Excited state relaxation dynamics of model green fluorescent protein chromophore analogs: evidence for cis-trans isomerism

Two green fluorescent protein (GFP) chromophore analogs (4Z)-4-(N,N-dimethylaminobenzylidene)-1-methyl-2-phenyl-1,4-dihydro-5H-imidazolin-5-one (DMPI) and (4Z)-4-(N,N-diphenylaminobenzylidene)-1-methyl-2-phenyl-1,4-dihydro-5H-imidazolin-5-one (DPMPI) were investigated using femtosecond fluorescence up-conversion spectroscopy and quantum chemical calculations with the results being substantiated by HPLC and NMR measurements. The femtosecond fluorescence transients are found to be biexponential in nature and the time constants exhibit a significant dependence on solvent viscosity and polarity. A multicoordinate relaxation mechanism is proposed for the excited state relaxation behavior of the model GFP analogs. The first time component (τ(1)) was assigned to the formation of twisted intramolecular charge transfer (TICT) state along the rotational coordinate of N-substituted amine group. Time resolved intensity normalized and area normalized emission spectra (TRES and TRANES) were constructed to authenticate the occurrence of TICT state in subpicosecond time scale. Another picosecond time component (τ(2)) was attributed to internal conversion via large amplitude motion along the exomethylenic double bond which has been enunciated by quantum chemical calculations. Quantum chemical calculation also forbids the involvement of hula-twist because of high activation barrier of twisting. HPLC profiles and proton-NMR measurements of the irradiated analogs confirm the presence of Z and E isomers, whose possibility of formation can be accomplished only by the rotation along the exomethylenic double bond. The present observations can be extended to p-HBDI in order to understand the role of protein scaffold in reducing the nonradiative pathways, leading to highly luminescent nature of GFP.     

Characterization of the mixed self-assembled monolayer at the molecular scale

The mixed SAM obtained by the self-assembly of the monothiolated calix[4]crown-5 receptor 1 and the subsequent addition of the thiolated alkylferrocene guest 3 was characterized at the molecular scale by the favorable receptor-guest interactions by using cyclic voltammetry (CV).     

Rapid Preparation and Easy Quality Control Procedures for 99mTc‐Tin‐Nano Colloid: A Lymphoscintigraphic Agent

^99mTc‐Tin‐nano colloid is a radiopharmaceutical that can be useful in evaluation of the patients with breast cancer. The current method for preparation requires a lengthy boiling water bath procedure, and the recommended quality control procedure is cumbersome and time consuming. Using a microwave oven, the heating time necessary to provide a maximum labeling efficiency has been reduced to 10 second. A new mini paper chromatography (MPC) system has been developed to analyze the radiochemical purity (RCP) of the labeled preparation involving two different developing solvents. The recommended thin layer chromatography (TLC) system involving the use of an Al₂O₃ coated plate requires an average time for drying and development of 34.5 ± 0.44 min (n = 30) to complete, whereas the new MPC system has an average developing time of 2.1 ± 0.2 min (n = 20). For RCP values the MPC and TLC methods are correlated closely (r = 0.94). The combined use of the microwave oven heating method and over quick quality control system will facilitate the rapid emergency use of ^99mTc‐Tin‐nano colloid.     

New aqua rhenium oxocomplex; synthesis,characterization, thermal studies,DFT calculations and catalytic oxidations

The aqua rhenium oxocomplex [ReO(OH)(H₂O)₄]^2? (1) has been prepared and characterized by spectroscopy, thermogravimetry, and elemental analysis and its reactivity towards triphenylphosphine has been evaluated. Complex (1) acts as a catalyst precursor in the presence of molecular oxygen for the oxidation of PPh₃ to OPPh₃. This proceeds through complex intermediates like [Re(PPh₃)_n]³⁺ (2), and [ReO(PPh₃)_n]³⁺ (3). The newly prepared complex (1) was also employed as catalyst for catalytic oxidation of cyclohexane. The geometry of [ReO(OH)(H₂O)₄]^2? has also been optimized in the singlet state by the DFT method with B3LYP level of theory.     

Radiocomplexation and biological characterization of the <Superscript>99m</Superscript>TcN-trovafloxacin dithiocarbamate: a novel methicillin-resistant <Emphasis Type="Italic">Staphylococcus aureus</Emphasis> infection imaging agent

Extraction of europium(III) from nitric acid medium by a solution of tri-n-butylphosphate (TBP) and n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) in the room temperature ionic liquid, 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (amimNTf₂ where a = butyl or hexyl or octyl), was studied. The distribution ratio of ^(152+154)Eu(III) in TBP-CMPO/bmimNTf₂ was measured as a function of various parameters such as the concentrations of nitric acid, CMPO and NaNO₃. Remarkably large distribution ratios were observed for the extraction of europium(III) when bmimNTf₂ acted as diluent. The stoichiometry of metal-solvate in organic phase was determined by the slope analysis of extraction data.     

Radiosynthesis and biological evolution of <Superscript>99m</Superscript>Tc(CO)<Subscript>3</Subscript>–sitafloxacin dithiocarbamate complex: a promising <Emphasis Type="Italic">Staphylococcus aureus</Emphasis> infection radiotracer

Garenoxacin (GXN) was modified to its dithiocarbamate followed by radiolabeling with technetium-99m (^99mTc) through [^99mTc-N]²⁺ core. The suitability of the ^99mTcN–Garenoxacin dithiocarbamate (GXND) complex as a potential multiresistant Staphylococcus aureus (MDRSA) and penicillin-resistant Streptococci (PRSC) infection radiotracer was assessed in artificially infected rats (AFRT). The radiolabeled complex was investigated for its radiochemical purity (RCP), permanence in serum using HPLC and TLC methods. In vitro binding with MDRSA and PRSC was performed at 37 °C. The ^99mTcN–GXND showed maximum RCP of 98.00 ± 0.22% and remained more than 90% stable up to 4 h. The ^99mTcN–GXND showed saturated in vitro binding with living MDRSA and PRSC, respectively. The complex showed normal biodistribution in healthy rats (HRT), however in AFRT, seven fold uptakes was observed in infected muscle as compared to inflamed and normal muscles. Based on the high RCP, stability in serum, better in vitro binding with bacteria, biodistribution behavior and the target to non-target (infected to inflamed muscle) ratio, we recommend the ^99mTcN–GXND complex for in vivo investigation of MDRSA and PRSC infection in human.     

Dissolution and Delignification of Bamboo Biomass Using Amino Acid-Based Ionic Liquid

In the present work, the dissolution of bamboo biomass was tested using a number of ionic liquids synthesized in laboratory. It was observed that one of the synthesized amino acid-based ionic liquids, namely 1-ethyl-3-methylimidazolium glycinate, was capable of dissolving the biomass completely. The dissolved biomass was then regenerated using a reconstitute solvent (acetone/water) and was characterized using Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy. The results were compared to preconditioned bamboo biomass. The regenerated biomass was found to have a more homogenous macrostructure, which indicates that the crystalline form and structure of its cellulose has changed from type Ι to type ΙΙ during the dissolution and regeneration process.     

Oscillator strength measurements of the 3p ↦ nd Rydberg transitions of sodium

We report new measurements of the oscillator strengths of the 3p ²P_3/2 ↦nd ²D_{5/2, 3/2} and 3p ²P_1/2 ↦ nd ²D_3/2 Rydberg transitions of sodium using a thermionic diode ion detector in conjunction with the Nd:YAG pumped dye lasers. The ns ²S_1/2 and nd ²D_5/2,3/2 Rydberg series have been recorded via two-step excitation, from the 3p ²P_3/2 and 3p ²P_1/2 intermediate states. Employing the saturation technique, the photoionization cross sections from the 3p ²P_3/2 and 3p ²P_1/2 intermediate states at the first ionization threshold are determined as 7.9(1.3) Mb and 6.7(1.1) Mb respectively. The f-values of the Rydberg transitions are calibrated with the photoionization cross section measured at the first ionization threshold and compared with the earlier data.     

New Carbonic Anhydrase-II Inhibitors from Marine Macro Brown Alga Dictyopteris hoytii Supported by In Silico Studies

In continuation of phytochemical investigations of the methanolic extract of Dictyopteris hoytii, we have obtained twelve compounds (1–12) through column chromatography. Herein, three compounds, namely, dimethyl 2-bromoterepthalate (3), dimethyl 2,6-dibromoterepthalate (4), and (E)-3-(4-(dimethoxymethyl)phenyl) acrylic acid (5) are isolated for the first time as a natural product, while the rest of the compounds (1, 2, 6–12) are known and isolated for the first time from this source. The structures of the isolated compounds were elucidated by advanced spectroscopic 1D and 2D NMR techniques including ¹H, ¹³C, DEPT, HSQC, HMBC, COSY, NEOSY, and HR-MS and comparison with the reported literature. Furthermore, eight compounds (13–20) previously isolated by our group from the same source along with the currently isolated compounds (1–12) were screened against the CA-II enzyme. All compounds, except 6, 8, 14, and 17, were evaluated for in vitro bovine carbonic anhydrase-II (CA-II) inhibitory activity. Eventually, eleven compounds (1, 4, 5, 7, 9, 10, 12, 13, 15, 18, and 19) exhibited significant inhibitory activity against CA-II with IC₅₀ values ranging from 13.4 to 71.6 μM. Additionally, the active molecules were subjected to molecular docking studies to predict the binding behavior of those compounds. It was observed that the compounds exhibit the inhibitory potential by specifically interacting with the ZN ion present in the active site of CA-II. In addition to ZN ion, two residues (His94 and Thr199) play an important role in binding with the compounds that possess a carboxylate group in their structure.