A General Strategy Toward pH-Resistant Phenolic Fluorophores for High-Fidelity Sensing and Bioimaging Applications

Aryl alcohol-type or phenolic fluorophores offer diverse opportunities for developing bioimaging agents and fluorescence probes. Due to the inherently acidic hydroxyl functionality, phenolic fluorophores provide pH-dependent emission signals. Therefore, except for developing pH probes, the pH-dependent nature of phenolic fluorophores should be considered in bioimaging applications but has been neglected. Here we show that a simple structural remedy converts conventional phenolic fluorophores into pH-resistant derivatives, which also offer “medium-resistant” emission properties. The structural modification involves a single-step introduction of a hydrogen-bonding acceptor such as morpholine nearby the phenolic hydroxyl group, which also leads to emission bathochromic shift, increased Stokes shift, enhanced photo-stability and stronger emission for several dyes. The strategy greatly expands the current fluorophores’ repertoire for reliable bioimaging applications, as demonstrated here with ratiometric imaging of cells and tissues.     

Effect of gamma radiation on growth and survival of common seed-borne fungi in India

The present work describes radiation-induced effects of major seeds like Oryza sativa Cv-2233, Oryza sativa Cv-Shankar, Cicer arietinum Cv-local and seed-borne fungi like Alternaria sp., Aspergillus sp., Trichoderma sp. and Curvularia sp. ⁶⁰Co gamma source at 25 °C emitting gamma ray at 1173 and 1332 keV energy was used for irradiation. Dose of gamma irradiation up to 3 kGy (0.12 kGy/h) was applied for exposing the seed and fungal spores. Significant depletion of the fungal population was noted with irradiation at 1–2 kGy, whereas germinating potential of the treated grain did not alter significantly. However, significant differential radiation response in delayed seed germination, colony formation of the fungal spores and their depletion of growth were noticed in a dose-dependent manner. The depletion of the fungal viability (germination) was noted within the irradiation dose range of 1–2 kGy for Alternaria sp. and Aspergillus sp., while 0.5–1 kGy for Trichoderma sp. and Curvularia sp. However, complete inhibition of all the selected fungi was observed above 2.5 kGy.     

Positron annihilation spectroscopic studies of solvothermally synthesized ZnO nanobipyramids and nanoparticles

Zinc oxide (ZnO) samples in the form of hexagonal-based bipyramids and particles of nanometer dimensions were synthesized through solvothermal route and characterized by x-ray diffraction and transmission electron microscopy. Positron annihilation experiments were performed to study the structural defects such as vacancies and surfaces in these nanosystems. From coincidence Doppler broadening measurements, the positron trapping sites were identified as Zn vacancies or Zn-O-Zn trivacancy clusters. The positron lifetimes, their relative intensities, and the Doppler broadened lineshape parameter S all showed characteristic changes across the nanobipyramid size corresponding to the thermal diffusion length of positrons. In large nanobipyramids, vacancies within the crystallites also trapped positrons and the effects of agglomeration of such vacancies due to increased temperatures of synthesis were reflected in the variation of the annihilation parameters with their base diameters. The sizes of the nanoparticles used were all in the limit of thermal diffusion length of positrons and the annihilation characteristics were in accordance with the decreasing contribution from surfaces with increasing particle size.     

Organophosphites: An Addition to the Arsenal of Organocatalysts

Organophosphites are nucleophilic in nature and can act as a good leaving group owing to the stability of the phosphite anion. This dual reactivity makes them good candidates for nucleophilic organocatalysis. However, phosphites were introduced only in 2004 as the umpolung catalyst for acylsilane substrates utilizing sequential Brook rearrangements. Very recently, phosphites have been reported to catalyze aza-rearrangements and radical reactions. In this review, we discuss the reactivity parameters to understand its lack of use, as well as the potential for catalysis.     

Efficient Palladium‐Assisted One‐Pot Deprotection of (Acetamidomethyl)Cysteine Following Native Chemical Ligation and/or Desulfurization To Expedite Chemical Protein Synthesis

The acetamidomethyl (Acm) moiety is a widely used cysteine protecting group for the chemical synthesis and semisynthesis of peptide and proteins. However, its removal is not straightforward and requires harsh reaction conditions and additional purification steps before and after the removal step, which extends the synthetic process and reduces the overall yield. To overcome these shortcomings, a method for rapid and efficient Acm removal using Pd^II complexes in aqueous medium is reported. We show, for the first time, the assembly of three peptide fragments in a one‐pot fashion by native chemical ligation where the Acm moiety was used to protect the N‐terminal Cys of the middle fragment. Importantly, an efficient synthesis of the ubiquitin‐like protein UBL‐5, which contains two native Cys residues, was accomplished through the one‐pot operation of three key steps, namely ligation, desulfurization, and Acm deprotection, highlighting the great utility of the new approach in protein synthesis.     

A direct route to angularly substituted hydrindanes. Formal synthesis of bakkenolide-A and synthesis of an advanced intermediate to umbellactal

A direct route for the synthesis of highly functionalized angularly substituted hydrindanes has been developed. The key step involves RO-RCM of an appropriately functionalized norbornene derivative. The hydrindane derivative obtained in this way has been used to accomplish a formal synthesis of bakkenolide-A. This protocol has also been extended for the synthesis of an advanced intermediate to the synthesis of the diterpene umbellactal.     

Gravity stabilizes itself

We show that a possible resolution to the stabilization of an extra spatial dimension (radion) can be obtained solely in the context of gravitational dynamics itself without the necessity of introducing any external stabilizing field. In this scenario the stabilized value of the radion field gets determined in terms of the parameters appearing in the higher curvature gravitational action. Furthermore, the mass of the radion field and its coupling to the standard model fields are found to be in the weak scale implying possible signatures in the TeV scale colliders. Some resulting implications are also discussed.     

Hydrogen-Bonding Induced Alternate Stacking of Donor (D) and Acceptor (A) Chromophores and their Supramolecular Switching to Segregated States

This paper reports comprehensive studies on the mixed assembly of bis-(trialkoxybenzamide)-functionalized dialkoxynaphthalene (DAN) donors and naphthalene-diimide (NDI) acceptors due the cooperative effects of hydrogen bonding, charge-transfer (CT) interactions, and solvophobic effects. A series of DAN as well as NDI building blocks have been examined (wherein the relative distance between the two amide groups in a particular chromophore is the variable structural parameter) to understand the structure-dependent variation in mode of supramolecular assembly and morphology (organogel, reverse vesicle, etc.) of the self-assembled material. Interestingly, it was observed that when the amide functionalities are introduced to enhance the self-assembly propensity, the mode of co-assembly among the DAN and NDI chromophores no longer remained trivial and was dictated by a relatively stronger hydrogen-bonding interaction instead of a weak CT interaction. Consequently, in a highly non-polar solvent like methylcyclohexane (MCH), although kinetically controlled CT-gelation was initially noticed, within a few hours the system sacrificed the CT-interaction and switched over to the more stable self-sorted gel to maximize the gain in enthalpy from the hydrogen-bonding interaction. In contrast, in a relatively less non-polar solvent such as tetrachloroethylene (TCE), in which the strength of hydrogen bonding is inherently weak, the contribution of the CT interaction also had to be accounted for along with hydrogen bonding leading to a stable CT-state in the gel or solution phase. The stability and morphology of the CT complex and rate of supramolecular switching (from CT to segregated state) were found to be greatly influenced by subtle structural variation of the building blocks, solvent polarity, and the DAN/NDI ratio. For example, in a given D-A pair, by introducing just one methylene unit in the spacer segment of either of the building blocks a complete change in the mode of co-assembly (CT state or segregated state) and the morphology (1D fiber to 2D reverse vesicle) was observed. The role of solvent polarity, structural variation, and D/A ratio on the nature of co-assembly, morphology, and the unprecedented supramolecular-switching phenomenon have been studied by detail spectroscopic and microscopic experiments in a gel as well as in the solution state and are well supported by DFT calculations.