Direct Evidence of Significantly Different Chemical Behavior and Excited‐State Dynamics of 1,7‐ and 1,6‐Regioisomers of Pyrrolidinyl‐Substituted Perylene Diimide

Novel bay‐functionalized perylene diimides with additional substitution sites close to the perylene core have been prepared by the reaction between 1,7(6)‐dibromoperylene diimide 6 (dibromo‐PDI) and 2‐(benzyloxymethyl)pyrrolidine 5 . Distinct differences in the chemical behaviors of the 1,7‐ and 1,6‐regioisomers have been discerned. While the 1,6‐dibromo‐PDI produced the corresponding 1,6‐bis‐substituted derivative more efficiently, the 1,7‐dibromo‐PDI underwent predominant mono‐debromination, yielding a mono‐substituted PDI along with a small amount of the corresponding 1,7‐bis‐substituted compound. By varying the reaction conditions, a controlled stepwise bis‐substitution of the bromo substituents was also achieved, allowing the direct synthesis of asymmetrical 1,6‐ and 1,7‐PDIs. The compounds were isolated as individual regioisomers. Fullerene (C₆₀) was then covalently linked at the bay region of the newly prepared PDIs. In this way, two separate sets of perylene diimide–fullerene dyads, namely single‐bridged (SB‐1,7‐PDI‐C₆₀ and SB‐1,6‐PDI‐C₆₀) and double‐bridged (DB‐1,7‐PDI‐C₆₀ and DB‐1,6‐PDI‐C₆₀), were synthesized. The fullerene was intentionally attached at the bay region of the PDI to achieve close proximity of the two chromophores and to ensure an efficient photoinduced electron transfer. A detailed study of the photodynamics has revealed that photoinduced electron transfer from the perylene diimide chromophore to the fullerene occurs in all four dyads in polar benzonitrile, and also occurs in the single‐bridged dyads in nonpolar toluene. The process was found to be substantially faster and more efficient in the dyads containing the 1,7‐regioisomer, both for the singly‐ and double‐bridged molecules. In the case of the single‐bridged dyads, SB‐1,7‐PDI‐C₆₀ and SB‐1,6‐PDI‐C₆₀, different relaxation pathways of their charge‐separated states have been discovered. To the best of our knowledge, this is the first observation of photoinduced electron transfer in PDI‐C₆₀ dyads in a nonpolar medium.     

Synthesis and computational studies of potent antimicrobial and anticancer indolone scaffolds with spiro cyclopropyl moiety as a novel design element

The indolones nucleus is the central core to develop new effective anticancer agents and its substitution at the 3-position can affect antitumor activity, 3-spirocyclopropyl-2-oxindoles have attracted the scientist's community to design and develop expedition's strategies towards their construction and explore the potential of this useful scaffold with their newer derivatives in medicinal world. The present paper describes the synthesis of 3-spirocyclopropyl-2-indolone derivatives in three steps via synthesis of ylide leading to methylene-indolinones followed by the formation of the final product spirocyclopropyl oxindole derivatives with improved yields. In this milieu we considered motivating to advance exploration the biological potencies and computational studies of our newly synthesized molecules. The aimed target molecules were screened for antimicrobial and anticancer activities where they exhibited substantial effective antimicrobial activities. Amongst them, potent compound, bromospirocyclopropyl indolone, 6d displayed encouraging MIC ranging from 0.007 to 0.49 μg/mL for gram positive microbes and also substantial anticancer activity with an IC₅₀ of 11.5 μg/mL. Finally, the computational modelling studies were performed to explore structure-activity relationship analysis. Active site of receptor protein shows docking scores of these molecules as - 5.78 kcal/mol and ?5.097 kcal/mol for the docked target proteins. The binding energy of the best score is found to be ?41.67 kcal/mol to ?44.67 kcal/mol. Thus, the present paper efficaciously validated spirocyclopropyl indolone framework for drug candidates as potent anticancer as well as antimicrobial compounds.     

Redox-Switchable Complexes Based on Nanographene-NHCs

A series of rhodium and iridium complexes with a N-heterocyclic carbene (NHC) ligand decorated with a perylene-diimide-pyrene moiety are described. Electrochemical studies reveal that the complexes can undergo two successive one-electron reduction events, associated to the reduction of the PDI moiety attached to the NHC ligand. The reduction of the ligand produces a significant increase on its electron-donating character, as observed from the infrared spectroelectrochemical studies. The rhodium complex was tested in the [3+2] cycloaddition of diphenylcyclopropenone and methylphenylacetylene, where it displayed a redox-switchable behavior. The neutral complex showed moderate activity, which was suppressed when the catalyst was reduced.     

Combinatorial Crystal Synthesis: Structural Landscape of Phloroglucinol:1,2‐bis(4‐pyridyl)ethylene and Phloroglucinol:Phenazine

A large number of crystal forms, polymorphs and pseudopolymorphs, have been isolated in the phloroglucinol‐dipyridylethylene (PGL:DPE) and phloroglucinol‐phenazine (PGL:PHE) systems. An understanding of the intermolecular interactions and synthon preferences in these binary systems enables one to design a ternary molecular solid that consists of PGL, PHE, and DPE, and also others where DPE is replaced by other heterocycles. Clean isolation of these ternary cocrystals demonstrates synthon amplification during crystallization. These results point to the lesser likelihood of polymorphism in multicomponent crystals compared to single‐component crystals. The appearance of several crystal forms during crystallization of a multicomponent system can be viewed as combinatorial crystal synthesis with synthon selection from a solution library. The resulting polymorphs and pseudopolymorphs that are obtained constitute a crystal structure landscape.     

Kinetics and thermoluminescence glow curve study of Ba2MgSi2O7:Eu3+, Dy3+

This paper reports thermoluminescence glow curves of Eu³⁺, Dy³⁺-doped Ba₂MgSi₂O₇ phosphor for different UV exposure times. Kinetic data were evaluated by the peak-shape method. The glow curves shift toward higher intensity with increasing exposure time to UV at 365 nm. When the heating rate was 5 °C s^?1, peaks were observed at 101.76, 109.69, 102.67, and 104.05 °C, respectively, after UV exposure for 5, 10, 15, and 20 min. The glow peaks are indicative of second-order kinetics. Different kinetic data, i.e. trap depth, order of kinetics, activation energy, and frequency factor were also calculated. To evaluate the persistence characteristics of the luminescence of the phosphor, the lifetime of the charge in the trap was calculated; it was 348, 660, 368, and 428 s for UV exposure of 5, 10, 15, and 20 min, which indicates the luminescence of the phosphor is persistent.     

Efficient Chemical Protein Synthesis using Fmoc-Masked N-Terminal Cysteine in Peptide Thioester Segments

We report an operationally simple method to facilitate chemical protein synthesis by fully convergent and one-pot native chemical ligations utilizing the fluorenylmethyloxycarbonyl (Fmoc) moiety as an N-masking group of the N-terminal cysteine of the middle peptide thioester segment(s). The Fmoc group is stable to the harsh oxidative conditions frequently used to generate peptide thioesters from peptide hydrazide or o-aminoanilide. The ready availability of Fmoc-Cys(Trt)-OH, which is routinely used in Fmoc solid-phase peptide synthesis, where the Fmoc group is pre-installed on cysteine residue, minimizes additional steps required for the temporary protection of the N-terminal cysteinyl peptides. The Fmoc group is readily removed after ligation by short exposure (<7 min) to 20 % piperidine at pH 11 in aqueous conditions at room temperature. Subsequent native chemical ligation reactions can be performed in presence of piperidine in the same solution at pH 7.     

Application of Coherent States to Anharmonic,Time-Dependent and Damped Oscillator Systems

The present review deals with coherent states, its application to various problems in physics, chemistry and biology and its important applications to anharmonic, time-dependent and damped oscillator systems. It is seen that use of these states overcomes certain theoretical difficulties.     

Temporal Instability of Acoustic Wave in a Semiconductor Plasma Medium under Momentum Mismatched Condition

Physics of the Solid State - Temporal instability of acoustic wave is investigated in an infinite semiconductor plasma using classical hydrodynamic approach. We consider a homogeneous semiconductor...     

Triazoles as complexing agents: Synthesis and structural studies of some bivalent metal ion complexes with Bi- and tridentate ligands

Summary Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes of 4-amino-5-mercapto-3-trifluoromethyl-s-triazole (AMTT) and 5-mercapto-4-salicylideneamino-3-trifluoromethyl-s-triazole (MSTT) have been synthesized and characterized on the basis of elemental analyses, magnetic measurements, infrared and electronic spectral data. The ligandsAMTT andMSTT were characterized by elemental analyses, infrared and¹H NMR spectral studies.AMTT, involving N and S as donor atoms, andMSTT, involving N, O and S as donor atoms, act as bi- and tridentate ligands, respectively. The geometry of the complexes has been assigned on the basis of magnetic and electronic spectral data. EPR parameters for copper (II) complexes have been calculated. Thermal stabilities of the complexes are also reported. Due to insolubility in water and common organic solvents and infusibility at higher temperatures, all the complexes are thought to be polymeric in nature.

---

Triazole als Komplexierungs-Agentien: Synthese und Strukturuntersuchungen an einigen bivalenten Metallionenkomplexen mit zwei- und dreizähnigen Liganden

Zusammenfassung Es wurden Co(II)-, Ni(II)-, Cu(II)-, Zn(II)- und Cd(II)-Komplexe von 4-Amino-5-mercapto-3-trifluormethyl-s-triazol (AMTT) und 5-Mercapto-4-salizylidenamino-3-trifluormethyl-s-triazol (MSTT) hergestellt und mittels Elementaranalyse, magnetischen Messungen, Infrarot- und Elektronenspektroskopie charakterisiert. Die LigandenAMTT undMSTT wurden elementaranalytisch und spektroskopisch (IR und¹H-NMR) charakterisiert.AMT wirkt über die N-und S-Donoratome als zweizähniger Ligand,MSTT über N, O und S als dreizähniger Ligand. Die Geometrie der Komplexe wurde auf der Basis von magnetischen und elektronenspektroskopischen Daten zugeordnet. Für die Cu(II)-Komplexe wurden die EPR-Parameter berechnet. Die thermischen Stabilitäten der Komplexe wurde ebenfalls untersucht. Wegen ihrer Unlöslichkeit in Wasser und gängigen organischen Lösungsmitteln und der Unschmelzbarkeit bei höheren Temperaturen wird eine polymere Natur der Komplexe angenommen.