Frustrated Radical Pairs: Insights from EPR Spectroscopy

Progress in frustrated Lewis pair (FLP) chemistry has revealed the importance of the main group elements in catalysis, opening new avenues in synthetic chemistry. Recently, new reactivities of frustrated Lewis pairs have been uncovered that disclose that certain combinations of Lewis acids and bases undergo single‐electron transfer (SET) processes. Here an electron can be transferred from the Lewis basic donor to a Lewis acidic acceptor to generate a reactive frustrated radical pair (FRP). This minireview aims to showcase the recent advancements in this emerging field covering the synthesis and reactivities of frustrated radical pairs, with extensive highlights of the results from Electron Paramagnetic Resonance (EPR) spectroscopy to explain the nature and stability of the different radical species observed.     

Complex Cascade Reaction Networks via Cross β Amyloid Nanotubes

Biocatalytic reaction networks integrate complex cascade transformations via spatial localization of multiple enzymes confined within the cellular milieu. Inspired by nature's ingenuity, we demonstrate that short peptide‐based cross‐β amyloid nanotubular hybrids can promote different kinds of cascade reactions, from simple two‐step, to multistep, to complex convergent cascades. The compartmentalizing ability of paracrystalline cross‐β phases was utilized to colocalize sarcosine oxidase (SOX) and hemin as an artificial peroxidase. Further, the catalytic potential of the amyloid nanotubes with ordered arrays of imidazoles were used as hydrolase mimic. The SOX‐hemin amyloid nanohybrids featuring a single extant enzyme could integrate different logic networks to access complex digital designs with the help of three concatenated AND gates and biologically relevant stimuli as inputs.     

A stereo-divergent route to aminocyclopentitol derivatives

A stereo-divergent synthetic strategy based on diastereoselective vinylation of an α-amino aldehyde, ring-closing metathesis reaction and diastereoselective dihydroxylation reaction as key steps has been developed for the synthesis of three aminocyclopentitol derivatives of chemical and biological relevance.     

Charged quark stars in f(R,T) gravity

Recent advances in nuclear theory and new astrophysical observations have led to the need for specific theoretical models applicable to dense-matter physics phenomena. Quantum chromodynamics (QCD) predicts the existence of non-nucleonic degrees of freedom at high densities in neutron-star matter, such as quark matter. Within a confining quark matter model, which consists of homogeneous, neutral 3-flavor interacting quark matter with \begin{document}$ \mathcal{O}(m_s^4) $\end{document} corrections, we examine the structure of compact stars composed of a charged perfect fluid in the context of \begin{document}$ f(R,T) $\end{document} gravity. The system of differential equations describing the structure of charged compact stars has been derived and numerically solved for a gravity model with \begin{document}$ f(R,T)= R+ 2\beta T $\end{document}. For simplicity, we assumed that the charge density is proportional to the energy density, namely, \begin{document}$ \rho_{\rm ch} = \alpha \rho $\end{document}. It is demonstrated that the matter-geometry coupling constant β and charge parameter α affect the total gravitational mass and the radius of the star.     

A stereodivergent route to two epimeric 2-pyrrolidinylglycine derivatives

A new route to two epimeric 2-pyrrolidinylglycine derivatives is developed, which features Mitsunobu amination of a chiral allyl alcohol and ring-closing metathesis as key steps.     

Boron Doped Carbon Dots with Unusually High Photoluminescence Quantum Yield for Ratiometric Intracellular pH Sensing

Herein we report that boron doping in carbon dots results in increased photoluminescence (PL) quantum yield, which could be used for ratiometric intracellular pH sensing in cancer cell lines. Using a mixture of citric acid monohydrate, thiourea, and boric acid, microwave-assisted synthesis of boron doped blue emitting carbon dots (B-Cdots) with an average size of 3.5±1.0 nm was achieved. For B-Cdots, the maximum quantum yield (QY) was observed to be 25.8 % (11.1 % (w/w) H₃BO₃ input concentration), whereas, the same was calculated to be 16.9 % and 11.4 % for Cdots (synthesized from citric acid monohydrate and thiourea only) and P-Cdots (phosphorus doped carbon dots; synthesized using citric acid monohydrate, thiourea and phosphoric acid) (11.1 % (w/w) H₃PO₄ input concentration), respectively. The observed luminescence efficiencies as obtained from steady state and time-resolved photoluminescence measurements suggest an alternative emission mechanism due to boron/phosphorus doping in carbon dots. We furthermore demonstrated facile composite formation using B-Cdots and another carbon dots with orange emission in presence of polyvinyl alcohol (PVA), resulting in white light emission (0.31, 0.32; λ_ex 380 nm). The white light emitting composite enabled ratiometric pH sensing in the aqueous medium and showed favorable uptake properties by cancerous cells for intracellular pH sensing as well.     

Analysis of pseudo jahn–teller distortion based on natural bond orbital theory: Case study for silicene

Ground state (GS) instability of nondegenerate molecules in high symmetric structures is understood through Pseudo Jahn–Teller mixing of the electronic states through the vibronic coupling. The general approach involves setting up of a Pseudo Jahn–Teller (PJT) problem wherein one or more symmetry allowed excited states couple to the GS to create vibrational instability along a normal mode. This faces two major complications namely (1) estimating the adiabatic potential energy surfaces for the excited states which are often difficult to describe in case the excited states have charge-transfer or multi-excitonic (ME) character and (2) finding out how many such excited states (all satisfying the symmetry requirements for vibronic coupling) of increasing energies need to be coupled with the GS for a particular PJT problem. An analogous alternative approach presented here for the well-known case of symmetry breaking of planar (D_6h) hexasilabenzene (Si₆H₆) to the buckled (D_3d) structure involves identifying the second-order donor–acceptor, hyperconjugative interactions (E²_{i → j}) that stabilize the distorted structure. Following the recent work of Nori-Shargh and Weinhold, one observes that the orbitals involved in the vibronic coupling between the S₀/S_n states and those for the donor (filled)–acceptor (empty) interactions are identical. In fact, deletion of any particular pair of E²_{i → j} interaction creates vibrational instability in the buckled structure and as a corollary, deleting it for the planar structure removes its instability. The one-to-one correlation between the natural bond orbital theory and PJT theory assists in an intuitive identification of the relevant (few) excited states from a manifold of computed ones that cause symmetry breaking by vibronic coupling. © 2019 Wiley Periodicals, Inc.     

On Structured Surfaces with Defects: Geometry,Strain Incompatibility,Stress Field,and Natural Shapes

In this paper we study the stress and deformation fields generated by nonlinear inclusions with finite eigenstrains in anisotropic solids. In particular, we consider finite eigenstrains in transversely isotropic spherical balls and orthotropic cylindrical bars made of both compressible and incompressible solids. We show that the stress field in a spherical inclusion with uniform pure dilatational eigenstrain in a spherical ball made of an incompressible transversely isotropic solid such that the material preferred direction is radial at any point is uniform and hydrostatic. Similarly, the stress in a cylindrical inclusion contained in an incompressible orthotropic cylindrical bar is uniform hydrostatic if the radial and circumferential eigenstrains are equal and the axial stretch is equal to a value determined by the axial eigenstrain. We also prove that for a compressible isotropic spherical ball and a cylindrical bar containing a spherical and a cylindrical inclusion, respectively, with uniform eigenstrains the stress in the inclusion is uniform (and hydrostatic for the spherical inclusion) if the radial and circumferential eigenstrains are equal. For compressible transversely isotropic and orthotropic solids, we show that the stress field in an inclusion with uniform eigenstrain is not uniform, in general. Nevertheless, in some special cases the material can be designed in order to maintain a uniform stress field in the inclusion. As particular examples to investigate such special cases, we consider compressible Mooney-Rivlin and Blatz-Ko reinforced models and find analytical expressions for the stress field in the inclusion.     

Temperature effect on an ultrasound-assisted paper de-inking process

The influence of temperature on an ultrasound-assisted ink removal process has been investigated. White copy paper was evenly soaked in black writing ink. After drying the paper to constant weight at 75 °C, ink removal was attempted under varying conditions. Results were assessed by monitoring the UV–vis absorbance of the aqueous phase and measuring the brightness of the paper. Sonication was observed to improve the brightness of the paper in the temperature range of 15–45 °C with an optimum effect at 35 °C. Monitoring UV–vis spectra of the aqueous phase provided evidence that modification of the chemical structure of the ink desorbed from the paper occured. Further investigation under the same conditions showed that ink, when not absorbed on paper, did not undergo the same chemical change. This supports the hypothesis that only the compound released from the ink absorbed onto the paper is sensitive to sonodegradation. One possible explanation is that the metal binding component of the ink stays absorbed on the paper, releasing the organic part, whose chemical structure can be altered by the effect of sonication. Inductively coupled plasma analysis was used to confirm that during the de-inking process of the paper, the metal binding component stays absorbed on the paper and only the organic part is released in the aqueous phase.     

A highly contorted push–pull naphthalenediimide dimer and evidence of intramolecular singlet exciton fission

Singlet fission is a process by which two molecular triplet excitons are generated subsequent to the absorption of one photon. Molecules that enable singlet fission have triplet state energy at least half of the bright singlet state energy. This stringent energy criteria have challenged chemists to device new molecular and supramolecular design principles to modulate the singlet–triplet energy gap and build singlet fission systems from a wide range of organic chromophores. Herein, we report for the first time intramolecular singlet fission in the seminal naphthalenediimide (NDI) scaffold constrained in a push–pull cyclophane architecture, while individually the NDI chromophore does not satisfy the energy criterion. The challenging synthesis of this highly contorted push–pull cyclophane is possible from the preorganized pincer-like precursor. The special architecture establishes the shortest co-facial NDI⋯NDI contacts (3.084 Å) realized to date. Using broadband femtosecond transient absorption, we find that the correlated T–T pair forms rapidly within 380 fs of photoexcitation. Electronic structure calculations at the level of state-averaged CASSCF (ne,mo)/XMCQDPT2 support the existence of the multi-excitonic T–T pair state, thereby confirming the first example of singlet exciton fission in a NDI scaffold.

We report for the first-time intramolecular singlet fission (SF) in the naphthalenediimide (NDI) scaffold constrained in a cyclophane architecture, while individually the NDI units does not satisfy the requisite energy criterion for SF.