Publications by authors named "Rajneesh Misra"

Background: There are still no consensus criteria on how to select the lower instrumented vertebra (LIV) for growing rods (GRs) at index surgery. The aim was to evaluate whether the criteria used for adolescent idiopathic scoliosis fusion adapts to early-onset scoliosis (EOS).

Materials And Methods: Retrospective analysis of prospectively collected data in a consecutive cohort of patients with EOS treated with GR, expanding from index surgery to 2 years after graduation.

View Article and Find Full Text PDF

A set of naphthalimide functionalized push-pull chromophores NPI 1-3 were designed and synthesized via Pd-catalyzed Sonogashira cross-coupling followed by [2 + 2] cycloaddition-electrocyclic ring-opening reaction. The 1,8-naphthalimide (NPI) and 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) moiety acts as an acceptor unit, whereas phenothiazine (PTZ) unit acts as a donor unit. Their photophysical, electrochemical properties, and charge carrier mobilities were investigated.

View Article and Find Full Text PDF

Nanotechnology is transforming contemporary medicine by providing cutting-edge tools for the treatment and diagnosis of complex disorders. Advanced techniques such as bioimaging and photodynamic therapy (PDT) combine early diagnosis and targeted therapy, offering a more precise approach than conventional treatments. However, a significant obstacle for PDT is the need to selectively deliver photosensitizers to disease sites while minimizing systemic side effects.

View Article and Find Full Text PDF

Among the several exceptional properties of fullerene, C, its electron acceptor property is a highly studied topic. This work demonstrates the superior electron acceptor property of C, even in the presence of a stronger electron acceptor(s) in multi-modular donor-acceptor constructs. For this, novel bis-phenothiazine-C donor-acceptor conjugates incorporating strong electron acceptors, tetracyanobutadiene (TCBD) or dicyanoquinodimethane (DCNQ), have been newly synthesized.

View Article and Find Full Text PDF

Understanding how electronic energy is funnelled towards a specific location in a large conjugated molecule is of primary importance for the development of a site-specific photochemistry. To this end, we investigate here how electronic excitation redistributes spatially in a series of electron donor-acceptor (D-A) molecules containing two different donors, D and D', and organised in both linear D-A-D' and symmetric double-branch D'-A-D-A-D' geometries. Using transient IR absorption spectroscopy to probe the alkyne spacers, we show that for both types of systems in non-polar solvents, excitation remains delocalised over the whole molecule.

View Article and Find Full Text PDF

The significance of perylenediimide (PDI) in promoting excited charge transfer in push-pull systems carrying TCBD-TPA and DCNQ-TPA, synthesised Pd(II)-catalysed Sonogashira cross-coupling reaction followed by [2+2] cycloaddition retroelectrocyclization (CA-RE) reaction, is demonstrated using femtosecond transient absorption and other pertinent methods.

View Article and Find Full Text PDF

A set of ferrocenyl functionalized phenothiazine derivatives Fc1-4 were designed and synthesized Pd-catalyzed Buchwald-Hartwig and Suzuki cross-coupling reactions. Phenothiazine was used as a central donor and ferrocenyl as a terminal donor unit. Herein we examine the impact of variation of substituents at the -position of phenothiazine, including H, phenyl, phenyl-linked ferrocenyl, and biphenyl-linked ferrocenyl units on the photophysical, electrochemical, and thermal behaviors.

View Article and Find Full Text PDF

Molecules exhibiting phosphorescence emission, with variation in its emission wavelength or intensity upon external mechanical force, are known as a phosphorescent mechanochromic materials (PMC). This review focuses on the development of organic mechanophosphorescent molecules and their emission in response to a mechanical stimulus, which can be used as smart materials in the field of luminescent switches, mechanosensors, security papers, data storage, and biological applications. In addition, the review provides clear understanding of underlying mechanism, exploring how the intermolecular interactions, crystal packing and suitable molecular design facilitate the RTP enhancement.

View Article and Find Full Text PDF

A set of ferrocene-functionalized phenothiazine (PTZ) derivatives 1-3 was designed and synthesized the Pd-catalyzed Buchwald-Hartwig cross-coupling reaction in good yields. 1-3 were treated with -chloroperbenzoic acid (-CPBA), which oxidizes the sulfur (S) atom in the thiazine ring to a sulfone, resulting in ferrocene substituted phenothiazine sulfone derivatives 4-6. The influence of the sulfur (S) oxidation state on the photophysical, redox, and spectroelectrochemical properties, and thermal stability of the phenothiazine and phenothiazine sulfone derivatives, containing the ferrocene unit at the , , and positions of the phenylene ring attached to the -position of phenothiazine and phenothiazine sulfone, was examined.

View Article and Find Full Text PDF

Mechanofluorochromic (MFC) materials are emerging as a versatile candidate for optoelectronic and biomedical applications. In the present work, we designed and synthesized four MFC materials, namely BT-PTZ-1, BT-PTZ-2, BT-PTZO-1, and BT-PTZO-2, using Suzuki cross-coupling reaction. These materials possess benzothiazole (BT) as an acceptor moiety and different donors, including phenothiazine (PTZ) and triphenylamine (TPA), with variations in their spacer units.

View Article and Find Full Text PDF

The pH effect on the photophysics of three push-pull compounds bearing dimethoxytriphenylamine (TPA-OMe) as electron donor and pyridine as electron acceptor, with different ortho-functionalization (-H, -Br, and -TPA-OMe), is assessed through steady-state and time-resolved spectroscopic techniques in DMSO/water mixed solutions and in water dispersions over a wide pH range. The enhanced intramolecular charge transfer upon protonation of the pyridinic ring leads to the acidochromic (from colorless to yellow) and acido(fluoro)chromic (from cyan to pink) behaviours of the investigated compounds. In dilute DMSO/buffer mixtures these molecules exhibited low pK values (≤3.

View Article and Find Full Text PDF

A set of ferrocenyl-functionalized perylenediimide (PDI) compounds and their 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) derivatives 1-5 were designed and synthesized using palladium-catalyzed Sonogashira cross-coupling, followed by a thermally activated [2 + 2] cycloaddition-retroelectrocyclization [CA-RE] reaction with a 1,1,2,2-tetracyanoethylene (TCNE) acceptor in good yields. The TCBD group works as an acceptor, whereas the ferrocenyl group acts as a donor at the central PDI core. The effects of varying the number of ferrocenyl and TCNE groups on the photophysical, thermal, electrochemical, and spectroelectrochemical properties were studied.

View Article and Find Full Text PDF
Article Synopsis
  • Researchers have synthesized push-pull compounds using naphthalimide as an electron acceptor and TPE/TPA/PTZ as electron donors, forming well-conjugated quadrupolar structures.
  • Time-resolved spectroscopic techniques show that these compounds exhibit rapid charge transfer and efficient spin-orbit charge transfer-induced intersystem crossing, particularly in TPA- and PTZ-based variations.
  • The study indicates that incorporating these fluorophores into solid-state host matrices significantly enhances thermally activated delayed fluorescence (TADF), producing strong emission in the orange-red region and suggesting potential for efficient TADF-based OLED applications.
View Article and Find Full Text PDF

Near-infrared (NIR) absorbing electron donor-acceptor (D-A) chromophores have been at the forefront of current energy research owing to their facile charge transfer (CT) characteristics, which are primitive for photovoltaic applications. Herein, we have designed and developed a new set of benzothiadiazole (BTD)-based tetracyanobutadiene (TCBD)/dicyanoquinodimethane (DCNQ)-embedded multimodular D-A systems (BTD1-BTD6) and investigated their inherent photo-electro-chemical responses for the first time having identical and mixed terminal donors of variable donicity. Apart from poor luminescence, the appearance of broad low-lying optical transitions extendable even in the NIR region (>1000 nm), particularly in the presence of the auxiliary acceptors, are indicative of underlying nonradiative excited state processes leading to robust intramolecular CT and subsequent charge separation (CS) processes in these D-A constructs.

View Article and Find Full Text PDF

Introduction: Thoracic myelopathy in neuro fibromatosis-1 (NF-1) is most commonly due to intra-spinal neurofibromas/dumb-bell tumors/intra-canal rib head penetration (RHP) causing cord compression. However, acute thoracic myelopathy due to rapid progression of the kyphoscoliotic curve alone in NF-1 without a significant spinal cord compression occurs very rarely. This case report discusses our experience with one such patient and we also discuss intraoperative and post-operative challenges encountered with this patient and a rare complication of hemothorax postoperatively.

View Article and Find Full Text PDF

Organic dyes that absorb light in the visible to near-infrared region have garnered significant interest, owing to their extensive utility in organic photovoltaics and various biomedical applications. Aza-boron-dipyrromethene (Aza-BODIPY) dyes are a class of chromophores with impressive photophysical properties such as tunable absorption from the visible region towards near infrared (NIR) region, high molar absorptivity, and fluorescence quantum yield. In this review, we discuss the developments in the aza-BODIPYs, related to their synthetic routes, photophysical properties and their applications.

View Article and Find Full Text PDF

Unraveling the intriguing aspects of the intramolecular charge transfer (ICT) phenomenon of multi-modular donor-acceptor-based push-pull systems are of paramount importance considering their promising applications, particularly in solar energy harvesting and light-emitting devices. Herein, a series of symmetrical and unsymmetrical donor-acceptor chromophores 1-6, are designed and synthesized by the Corey-Fuchs reaction via Evano's condition followed by [2+2] cycloaddition retroelectrocyclic ring-opening reaction with strong electron acceptors TCNE and TCNQ in good yields (~60-85 %). The photophysical, electrochemical, and computational studies are investigated to explore the effect of incorporation of strong electron acceptors 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) and dicyanoquinodimethane (DCNQ) with phenothiazine (PTZ) donor.

View Article and Find Full Text PDF

A series of near-IR absorbing 2,6-diarylated BF-chelated aza-boron-dipyrromethenes (aza-BDPs) derivatives bearing different electron donors (benzene, naphthalene, phenanthrene, phenothiazine and carbazole) were designed and synthesized. The effect of different electron donor substitutions on the photophysical properties was studied by steady-state UV-vis absorption and fluorescence spectra, electrochemical, time-resolved nanosecond transient absorption (ns-TA) spectroscopy and theoretical computations. The UV-vis absorption spectra of AzaBDP-PTZ and AzaBDP-CAR (λ=710 nm in toluene) showed a bathochromic absorption profile compared with the reference AzaBDP-Ph (λ=685 nm in toluene), indicating the non-negligible electronic interaction at the ground state between donor and acceptor moieties.

View Article and Find Full Text PDF

A series of symmetrical and unsymmetrical donor-acceptor type phenothiazine derivatives - were designed and synthesized via Pd-catalyzed Sonogashira cross-coupling and [2 + 2] cycloaddition-retroelectrocyclization reactions. The incorporation of cyano-based acceptors 1,1,4,4-tetracyanobutadiene (TCBD) and dicyanoquinodimethane (DCNQ) in the phenothiazine derivatives resulted in systematic variation in the photophysical, thermal, and electrochemical properties. The electronic absorption spectra of the phenothiazine derivatives with strong acceptors , , , , , , , , , , , and show red-shifted absorption as compared to phenothiazine derivatives , , , , , and in the near-IR region due to a strong intramolecular charge transfer (ICT) transition.

View Article and Find Full Text PDF

Singlet oxygen (O) producing photosensitizers are highly sought for developing new photodynamic therapy agents and facilitating O-involved chemical reactions. Often singlet oxygen is produced by the reaction of triplet-excited photosensitizers with dioxygen via an energy transfer mechanism. In the present study, we demonstrate a charge transfer mechanism to produce singlet oxygen involving push or pull functionalized porphyrins.

View Article and Find Full Text PDF

Using the popular metal-ligand axial coordination self-assembly approach, donor-acceptor conjugates have been constructed using zinc tetrapyrroles (porphyrin (ZnP), phthalocyanine (ZnPc), and naphthalocyanine (ZnNc)) as electron donors and imidazole functionalized tetracyanobutadiene (Im-TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded-tetracyanobutadiene (Im-DCNQ) as electron acceptors. The newly formed donor-acceptor conjugates were fully characterized by a suite of physicochemical methods, including absorption and emission, electrochemistry, and computational methods. The measured binding constants for the 1 : 1 complexes were in the order of 10 -10  M in o-dichlorobenzene.

View Article and Find Full Text PDF

To solve the toxicity issues related to lead-based halide perovskite solar cells, the lead-free double halide perovskite CsAgBiBr is proposed. However, reduced rate of charge transfer in double perovskites affects optoelectronic performance. We designed a series of pyridine-based small molecules with four different arms attached to the pyridine core as hole-selective materials by using interface engineering.

View Article and Find Full Text PDF

A far-red absorbing sensitizer, BF -chelated azadipyrromethane (azaBODIPY) has been employed as an electron acceptor to synthesize a series of push-pull systems linked with different nitrogenous electron donors, viz., N,N-dimethylaniline (NND), triphenylamine (TPA), and phenothiazine (PTZ) via an acetylene linker. The structural integrity of the newly synthesized push-pull systems was established by spectroscopic, electrochemical, spectroelectrochemical, and DFT computational methods.

View Article and Find Full Text PDF

The excited-state properties of an asymmetric triphenylamine-quinoxaline push-pull system wherein triphenylamine and quinoxaline take up the roles of an electron donor and acceptor, respectively, are initially investigated. Further, in order to improve the push-pull effect, powerful electron acceptors, viz., 1,1,4,4-tetracyanobutadiene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded tetracyanobutadiene (also known as expanded-TCBD or exTCBD), have been introduced into the triphenylamine-quinoxaline molecular framework using a catalyst-free [2 + 2] cycloaddition-retroelectrocyclization reaction.

View Article and Find Full Text PDF

Triphenylamine (TPA) substituted π-conjugated chromophores TPA1-TPA5 were designed and synthesized Pd-catalysed Sonogashira cross-coupling followed by [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) reactions. The effects of acceptor 1,1,4,4-tetracyanobutadiene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD (DCNQ) units in the photophysical studies and the HOMO-LUMO energy levels of the phenothiazine sulfones TPA1-TPA5 were evaluated. The absorption spectra of chromophores TPA4 and TPA5 show a significant change due to the incorporation of DCNQ units, resulting in bathochromically shifted broad absorption in the NIR region.

View Article and Find Full Text PDF