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1.
Food Res Int ; 174(Pt 1): 113580, 2023 12.
Article in English | MEDLINE | ID: mdl-37986448

ABSTRACT

Pineapple-peel-based chitosan film was employed to extend the shelf life of Indian Cottage Cheese, commonly termed "paneer" in the Indian subcontinent. Pineapple peel extracts (PPE) at 3 different concentrations (1-3 %) were incorporated into the chitosan matrix. In comparison to control samples (unpacked paneer), packaged paneer samples exhibited reduced weight loss, lipid peroxidation, and pH changes. The microbiological shelf life of paneer got extended till 9th day at 4 °C when packaged in chitosan-PPE films. Korsmeyer-Peppas's model suggested that the release of polyphenols from the chitosan-PPE film followed Fickian diffusion. As per sensory evaluation on a 9-point hedonic scale, packaged paneer samples were superior in juiciness, texture, color, flavor, and overall acceptability compared to unpackaged paneer samples. As compared to the control sample (CS), the overall acceptance was higher for the film with 1 % pineapple peel extract (CS PPE 1), followed by films with 2 % and 3 % pineapple peel extracts (CS-PPE 2 and CS-PPE 3). The bio-accessibility study utilized the dynamic gastric model to simulate digestion in the upper gastrointestinal tract and revealed 40-60 % recovery rate of polyphenols from the chitosan-pineapple peel film.


Subject(s)
Ananas , Cheese , Chitosan , Antioxidants , Polyphenols , Plant Extracts
2.
Food Chem ; 402: 134249, 2023 Feb 15.
Article in English | MEDLINE | ID: mdl-36137377

ABSTRACT

To extend the oxidative stability of soybean oil with encapsulated natural antioxidants, eggplant peel-based water-in-oil (W/O) nanoemulsions were formulated. The nanoemulsions were developed with eggplant peel extract (1000-9000 ppm) and CR-310 emulsifier (8-10 %) via ultrasonication. Seven W/O nanoemulsion formulations exhibited high sedimentation stability (sedimentation index > 92.58 %), a mean droplet diameter < 100 nm and low polydispersity index (<0.25) during 30 days storage. These nanoemulsions achieved controlled release of polyphenols. The low conjugated diene and p-anisidine value (Schaal oven parameters) of the nanoemulsions compared to pure soybean oil and commercial soybean oil suggested that these W/O nanoemulsions restricted oxidation better than these oils. Moreover, they could control the oxidation of soybean oil for approximately 10-15 days under accelerated storage conditions. Further, the induction period in Rancimat also indicated that the nanoemulsions possessed higher oxidative stability compared to pure soybean oil while three nanoemulsions even exhibited higher induction period than commercial soybean oil.


Subject(s)
Solanum melongena , Soybean Oil , Emulsions , Delayed-Action Preparations , Oils , Plant Extracts , Water , Oxidative Stress
3.
Food Res Int ; 156: 111172, 2022 06.
Article in English | MEDLINE | ID: mdl-35651095

ABSTRACT

Acrylamide is a process contaminant and neurotoxic with growing evidence of cancer in human. Potato-based products majorly contribute towards acrylamide dietary intake thereby posing major food safety threat that necessitates formulation of acrylamide reduction strategies. This review highlights the recent research work on acrylamide formation mechanism, dietary intake, toxicity and potential reduction strategies at various levels in the food supply chain to ensure safety of potato-based products. Acrylamide formation in potato-based products depends on several factors involved in potato supply chain. Depending on the variety, application of nitrogen and sulphur fertilization may show positive, negative, or no effect on acrylamide formation. Heat and water stress faced by potato crops may increase the risk of acrylamide formation in processed products. Various pre-processing (e.g., blanching, chemical treatments etc.) and processing (e.g., methods, temperature, time) strategies may also reduce acrylamide formation (37-98%) in potato-based products at commercial and domestic levels. The acrylamide reduction strategies from farm to fork level have been discussed with special emphasis on mechanism of chemical treatments with pictorial representation.


Subject(s)
Acrylamide , Solanum tuberosum , Eating , Hot Temperature , Humans , Snacks
4.
Integr Med (Encinitas) ; 21(1): 36-44, 2022 Feb.
Article in English | MEDLINE | ID: mdl-35431690

ABSTRACT

Introduction: We report the successful management of a patient with persistent severe SARS-CoV-2 (covid-19) with poor prognosis, by using ayurvedic dietary guidelines and supporting herbal and herbomineral formulations. Case presentation: After two ICU admissions and at the end of conventional care options for Covid-19 infection, this 71-year-old patient presented online with persistent severe shortness of breath (spO2 85% on room air and spO2 75% with minimal exertion), methylprednisolone dependence of 32 mg/day, and CT Severity Score of 23/25. Upon initiating specific ayurvedic dietary guidelines (ahara) and supportive formulations to increase digestive metabolism and induce respiratory repair, the patient improved clinically (PCFS grade 4 to 2) within 3 weeks, and radiologically (CT severity 23/25 to 12/25) within 6 weeks. Conclusion: Ayurveda provides valuable clinical algorithmic insights into the mechanism of hyperinflammatory surges and dysregulated host response that characterize not only Covid-19 but also most infectious diseases. Ayurveda posits that diet incompatible with the individual's current metabolic state is the key element in inflammatory host response, providing detailed dietary guidelines, and tools that syncretize using a whole systems approach.

5.
Food Technol Biotechnol ; 59(1): 31-43, 2021 Mar.
Article in English | MEDLINE | ID: mdl-34084078

ABSTRACT

RESEARCH BACKGROUND: Sorghum bran, although considered as an agricultural waste, is an abundant source of various bioactive compounds. These bioactive compounds require specific extraction with particular solvents and therefore ionic liquid and three different conventional solvents, viz. anhydrous methanol, acidified methanol and water were used in this work. EXPERIMENTAL APPROACH: To evaluate the phytochemicals in the different sorghum bran extracts, total phenol content, flavonoids, condensed tannins and anthocyanins were determined as per standard protocols. Liquid chromatography with tandem mass spectrometryanalysis of extracts was also performed for their phenolic profiling. The antioxidant activity of the extracts was estimated via three assays: 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging assay, 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical cation decolourization assay and Cu2+ reducing antioxidant capacity (CUPRAC) method. The antibacterial activity against two most opportunistic foodborne pathogens: Escherichia coli and Staphylococcus aureus was measured by agar well diffusion assay and minimum inhibitory concentration (MIC) was determined by serial dilution method. RESULTS AND CONCLUSIONS: Ionic liquid extract of sorghum bran gave the highest yield ((14.9±0.7) %), which indicated that various possible interactions like Van der Waals forces, H-bonding, hydrophobic and cation-π bonding can occur when ionic liquid is used as an extractant compared to other conventional solvents, although total phenol mass fraction expressed as gallic acid equivalents on dry mass basis was only (7.4±0.7) mg/g. The hydrophobicity of the ionic liquid also helped in efficient extraction of condensed tannins ((63.2±2.1) mg/g expressed on dry mass basis), which resulted in significant antioxidant activity of the ionic liquid extract ((85.2±1.2) µmol/g in DPPH assay, (100.8±0.9) µmol/g in ABTS assay and (63.2±1.9) µmol/g in CUPRAC). An interesting revelation reported in this work is the inability of DPPH assay to evaluate the antioxidant activity in acidic environment. The anhydrous methanolic extract of sorghum bran displayed pH sensitivity, making the extract beneficial for certain applications. Qualitative analysis of extracts revealed greater number of phenolic compounds to be present in methanol and distilled water extracts. Moreover, various derivatives of apigenin and luteolin were also observed in all four extracts. In addition, the acidified methanol extract of the sorghum bran exhibited antimicrobial property at a concentration of 12 mg/mL. A larger inhibition zone was observed against Escherichia coli than Staphylococcus aureus, while the MIC against these two bacteria was 2.2 and 1.1 mg/mL, respectively. NOVELTY AND SCIENTIFIC CONTRIBUTION: This paper presents the first information on the application of ionic liquids as extracting phase for sorghum bran polyphenols and the quantification of such extracts. As evident from the study, each solvent has its own role in the extraction of bioactive compounds. This work also proves that sorghum bran imparts antibacterial activity against foodborne pathogens.

6.
Proc Natl Acad Sci U S A ; 117(30): 17864-17875, 2020 07 28.
Article in English | MEDLINE | ID: mdl-32669432

ABSTRACT

Early pregnancy loss affects ∼15% of all implantation-confirmed human conceptions. However, evolutionarily conserved molecular mechanisms that regulate self-renewal of trophoblast progenitors and their association with early pregnancy loss are poorly understood. Here, we provide evidence that transcription factor TEAD4 ensures survival of postimplantation mouse and human embryos by controlling self-renewal and stemness of trophoblast progenitors within the placenta primordium. In an early postimplantation mouse embryo, TEAD4 is selectively expressed in trophoblast stem cell-like progenitor cells (TSPCs), and loss of Tead4 in postimplantation mouse TSPCs impairs their self-renewal, leading to embryonic lethality before embryonic day 9.0, a developmental stage equivalent to the first trimester of human gestation. Both TEAD4 and its cofactor, yes-associated protein 1 (YAP1), are specifically expressed in cytotrophoblast (CTB) progenitors of a first-trimester human placenta. We also show that a subset of unexplained recurrent pregnancy losses (idiopathic RPLs) is associated with impaired TEAD4 expression in CTB progenitors. Furthermore, by establishing idiopathic RPL patient-specific human trophoblast stem cells (RPL-TSCs), we show that loss of TEAD4 is associated with defective self-renewal in RPL-TSCs and rescue of TEAD4 expression restores their self-renewal ability. Unbiased genomics studies revealed that TEAD4 directly regulates expression of key cell cycle genes in both mouse and human TSCs and establishes a conserved transcriptional program. Our findings show that TEAD4, an effector of the Hippo signaling pathway, is essential for the establishment of pregnancy in a postimplantation mammalian embryo and indicate that impairment of the Hippo signaling pathway could be a molecular cause for early human pregnancy loss.


Subject(s)
Cell Self Renewal/genetics , DNA-Binding Proteins/genetics , Embryonic Development/genetics , Muscle Proteins/genetics , Transcription Factors/genetics , Trophoblasts/cytology , Trophoblasts/metabolism , Abortion, Habitual/etiology , Abortion, Habitual/metabolism , Abortion, Spontaneous/etiology , Abortion, Spontaneous/metabolism , Animals , Biomarkers , DNA-Binding Proteins/metabolism , Disease Models, Animal , Disease Susceptibility , Embryo Implantation , Female , Fluorescent Antibody Technique , Gene Expression Regulation, Developmental , Humans , Immunohistochemistry , Mice , Muscle Proteins/metabolism , Placenta/metabolism , Pregnancy , TEA Domain Transcription Factors , Transcription Factors/metabolism
7.
Proc Natl Acad Sci U S A ; 117(25): 14280-14291, 2020 06 23.
Article in English | MEDLINE | ID: mdl-32513715

ABSTRACT

In utero mammalian development relies on the establishment of the maternal-fetal exchange interface, which ensures transportation of nutrients and gases between the mother and the fetus. This exchange interface is established via development of multinucleated syncytiotrophoblast cells (SynTs) during placentation. In mice, SynTs develop via differentiation of the trophoblast stem cell-like progenitor cells (TSPCs) of the placenta primordium, and in humans, SynTs are developed via differentiation of villous cytotrophoblast (CTB) progenitors. Despite the critical need in pregnancy progression, conserved signaling mechanisms that ensure SynT development are poorly understood. Herein, we show that atypical protein kinase C iota (PKCλ/ι) plays an essential role in establishing the SynT differentiation program in trophoblast progenitors. Loss of PKCλ/ι in the mouse TSPCs abrogates SynT development, leading to embryonic death at approximately embryonic day 9.0 (E9.0). We also show that PKCλ/ι-mediated priming of trophoblast progenitors for SynT differentiation is a conserved event during human placentation. PKCλ/ι is selectively expressed in the first-trimester CTBs of a developing human placenta. Furthermore, loss of PKCλ/ι in CTB-derived human trophoblast stem cells (human TSCs) impairs their SynT differentiation potential both in vitro and after transplantation in immunocompromised mice. Our mechanistic analyses indicate that PKCλ/ι signaling maintains expression of GCM1, GATA2, and PPARγ, which are key transcription factors to instigate SynT differentiation programs in both mouse and human trophoblast progenitors. Our study uncovers a conserved molecular mechanism, in which PKCλ/ι signaling regulates establishment of the maternal-fetal exchange surface by promoting trophoblast progenitor-to-SynT transition during placentation.


Subject(s)
Cell Differentiation/physiology , Isoenzymes/metabolism , Maternal-Fetal Exchange/physiology , Placenta/metabolism , Protein Kinase C/metabolism , Trophoblasts/physiology , Animals , DNA-Binding Proteins/metabolism , Female , GATA2 Transcription Factor/metabolism , Humans , Isoenzymes/genetics , Male , Mice , Mice, Knockout , Models, Animal , PPAR gamma/metabolism , Placenta/cytology , Placentation/physiology , Pregnancy , Protein Kinase C/genetics , Signal Transduction , Stem Cells/cytology , Transcription Factors/metabolism , Trophoblasts/cytology
8.
J Biol Chem ; 294(46): 17301-17313, 2019 11 15.
Article in English | MEDLINE | ID: mdl-31591264

ABSTRACT

A successful pregnancy is critically dependent upon proper placental development and function. During human placentation, villous cytotrophoblast (CTB) progenitors differentiate to form syncytiotrophoblasts (SynTBs), which provide the exchange surface between the mother and fetus and secrete hormones to ensure proper progression of pregnancy. However, epigenetic mechanisms that regulate SynTB differentiation from CTB progenitors are incompletely understood. Here, we show that lysine-specific demethylase 1 (LSD1; also known as KDM1A), a histone demethylase, is essential to this process. LSD1 is expressed both in CTB progenitors and differentiated SynTBs in first-trimester placental villi; accordingly, expression in SynTBs is maintained throughout gestation. Impairment of LSD1 function in trophoblast progenitors inhibits induction of endogenous retrovirally encoded genes SYNCYTIN1/endogenous retrovirus group W member 1, envelope (ERVW1) and SYNCYTIN2/endogenous retrovirus group FRD member 1, envelope (ERVFRD1), encoding fusogenic proteins critical to human trophoblast syncytialization. Loss of LSD1 also impairs induction of chorionic gonadotropin α (CGA) and chorionic gonadotropin ß (CGB) genes, which encode α and ß subunits of human chorionic gonadotrophin (hCG), a hormone essential to modulate maternal physiology during pregnancy. Mechanistic analyses at the endogenous ERVW1, CGA, and CGB loci revealed a regulatory axis in which LSD1 induces demethylation of repressive histone H3 lysine 9 dimethylation (H3K9Me2) and interacts with transcription factor GATA2 to promote RNA polymerase II (RNA-POL-II) recruitment and activate gene transcription. Our study reveals a novel LSD1-GATA2 axis, which regulates human trophoblast syncytialization.


Subject(s)
Cell Differentiation/genetics , GATA2 Transcription Factor/genetics , Histone Demethylases/genetics , Trophoblasts/metabolism , Chorionic Villi/growth & development , Chorionic Villi/metabolism , Epigenesis, Genetic/genetics , Female , Gene Expression Regulation, Developmental/genetics , Gene Products, env/genetics , Humans , Mother-Child Relations , Placentation/genetics , Pregnancy , Pregnancy Proteins/genetics , RNA Polymerase II/genetics , Signal Transduction/genetics
9.
Development ; 145(19)2018 10 01.
Article in English | MEDLINE | ID: mdl-30201685

ABSTRACT

Early mammalian development is crucially dependent on the establishment of oxidative energy metabolism within the trophectoderm (TE) lineage. Unlike the inner cell mass, TE cells enhance ATP production via mitochondrial oxidative phosphorylation (OXPHOS) and this metabolic preference is essential for blastocyst maturation. However, molecular mechanisms that regulate establishment of oxidative energy metabolism in TE cells are incompletely understood. Here, we show that conserved transcription factor TEAD4, which is essential for pre-implantation mammalian development, regulates this process by promoting mitochondrial transcription. In developing mouse TE and TE-derived trophoblast stem cells (TSCs), TEAD4 localizes to mitochondria, binds to mitochondrial DNA (mtDNA) and facilitates its transcription by recruiting mitochondrial RNA polymerase (POLRMT). Loss of TEAD4 impairs recruitment of POLRMT, resulting in reduced expression of mtDNA-encoded electron transport chain components, thereby inhibiting oxidative energy metabolism. Our studies identify a novel TEAD4-dependent molecular mechanism that regulates energy metabolism in the TE lineage to ensure mammalian development.


Subject(s)
DNA-Binding Proteins/metabolism , Embryonic Development/genetics , Energy Metabolism , Mammals/embryology , Mammals/genetics , Mitochondria/genetics , Muscle Proteins/metabolism , Transcription Factors/metabolism , Transcription, Genetic , Animals , Blastocyst/cytology , Blastocyst/metabolism , Blastocyst/ultrastructure , DNA, Mitochondrial/genetics , DNA-Binding Proteins/deficiency , DNA-Binding Proteins/genetics , DNA-Directed RNA Polymerases/metabolism , Ectoderm/cytology , Electron Transport , Energy Metabolism/genetics , Mice , Mitochondria/ultrastructure , Models, Biological , Muscle Proteins/deficiency , Muscle Proteins/genetics , Oxidation-Reduction , Stem Cells/cytology , Stem Cells/metabolism , TEA Domain Transcription Factors , Transcription Factors/deficiency , Transcription Factors/genetics , Trophoblasts/cytology
10.
Placenta ; 60 Suppl 1: S61-S66, 2017 12.
Article in English | MEDLINE | ID: mdl-28526138

ABSTRACT

Mammalian reproduction is critically dependent on trophoblast cells, which ensure embryo implantation and placentation. Development of trophoblast cell lineages is a multi-step process and relies upon proper spatial and temporal gene expression, which is regulated by multiple transcription factors. However, most of the transcription factors that are implicated in trophoblast development regulate gene expression at a specific developmental stage or in a specific trophoblast subtype. In contrast, recent studies from our group and other laboratories indicate that conserved GATA family of transcription factors, GATA2 and GATA3, are important to regulate gene expression at multiple stages of trophoblast development. Furthermore, our conditional gene deletion studies revealed that functional redundancy of GATA2 and GATA3 ensures both self-renewal of trophoblast stem and progenitor cells and their differentiation to trophoblast cells of a matured placenta. Together these findings indicate that GATA2/GATA3 are the master orchestrators of gene expression in trophoblast cells and they fine tune gene regulatory network to establish distinct trophoblast cell types during placentation.


Subject(s)
Embryonic Stem Cells/metabolism , GATA Transcription Factors/metabolism , Gene Expression Regulation, Developmental , Placentation , Trophoblasts/metabolism , Animals , Blastocyst/cytology , Blastocyst/metabolism , Blastocyst/pathology , Embryonic Development , Embryonic Stem Cells/cytology , Embryonic Stem Cells/pathology , Female , Humans , Placenta/cytology , Placenta/metabolism , Placenta/pathology , Pregnancy , Pregnancy Complications/metabolism , Pregnancy Complications/pathology , Trophoblasts/cytology , Trophoblasts/pathology
11.
Development ; 144(5): 876-888, 2017 03 01.
Article in English | MEDLINE | ID: mdl-28232602

ABSTRACT

GATA transcription factors are implicated in establishing cell fate during mammalian development. In early mammalian embryos, GATA3 is selectively expressed in the extraembryonic trophoblast lineage and regulates gene expression to promote trophoblast fate. However, trophoblast-specific GATA3 function is dispensable for early mammalian development. Here, using dual conditional knockout mice, we show that genetic redundancy of Gata3 with paralog Gata2 in trophoblast progenitors ensures the successful progression of both pre- and postimplantation mammalian development. Stage-specific gene deletion in trophoblasts reveals that loss of both GATA genes, but not either alone, leads to embryonic lethality prior to the onset of their expression within the embryo proper. Using ChIP-seq and RNA-seq analyses, we define the global targets of GATA2/GATA3 and show that they directly regulate a large number of common genes to orchestrate stem versus differentiated trophoblast fate. In trophoblast progenitors, GATA factors directly regulate BMP4, Nodal and Wnt signaling components that promote embryonic-extraembryonic signaling cross-talk, which is essential for the development of the embryo proper. Our study provides genetic evidence that impairment of trophoblast-specific GATA2/GATA3 function could lead to early pregnancy failure.


Subject(s)
GATA2 Transcription Factor/physiology , GATA3 Transcription Factor/physiology , Placenta/physiology , Stem Cells/cytology , Trophoblasts/cytology , Animals , Cell Differentiation , Cell Lineage , Embryo Implantation , Embryonic Development , Female , Gene Deletion , Humans , Mice , Mice, Knockout , Pregnancy , Pregnancy, Animal , Sequence Analysis, RNA
12.
Biochemistry ; 52(44): 7798-806, 2013 Nov 05.
Article in English | MEDLINE | ID: mdl-24151934

ABSTRACT

The structures of two major tyrocidines, antibiotic peptides from Bacillus aneurinolyticus, in an aqueous environment were studied using nuclear magnetic resonance spectroscopy, restrained molecular dynamics (MD), circular dichroism, and mass spectrometry. TrcA and TrcC formed ß-structures in an aqueous environment. Hydrophobic and hydrophilic residues were not totally separated into nonpolar and polar faces of the peptides, indicating that tyrocidines have low amphipathicity. In all the ß-structures, residues Trp(4)/Phe(4) and Orn(9) were on the same face. The ability of the peptides to form dimers in aqueous environment was studied by replica exchange MD simulations. Both peptides readily dimerize, and predominant complex structures were characterized through cluster analysis. The peptides formed dimers by either associating sideways or stacking on top of each other. Dimers formed through sideways association were mainly stabilized by hydrogen bonding, while the other dimers were stabilized by hydrophobic interactions. The ability of tyrocidine peptides to form different types of dimers with different orientations suggests that they can form larger aggregates, as well.


Subject(s)
Anti-Bacterial Agents/chemistry , Bacillus/metabolism , Tyrocidine/chemistry , Anti-Bacterial Agents/metabolism , Bacillus/chemistry , Dimerization , Magnetic Resonance Spectroscopy , Molecular Dynamics Simulation , Protein Structure, Secondary , Tyrocidine/metabolism
13.
Proc Natl Acad Sci U S A ; 108(36): 14825-30, 2011 Sep 06.
Article in English | MEDLINE | ID: mdl-21873247

ABSTRACT

Efficient and reproducible construction of signaling and sorting complexes, both on the surface and within the living cell, is contingent on local regulation of biochemical reactions by the cellular milieu. We propose that in many cases this spatiotemporal regulation can be mediated by interaction with components of the dynamic cytoskeleton. We show how the interplay between active contractility and remodeling of the cytoskeleton can result in transient focusing of passive molecules to form clusters, leading to a dramatic increase in the reaction efficiency and output levels. The dynamic cytoskeletal elements that drive focusing behave as quasienzymes catalyzing the chemical reaction. These ideas are directly applicable to the cortical actin-dependent clustering of cell surface proteins such as lipid-tethered GPI-anchored proteins, Ras proteins, as well as many proteins that have domains that confer the ability to interact with the actin cytoskeleton. In general such cytoskeletal driven clustering of proteins could be a cellular mechanism to spatiotemporally regulate and amplify local chemical reaction rates in a variety of contexts such as signaling, transcription, sorting, and endocytosis.


Subject(s)
Actins/metabolism , Cytoskeleton/metabolism , GPI-Linked Proteins/metabolism , Models, Biological , Actins/chemistry , Cytoskeleton/chemistry , GPI-Linked Proteins/chemistry , Models, Chemical
14.
J Biomed Nanotechnol ; 7(1): 66-7, 2011 Feb.
Article in English | MEDLINE | ID: mdl-21485806

ABSTRACT

The validity of herbometallic bhasmas described in Ayurveda is nowhere acknowledged by biomedical science. To unravel the knowledge of bhasmas, an algorithm integrating ayurveda- and science-based experiments needs to connect the basic science of rasa shastra, the study of herbometallic medicines in ayurveda, to clinical data.


Subject(s)
Evidence-Based Medicine/methods , Medicine, Ayurvedic , Metal Nanoparticles/chemistry , Metal Nanoparticles/therapeutic use
15.
J Chem Phys ; 134(4): 044535, 2011 Jan 28.
Article in English | MEDLINE | ID: mdl-21280776

ABSTRACT

Multiple emissions have been observed from benzil under different conditions in solutions at room temperature as well as in low temperature glass matrices at 77 K. Low temperature emission has been monitored in rigid matrices frozen under different conditions of illumination. Steady state and time-resolved results together with the ab initio quantum chemical calculations provide, for the first time, the assignments of the different fluorescence bands to the different geometries and∕or electronic states of the fluorophore molecule. It is revealed that the skew form of benzil emits from the first (S(1)) as well as the second excited singlet (S(2)) states depending on the excitation wavelength, while the relaxed transplanar conformer fluoresces only from the S(1) state. The yet unexplored emission band peaking at around 360 nm has been assigned to originate from the S(2) state. Ab initio calculations using the density functional theory at B3LYP∕6-31G∗∗ level corroborate well with the experimental observations.

16.
J Colloid Interface Sci ; 353(1): 181-7, 2011 Jan 01.
Article in English | MEDLINE | ID: mdl-20889159

ABSTRACT

Room temperature ionic liquids are rapidly emerging as a new class of media that are ideally suited for various applications including carrying out chemical reactions. In the present article, we report the photophysics of a ß-carboline analogue, namely, 3-acetyl-4-oxo-6,7-dihydro-12H indolo-[2,3-a] quinolizine (AODIQ), in three room temperature ionic liquids (RTILs), 1-butyl-3-methylimidazolium methyl sulfate ([BMIM][MeSO(4)]), 1-butyl-3-methylimidazolium octyl sulfate ([BMIM][C(8)SO(4)]) and 1-ethyl-3-methylimidazolium methyl sulfate ([EMIM][MeSO(4)]). Out of these, [BMIM][C(8)SO(4)] is a typical RTIL that forms micellar aggregates above a critical micellar concentration (CMC). Steady state absorption, steady state and time resolved fluorescence techniques are used to probe the properties of these systems. The investigation reveals that the photophysics of AODIQ is modified significantly in the micelle-forming RTIL as compared to that in the other two. A comparative study with the fluorophore in [BMIM][C(8)SO(4)] and a conventional anionic surfactant of a similar hydrophobic chain length from the sodium-n-alkyl sulfate series, viz., sodium octyl sulfate (S(8)S), reveals that the fluorophore experiences a more constrained environment in the RTIL micelle as compared to the conventional anionic micelle.

17.
J Colloid Interface Sci ; 347(2): 252-9, 2010 Jul 15.
Article in English | MEDLINE | ID: mdl-20399444

ABSTRACT

The interaction of beta-cyclodextrin with the non-ionic micelle-forming surfactant Triton X-165 (TX-165) has been studied using steady state fluorescence and fluorescence anisotropy techniques. Both extrinsic and intrinsic fluorescence have been exploited for the purpose. Phenosafranin (PSF), a cationic phenazinium dye, has been used as the extrinsic probe while fluorescence of TX-165 has served as the intrinsic one. PSF shows discernible interactions with both TX-165 and beta-CD. The experimental results reveal that the extent of interaction of PSF with TX-165 is greater than with beta-CD. However, addition of beta-CD to a micellar solution of TX-165 containing PSF leads to a disruption of the micelles whereby the fluorophore is released from the micellar environment to the bulk aqueous phase. It has been substantiated that an inclusion complex is formed between the non-ionic surfactant and the cyclodextrin. A 1:1 stoichiometry of the TX-165-beta-CD inclusion complex has been proposed. Such a complexation between TX-165 and beta-CD results in an inhibition in the micellization process of TX-165 leading to an enhancement in the apparent CMC value. The inferences are drawn from a series of experiments, viz., binding studies, determination of micropolarity, heavy-ion quenching studies and steady state fluorescence anisotropy experiments monitoring both extrinsic and intrinsic fluorescences.


Subject(s)
Benzene Derivatives/chemistry , Fluorescence , Polyethylene Glycols/chemistry , Surface-Active Agents/chemistry , beta-Cyclodextrins/chemistry , Fluorescence Polarization , Fluorescent Dyes , Micelles , Phenazines
18.
J Phys Chem B ; 113(7): 2143-50, 2009 Feb 19.
Article in English | MEDLINE | ID: mdl-19199686

ABSTRACT

Interaction of bovine serum albumin (BSA) with two series of dipolar molecules having both rigid and flexible structures has been studied by monitoring the spectral and temporal behavior of the intramolecular charge transfer fluorescence of the systems. The binding sites of the molecular systems in BSA have been located with the help of docking studies. Three different sites of varying hydrophobicity have been identified where these molecules are located. Binding in the hydrophobic domains of BSA leads to a blue shift of the fluorescence spectra and an enhancement of fluorescence intensity and lifetime. This enhancement is found to be the largest for flexible systems in which internal motion serves as a nonradiative decay route. In the BSA-bound condition, some of the dipolar molecules exhibit not-so-common "dip-rise-dip" time-resolved fluorescence anisotropy profiles. It is shown that a large difference of the fluorescence lifetimes of the protein-bound and unbound molecules is one of the factors that contributes to this kind of anisotropy profiles. As internal motion is often responsible for the short fluorescence lifetime of the flexible dipolar molecules, a large increase in the fluorescence lifetime of these systems occurs if binding to BSA leads to disruption/prevention of this motion. It thus appears that it might be possible to obtain information on the prevention/disruption of nonradiative pathway on protein binding from the anisotropy profiles of the kind discussed above. However, since the present study reveals cases where a large change in fluorescence lifetime also occurs due to other reasons, one needs to be careful prior to making any conclusion.


Subject(s)
Fluorescence , Models, Chemical , Serum Albumin, Bovine/chemistry , Animals , Binding Sites , Cattle , Hydrophobic and Hydrophilic Interactions , Molecular Structure , Time Factors
19.
J Phys Chem B ; 112(33): 10101-6, 2008 Aug 21.
Article in English | MEDLINE | ID: mdl-18661938

ABSTRACT

Excited-state proton transfer (ESPT) reaction of 7-hydroxyquinoline (7-HQ) mediated by methanol molecules has been studied in two room temperature ionic liquids (RTILs) using steady-state and time-resolved fluorescence measurements. While no ESPT is observable in neat RTILs, characteristic tautomer fluorescence of 7-HQ could be observed in the presence of small quantity of methanol (0.5-4.1 M). The observation of a rise time (350 ps-1.4 ns) associated with the tautomer fluorescence suggests that proton transfer in 7-HQ is indeed an excited-state phenomenon that requires considerable solvent reorganization prior to the relay of proton from the hydroxyl group to the distant ring nitrogen atom through suitably organized dimeric chain of methanol molecules. The rise time of the tautomer fluorescence, which has been found to decrease with increasing methanol concentration, is attributed to the change of viscosity of the medium upon methanol addition. While the influence of viscosity on the ESPT kinetics is evident from the data, lack of any definite correlation between the bulk viscosity and the rise time has been interpreted in terms of the microheterogeneous nature of the media that does not allow assessment of the microviscosity around 7-HQ from the bulk viscosity.

20.
J Phys Chem A ; 112(15): 3302-10, 2008 Apr 17.
Article in English | MEDLINE | ID: mdl-18338875

ABSTRACT

Photophysical behavior of several structurally related electron donor-acceptor flavone derivatives, which have been synthesized and characterized, has been studied as a function of the polarity of the media. Significant variation of the absorption and fluorescence response of the systems has been observed with change in the polarity of the medium. The results show an increase in the radiative rate constant and a decrease in the nonradiative rate constant of the systems with increase in the polarity of the media. This finding has been attributed to the change in the nature of the emitting state from a mixed n-pi* and pi-pi* state to a dominant pi-pi* state with increase in the polarity of the medium. The results of single-crystal diffraction studies and theoretical calculations based on density functional method support the idea of close proximity of the n-pi* and pi-pi* states and the change in their relative contributions toward the emission process with the polarity of the medium. Laser flash photolysis studies show that the triplet state is not involved in the variation of the fluorescence response of the systems.

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