<sup>–</sup> with a Single-Emissive Iridium(III) Complex: A Mild Approach to Conversion of Non-AIEE to AIEE Complex
A greenish-blue emissive bis-cyclometalated
iridiumÂ(III) complex
with octahedral geometry was synthesized in a convenient route where
a bulky substituted ligand, <i>N</i><sup>1</sup><b>-</b>tritylethane-1,2-diamine ligand (trityl-based rotating unit) (<b>L</b><sub><b>1</b></sub>), was coordinated to iridiumÂ(III)
in nonchelating mode, [IrÂ(F<sub>2</sub>ppy)<sub>2</sub>(L<sub>1</sub>)Â(Cl)], [F<sub>2</sub>ppy = 2-(2′,4′-difluoro)Âphenylpyridine; <b>L</b><sub><b>1</b></sub> = <i>N</i><sup>1</sup>-tritylethane-1,2-diamine], <b>1</b>. The purpose of introducing
a rotor in <b>1</b> was anticipated to initiate aggregation-induced
emission (AIE) activity in it. The presence of a secondary amine in <b>L</b><sub><b>1</b></sub> has attributed to <b>1</b> the ability to sense acids. The mechanism of this change in <b>1</b> under acidic medium was explored. A bright yellow emissive
complex was formed on exposing <b>1</b> to hydroxide ion, which
was isolated, characterized, and identified as a new aggregation-induced
enhanced emission (AIEE) active complex. The detection limit of hydroxide
ion was determined to 126 nM. Ground- and excited-state properties
of <b>1</b> were investigated using DFT- and TD-DFT-based calculations,
and several important aspects of the experimental facts were validated
Highly Selective Detection of H<sup>+</sup> and OH<sup>–</sup> with a Single-Emissive Iridium(III) Complex: A Mild Approach to Conversion of Non-AIEE to AIEE Complex
A greenish-blue emissive bis-cyclometalated
iridiumÂ(III) complex
with octahedral geometry was synthesized in a convenient route where
a bulky substituted ligand, <i>N</i><sup>1</sup><b>-</b>tritylethane-1,2-diamine ligand (trityl-based rotating unit) (<b>L</b><sub><b>1</b></sub>), was coordinated to iridiumÂ(III)
in nonchelating mode, [IrÂ(F<sub>2</sub>ppy)<sub>2</sub>(L<sub>1</sub>)Â(Cl)], [F<sub>2</sub>ppy = 2-(2′,4′-difluoro)Âphenylpyridine; <b>L</b><sub><b>1</b></sub> = <i>N</i><sup>1</sup>-tritylethane-1,2-diamine], <b>1</b>. The purpose of introducing
a rotor in <b>1</b> was anticipated to initiate aggregation-induced
emission (AIE) activity in it. The presence of a secondary amine in <b>L</b><sub><b>1</b></sub> has attributed to <b>1</b> the ability to sense acids. The mechanism of this change in <b>1</b> under acidic medium was explored. A bright yellow emissive
complex was formed on exposing <b>1</b> to hydroxide ion, which
was isolated, characterized, and identified as a new aggregation-induced
enhanced emission (AIEE) active complex. The detection limit of hydroxide
ion was determined to 126 nM. Ground- and excited-state properties
of <b>1</b> were investigated using DFT- and TD-DFT-based calculations,
and several important aspects of the experimental facts were validated
A Bis(Aquated) Mn(II)-Based MRI Contrast Agent with a Rigid Hydroquinazoline Unit: Synthesis, Characterization, and <i>in Vivo</i> MR Imaging Study
Since
the finding of nephrogenic systemic fibrosis (NFS) in patients
with renal impairment and the long-term accumulation of Gd(III) ions
in the central nervous system, the search for nongadolinium ion-based
MRI contrast agents made of nutrient metal ions has drawn paramount
attention. In this context, the development of Mn(II)-based MRI contrast
agents has been a subject of interest for the last few decades. Herein,
we report a pentadentate ligand (Li2[BenzPic2]) composed of two picolinate moieties and a rigid 1,2,3,4-tetrahydroquinazoline
unit and the corresponding bis(aquated) Mn(II) complex (Complex 1). The complex exhibited high thermodynamic stability (log Kcond = 11.62) and kinetic inertness similar
to that of the clinically approved Gd(III)-based contrast agent Magnevist.
Complex 1 exerted longitudinal relaxivity (r1) of 5.32 mM–1 s–1 at 1.41 T, 37 °C, pH 7.4, and it increased by 3.6-fold in the
presence of serum albumin protein, confirming a substantial rigidifying
interaction (albumin association constant KA = 1.66 × 103 M–1) between the
protein and the amphiphilic (log P = −0.45)
contrast agent. An intravenous dose of 0.08 mmol/kg in a healthy mouse,
excellent MRI signal intensity enhancement in the vasculature of the
mouse liver, and brightened images of the gallbladder, kidney, and
liver were realized
A New Bis(aquated) High Relaxivity Mn(II) Complex as an Alternative to Gd(III)-Based MRI Contrast Agent
Disclosed here are a piperazine,
a pyridine, and two carboxylate groups containing pentadentate ligand
H<sub>2</sub>pmpa and its corresponding water-soluble MnÂ(II) complex
(<b>1</b>). DFT-based structural optimization implied that the
complex had pentagonal bipyramidal geometry where the axial positions
were occupied by two water molecules, and the equatorial plane was
constituted by the ligand ON<sub>3</sub>O donor set. Thus, a bisÂ(aquated)
disc-like MnÂ(II) complex has been synthesized. The complex showed
higher stability compared with MnÂ(II)–EDTA complex [log<i>K</i><sub>MnL</sub> = 14.29(3)] and showed a very high <i>r</i><sub>1</sub> relaxivity value of 5.88 mM<sup>–1</sup> s<sup>–1</sup> at 1.41 T, 25 °C, and pH = 7.4. The relaxivity
value remained almost unaffected by the pH of the medium in the range
of 6–10. Although the presence of 200 equiv of fluoride and
bicarbonate anions did not affect the relaxivity value appreciably,
an increase in the value was noticed in the presence of phosphate
anion due to slow tumbling of the complex. Cell viability measurements,
as well as phantom MR images using clinical MRI imager, consolidated
the possible candidature of complex <b>1</b> as a positive contrast
agent