Ionic Assembly,Anion–π, Magnetic,and Electronic Attributes of Ambient Stable Naphthalenediimide Radical Ions

Organic spin-based molecular materials are considered to be attractive for the generation of functional materials with emergent optoelectronic, magnetic, or magneto-conductive properties. However, the major limitations to the utilization of organic spin-based systems are their high reactivity, instability, and propensity for dimerization. Herein, we report the synthesis, characterization, and magnetic and electronic studies of three ambient stable radical ions ( 1 a^.+ , 1 b^.+ , and 1 c^.+ ). The radical ions 1 b^.+ and 1 c^.+ with BPh₄⁻ and BF₄⁻ counter anions, respectively, were synthesized in excellent yields by means of anion metathesis of 1 a^.+ with Br⁻ as its counter anion. Notably, synthesis of 1 a^.+ was achieved in an ecofriendly, solvent-free protocol. The radical ions were characterized by means of single-crystal X-ray diffraction studies, which revealed the discrete nature of the radical ions and extensive hydrogen-bonding interactions within the radical ions and with the counter anions. Thus, radical ions can be organized to form infinite supramolecular arrays using weak noncovalent interactions. In addition, the Br⁻, BF₄⁻, and BPh₄⁻ anions formed diverse types of anion–π interactions with the naphthalene and imide rings of the radical ions. The radical ions were characterized by means of X-band electron paramagnetic resonance (EPR) spectroscopy in solution and in the solid state. Magnetic studies revealed their paramagnetic nature in the range of 10 to 300 K. The radical ions exhibited high resistivity approaching the gigaohm (GΩ) scale. In addition, the radical ions exhibited panchromism.     

Design and Synthesis of Imidazole and Triazole Pyrazoles as Mycobacterium Tuberculosis CYP121A1 Inhibitors

The emergence of untreatable drug-resistant strains of Mycobacterium tuberculosis is a major public health problem worldwide, and the identification of new efficient treatments is urgently needed. Mycobacterium tuberculosis cytochrome P450 CYP121A1 is a promising drug target for the treatment of tuberculosis owing to its essential role in mycobacterial growth. Using a rational approach, which includes molecular modelling studies, three series of azole pyrazole derivatives were designed through two synthetic pathways. The synthesized compounds were biologically evaluated for their inhibitory activity towards M. tuberculosis and their protein binding affinity (K_D). Series 3 biarylpyrazole imidazole derivatives were the most effective with the isobutyl ( 10 f ) and tert-butyl ( 10 g ) compounds displaying optimal activity (MIC 1.562 μg/mL, K_D 0.22 μM ( 10 f ) and 4.81 μM ( 10 g )). The spectroscopic data showed that all the synthesised compounds produced a type II red shift of the heme Soret band indicating either direct binding to heme iron or (where less extensive Soret shifts are observed) putative indirect binding via an interstitial water molecule. Evaluation of biological and physicochemical properties identified the following as requirements for activity: LogP >4, H-bond acceptors/H-bond donors 4/0, number of rotatable bonds 5–6, molecular volume >340 ų, topological polar surface area <40 Ų.     

Direct Hydrogenation of Nitroaromatics at Room Temperature Catalyzed by Magnetically Recoverable Cu@Fe2O3 Nanoparticles

Metal embedded in metal oxide nanoparticles are active as catalyst in plethora of industrially important reactions. Herein, embedded Cu@Fe₂O₃ nanoparticles was synthesized via a one step hydrothermal strategy which selectively catalyzes the hydrogenation of diverse nitroaromatics in H₂O at room temperature. The remarkable catalytic performance is due to the successful hybridization of metallic Cu and Fe₂O₃ which in turn allows easy electroflipping between various oxidation states of Cu and Fe. Azo- and azoxy-compounds are not formed during the catalyzed process. This evidently establish that the hydrogenation of nitroaromatics proceeds via direct route with >99% selectivity to the corresponding anilines.     

Quantitative Analysis of Phytochemicals from Inula cappa Roots

JPC – Journal of Planar Chromatography – Modern TLC - Inula cappa (family Compositae) is used in the Ayurvedic medicinal system for the treatment of bronchitis, diabetes, fever,...     

Control over Kinetic and Thermodynamically Driven Pathways of Crystallization to Yield Cofacial and Slipped-Stack Dimers in Single Crystals

Control over the molecular packing in the solid state is of utmost importance in regulating the bulk optical properties of organic semiconductors. The electronic coupling between the molecules makes it possible to improve the properties of the bulk materials. This work reports an example of control over the selective formation of polymorphic single crystals of donor–acceptor-type small-molecule compound 25TR by 1) kinetic or 2) thermodynamic course of crystallisation to yield slipped stack (S) and cofacial (C) dimers in the single crystals. The distinct optical characteristics of the C-dimer and S-dimer are summarised. Both forms show significant excitonic interactions in the solid state, and the S-dimeric form has strong yellowish orange fluorescence, whereas the C-dimeric form is non-fluorescent in the crystalline state. DFT calculations and differential scanning calorimetric experiments revealed that the C-dimer polymorph is the thermodynamically stable form with a free energy offset of 0.43 eV in comparison with the S-dimer. Interestingly, the thermodynamically driven non-fluorescent single crystal was found to be convertible to its fluorescent form irreversibly by thermal trigger. The charge-carrier-transport characteristics of these two polymorphs were computed by using the Marcus–Hush formalism. The computations of the charge-carrier-transport behaviour revealed that the S-dimer ( 25TR_(R) ) is ambipolar, whereas the C-dimer ( 25TR_(Y) ) is predominantly n-type.     

Spectrophotometric Label-Free Determination of Lead Using Thiol-Functionalized Gold Nanoparticles

A method for the determination of lead is described using thiol-functionalized gold nanoparticle. The detection method is based on the prevention of thiol-induced aggregation of gold nanoparticles by lead. Among six thiols, e.g., 4-mercapto-1-butanol, meso-2, 3-dimercaptosuccinic acid, mercaptosuccinic acid, 6-mercapto-1-hexanol, 4-(methylthio)-1-butanol, 1-propanethiol, four (4-mercapto-1-butanol, 6-mercapto-1-hexanol, 4-(methylthio)-1-butanol and 1-propanethiol) induced the aggregation of the gold nanoparticles which was measured by the change in absorbance at 520 and 650?nm. Prior incubation of the gold nanoparticles with lead decreased the 4-(methylthio)-1-butanol-induced aggregation of gold nanoparticles in a dose-dependent manner. A linear inverse relationship between the logarithmic concentration of lead and the ratio of absorbance at 650 to 520 was noted. The method has a dynamic range from 10?nM to 100?µM. However, metals such as mercury and chromium were more effective in comparison with lead in preventing the 4-methylthio-1-butanol-induced aggregation of gold nanoparticles. The method can be used for assessing the heavy metal load in water samples.     

Organocatalytic mediated green approach: A versatile new L-valine promoted synthesis of diverse and densely functionalized 2-amino-3-cyano-4H-pyrans

The discovery of a new L-valine promoted facile and versatile green synthesis of diversified 2-amino-3-cyano-4H-pyrans using a one pot multicomponent-tandem reaction of aromatic aldehydes, malononitrile, and diverse electron-rich enolizable carbonyl compounds is described. To the best of our knowledge this is the first report on the use of native L-valine as a catalyst in organic synthesis. Environmental friendly, mild reaction conditions, use of easily available inexpensive starting materials, short reaction time, excellent yields, high atom economy, and recyclability of organocatalyst are the major advantages of the disclosed protocol.     

An efficient chemoselective etherification of phenols in polyfunctional aromatic compounds

A simple and efficient chemoselective alkylation of phenols in polyfunctional aromatic compounds with different alkyl halides in the presence of K₂CO₃/TBAB is reported. The method is successful with various hydroxy aromatic acids or oximes possessing other functional groups.