No abstract

Carbon atoms have the potential to produce a variety of fascinating all-carbon structures with amazing electronic and mechanical properties. Over the last few decades, several efforts have been made using experimental and computational techniques to functionalize graphene, carbon nanotubes and fullerenes for potential use in modern hi-tech electronic, medicinal, optical and nonlinear optical (NLO) applications. Since photons replaced electrons as a carrier of information, the field of NLO material design has drawn immense interest in contemporary materials science. There have been several reports of bridging the gap between the exciting fields of carbon nanomaterials and NLO materials by functionalizing carbon nanomaterials for potential NLO applications. In contrast to previous reports of the design of third-order NLO materials using conventional closed-shell materials, a novel strategy using open-shell diradical molecular systems has recently been proposed. Quantum chemically, diradical character is explained in terms of the instability of the chemical bonds in open-shell molecular systems. Interestingly, several carbon nanomaterials, which naturally possess open-shell singlet configurations, have recently gained momentum in the design of these classes of open-shell NLO materials with excellent NLO properties, stability and diversity. The present review establishes a systematic sequence of different studies (spanning over two decades of intense research efforts), starting from the simplest theoretical two-site diradical model, continuing to its experimental and theoretical realization in actual chemical systems, and finally applying the abovementioned model/rule to novel carbon nanomaterials to tune their NLO properties, particularly their second hyperpolarizability (γ). In the present report, we highlight several recent efforts to functionalize carbon nanomaterials by exploiting their open-shell diradical character to achieve efficient third-order NLO properties. Several issues and opportunities are discussed, including the inherited disadvantages of both experimental (the high reactivity and short life of diradical compounds) and quantum (need for multi-reference methodology) techniques when dealing with carbon nanomaterials. A comparative analysis of several quantum chemical investigations, along with contemporary experimental results, will be performed to emphasize the core issues and opportunities related to carbon nanomaterials with singlet open-shell diradical character. Thus, the present review will highlight carbon nanomaterials with diradical/biradical character for their prospective applications in the NLO field.

No abstract

Molecular engineering of triphenylamine (TPA) units produced multi-stimuli-responsive solid state fluorescent materials.

No abstract

In the present investigation, for the first time, we have performed a thorough study about different functionals and basis sets for linear and nonlinear optical (NLO) properties of para-nitroaniline ([Formula: see text]-NA), which is considered as proto-type NLO molecule, among organic NLO materials. There is a dire need of such data base for [Formula: see text]-NA because many investigators are using such values of [Formula: see text]-NA for comparative analysis. A range of different functionals including HF, BLYP, PW91, PBE, B3LYP, M06, M06-2X, PBE0, BHandHLYP, CAM-B3LYP, LC-BLYP, and B3LYP-D3 are applied in conjugation with several commonly basis sets such as 6-31G*, 6-311G*, 6-311G**, 6-311+G**, cc-pVDZ, and cc-pVTZ. A variety of functional and basis sets combinations are calculated and graphically compared with each other. The calculated total dipole moment for the [Formula: see text]-NA is found to be 6.79[Formula: see text]D which is quite closer to experimentally determined value. The lowest calculated value for linear isotropic polarizability at HF/6-31G* level of theory is [Formula: see text] esu while higher values observed with remaining all methods especially 14% polarizability increases in presence of basis set with diffuse functions and similar trend of variation is also observed in linear anisotropic polarizability. Similarly, the calculated value of frequency dependent second-order polarizability is found to be [Formula: see text] esu at PBE0/6-311+G** level of theory which is quite closer to experimental value of [Formula: see text] esu. A comparison between the calculated and experimental results shows good agreement among geometries, dipole moments and NLO polarizabilities for [Formula: see text]-NA. Moreover, the frontier molecular orbital (FMO) and electron density difference map (EDDM) analysis along with density of state (DOS) plots are also presented to get more physical intuitions into the structure–property relationship and electronic communications between terminal accepter and donor groups through [Formula: see text]-conjugation. The present investigation provides benchmark data including various commonly used functionals and basis sets for the calculation of NLO properties of [Formula: see text]-NA. Thus, the present investigation will put straight several future studies when it comes to comparative NLO study of organic materials.

The outbreak of the COVID-19 pandemic is partially due to the challenge of identifying asymptomatic and pre-symptomatic carriers of the virus, and thus highlights a strong motivation for diagnostics that can be rapidly deployed with high sensitivity. On the other hand, several concerned SARS-CoV-2 variants, including the Omicron, are required to be identified as soon as the samples are identified as ‘positive’. Unfortunately, a traditional PCR test does not allow their specific identification. Herein, for the first time, we have developed MOPCS (Methodologies of Photonic CRISPR Sensing), which combines an optical sensing technology-surface plasmon resonance (SPR), and the ‘gene scissors’ CRISPR technique to achieve both high sensitivity and specificity of viral variants’ measurement. MOPCS is a low-cost, CRISPR/Cas12a system-empowered SPR gene detecting platform that can analyze viral RNA, without the need for amplification, within 38 min from sample input to results output, and achieve a limit of detection of 15 fM. MOPCS achieves a highly sensitive analysis of SARS-CoV-2 and mutations appear in variants B.1.617.2 (Delta), B.1.1.529 (Omicron), and BA.1 (a subtype of Omicron). This platform was also used to analyze some recently collected patient samples from a local outbreak in China and identified by the Centers for Disease Control and Prevention. This innovative CRISPR-empowered SPR platform will further contribute to various fast, sensitive, and accurate detection of target nucleic acid sequences with single-base mutations.

Substitutional change and controlling intra and intermolecular interactions of ESIPT molecules resulted in realizing multifunctional fluorescence properties.