DOCSLIB.ORG

Glycerol Role in Nano Oxides Synthesis and Catalysis

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Glycerol Role in Nano Oxides Synthesis and Catalysis catalysts Review Glycerol Role in Nano Oxides Synthesis and Catalysis Ana F. Cristino 1, Inês A. S. Matias 2 , David E. N. Bastos 2,3, Rui Galhano dos Santos 3 , Ana P. C. Ribeiro 2,* and Luísa M. D. R. S. Martins 2,* 1 Centro de Química Estrutural, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal; [email protected] 2 Centro de Química Estrutural, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal; [email protected] (I.A.S.M.); [email protected] (D.E.N.B.) 3 CERENA—Centre for Natural Resources and the Environment, Instituto Superior Técnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal; [email protected] * Correspondence: [email protected] (A.P.C.R.); [email protected] (L.M.D.R.S.M.); Tel.: +351-218419389 (L.M.D.R.S.M.) Received: 30 October 2020; Accepted: 30 November 2020; Published: 2 December 2020 Abstract: The transformation of biomass and the utilization of all the by products derived from chemical conversion of biomass resources is one of the most important challenges nowadays. The impact in society and the level of awareness that already exists inside and outside the scientific community, makes the challenge of improving conversion of biomass to commodities a hot topic. Glycerol, a by-product obtained from the biodiesel production, is a key player compound due to its chemical versatility. The possibility of being used as solvent, reagent, reducing agent (in the polyol method), and so forth, makes glycerol an extremely appealing commodity. When used within nanotechnology, namely combined with nanomaterials, its potential becomes even higher. This review summarizes the work developed by the scientific community, during the last five years, in the use of glycerol with nano oxides. The analysis goes from the simple role of solvent to the oxidation of glycerol by nano oxides. Keywords: glycerol; oxidation; nano oxide; catalyst; nanoparticles 1. Introduction Global warming is one of humanity’s major concerns in view of the continuous increase of greenhouse gas emissions that results from the anthropogenic activities (consequence of rapid population growing). Currently, fossil fuels carbon sources (e.g., natural gas, oil, or coal) constitute over 80% of the world’s primary energy supply. As an outcome, the climate stability of the biosphere is affected with countless consequences. In December 2015, the 21st Conference of the Parties, COP21 (the United Nations conference on climate change), brought public awareness to the measures required to slow down global warming. Moreover, a framework to mitigate climate change was set, by agreeing on 17 SDGs—sustainable development goals. In addition, the Intergovernmental Panel on Climate Change (IPCC) set as an aim to keep the warming under 2 ◦C above preindustrial levels and to pursue efforts to restrict the temperature increase to a limit of 1.5 ◦C above preindustrial levels, whereas the European Union set the aim of reducing 80% of domestic emissions by 2050 (when compared to 1990) [1]. The use of greener fuels to address such envisaged goals is pointed out as one of the most promising solutions, unlocking a competitive, low carbon, and energy efficient future. By using wastes and emissions as feedstock to produce fuels, a new sustainable alternative to traditional petrochemical feedstock processes (avoiding their uncertain availability, and their Catalysts 2020, 10, 1406; doi:10.3390/catal10121406 www.mdpi.com/journal/catalysts Catalysts 2020, 10, x FOR PEER REVIEW 2 of 18 By using wastes and emissions as feedstock to produce fuels, a new sustainable alternative to traditionalCatalysts 2020 , petrochemical10, 1406 feedstock processes (avoiding their uncertain availability, and 2their of 17 environmental concerns) can be attained, which is imperative, especially to the transport sector [2]. However,environmental there concerns) is still much can beto attained, overcome which to achieve is imperative, a cost-effective especially and to theoperationally transport sector feasible [2]. methodologyHowever, there that is can still be much incorporated to overcome in a bioref to achieveinery, awhere, cost-e throughffective andjointly operationally applied conversion feasible technologies,methodology almost that can all betypes incorporated of biomass in feedstocks a biorefinery, can be where, transformed through into jointly different applied classes conversion of bio- fuelstechnologies, and chemicals. almost all types of biomass feedstocks can be transformed into different classes of bio- fuelsThere and chemicals. are several methods to produce biodiesel that includes transesterification, blending of raw oils, Theremicroemulsion, are several dilution, methods and to produce pyrolysis biodiesel or thermal that includescracking. transesterification, The predominant blending biodiesel of productionraw oils, microemulsion, process, which dilution, is also andthe pyrolysiseasiest ro orute, thermal being cracking.consequently The the predominant most cost-effective biodiesel approach,production involves process, whicha step isof also transesterification the easiest route, yielding being consequently glycerol (1,2,3-propanetriol, the most cost-effective Figure approach, 1) as a by-productinvolves a step [3]. of transesterification yielding glycerol (1,2,3-propanetriol, Figure1) as a by-product [ 3]. OH HO OH Figure 1. Glycerol (1,2,3-propanetriol) structure. Figure 1. Glycerol (1,2,3-propanetriol) structure. Increases in biodiesel production in many countries, to replace the traditional petroleum-based energyIncreases have led in tobiodiesel an excess production of crude glycerol.in many countries, This represents to replace the mainthe traditional bottleneck petroleum-based in the biodiesel energyproduction have chain. led to Simultaneously, an excess of crude such glycerol. a glycerol This surplus represents has created the main new challengesbottleneck toinits the sustainable biodiesel productionuse. In fact, chain. although Simultaneously, available on thesuch market a glycerol at a verysurplus low cost,has created glycerol new contains challenges a number to its of sustainableimpurities (e.g., use. un-reacted In fact, although glycerides, available water, methanol,on the market free fatty at a acids, very methyllow cost, esters glycerol and other contains organic a numbermaterials of or impurities inorganic (e.g., salts un-reacted [4–6]), which glycerides, affects its water, properties methanol, (biological, free fatty chemical, acids, methyl and physical) esters and and othertherefore organic inhibits materials its direct or inorganic usage in industries.salts [4–6]), which affects its properties (biological, chemical, and physical)The compositionand therefore of inhibits crude glycerol its direct depends usage in on industries. the process used for the production of the biodiesel as wellThe as composition on the nature of of crude feedstock glycerol [7]. Asdepends such, thereon the is aprocess wide variety used for of potential the production alternatives of the to biodieseladd value as to well glycerol, as on which the nature fall into of the feedstock following [7]. main As such, categories there of is applications: a wide variety (i) manufactureof potential alternativesof commodities; to add (ii) value production to glycerol, of polymers; which fall (iii) into production the following of biofuels main categories and biogas; of applications: and (iv) use (i) of manufacturepurified glycerol. of commodities; Thus, the multifunctionality (ii) production of ofpolyme glycerolrs; (iii) makes production it a suitable of biofuels bio-renewable and biogas; platform and (iv)chemical. use of purified Figure2 presentsglycerol. diThus,fferent the chemicalmultifunctionality reaction pathways of glycerol of makes glycerol. it a suitable bio-renewable platformGlycerol chemical. is considered Figure 2 apresents particularly differen interestingt chemical building reaction block pathways to provide of glycerol. added-value bio-based compounds. In the chemicals market, the production of bio-based products has become a priority for the industries of plastics, solvents, lubricants, and surfactants. The forecast period of 2019–2027 [8] expects an increase at a compound annual growth rate (CAGR) of 16.67%. The production of bio-based compounds offers an excellent alternative to reduce the dependence of petroleum-based feedstocks, to improve the environmental balance (decreasing CO2 emissions), to boost cleaner, more efficient, modern and future oriented industries, and to meet the increasing of consumers demand for healthier and safer products. Besides the several pathways to obtain molecules derived from glycerol (Figure2), there is a much less explored application of glycerol that can be as important and relevant as the currently most known ones: the production of nanomaterials. In fact, nanosciences and nanotechnology assume a pivotal role in the processes of accelerating the energy transition to the use of renewable sources through the development of new materials, which increase the efficiency of processes, rationalize the use of resources and raw materials, and help to reduce the costs. The use of glycerol as solvent for the dispersion of metal oxide nanoparticles presenting catalytic abilities (Figure3), increasing their lifetime, is also an emerging field of research. Catalysts 2020, 10, 1406 3 of 17 Catalysts 2020, 10, x FOR PEER REVIEW 3 of 18 Figure
Load more

Recommended publications
  • Electric Dipole Moments of the Fluorescent Probes Prodan and Laurdan: Experimental and Theoretical Evaluations
    Electric dipole moments of the fluorescent probes Prodan and Laurdan: experimental and theoretical evaluations Cíntia C. Vequi-Suplicy, Kaline Coutinho & M. Teresa Lamy Biophysical Reviews ISSN 1867-2450 Volume 6 Number 1 Biophys Rev (2014) 6:63-74 DOI 10.1007/s12551-013-0129-8 1 23 Your article is protected by copyright and all rights are held exclusively by International Union for Pure and Applied Biophysics (IUPAB) and Springer-Verlag Berlin Heidelberg. This e-offprint is for personal use only and shall not be self-archived in electronic repositories. If you wish to self- archive your article, please use the accepted manuscript version for posting on your own website. You may further deposit the accepted manuscript version in any repository, provided it is only made publicly available 12 months after official publication or later and provided acknowledgement is given to the original source of publication and a link is inserted to the published article on Springer's website. The link must be accompanied by the following text: "The final publication is available at link.springer.com”. 1 23 Author's personal copy Biophys Rev (2014) 6:63–74 DOI 10.1007/s12551-013-0129-8 REVIEW Electric dipole moments of the fluorescent probes Prodan and Laurdan: experimental and theoretical evaluations Cíntia C. Vequi-Suplicy & Kaline Coutinho & M. Teresa Lamy Received: 13 August 2013 /Accepted: 3 December 2013 /Published online: 14 January 2014 # International Union for Pure and Applied Biophysics (IUPAB) and Springer-Verlag Berlin Heidelberg 2014 Abstract Several experimental and theoretical approaches Keywords Prodan . Laurdan . Optical absorption and can be used for a comprehensive understanding of solvent fluorescence .
    [Show full text]
  • New Insights on the Fluorescent Emission Spectra of Prodan and Laurdan
    J Fluoresc (2015) 25:621–629 DOI 10.1007/s10895-015-1545-x ORIGINAL PAPER New Insights on the Fluorescent Emission Spectra of Prodan and Laurdan Cíntia C. Vequi-Suplicy & Kaline Coutinho & M. Teresa Lamy Received: 12 December 2014 /Accepted: 23 February 2015 /Published online: 10 March 2015 # Springer Science+Business Media New York 2015 Abstract Prodan and Laurdan are fluorescent probes largely Introduction used in biological systems. They were synthetized to be sen- sitive to the environment polarity, and their fluorescent emis- The fluorescent probes Prodan (2-dimethylamino-6- sion spectrum shifts around 120 nm, from cyclohexane to propionylnaphthalene) and Laurdan (2-dimethylamino-6- water. Although accepted that their emission spectrum is com- dodecanoylnaphthalene) have been widely used in biological posed by two emission bands, the origin of these two bands is relevant systems [1–7]. They were synthetized [1]tobesen- still a matter of discussion. Here we analyze the fluorescent sitive to the environment polarity, so their emission spectra spectra of Prodan and Laurdan in solvents of different polar- shifts about 120 nm from cyclohexane to water [1, 8, 9]. ities, both by decomposing the spectrum into two Gaussian Moreover, when inserted into membranes, their emission bands and by computing the Decay Associated Spectra spectra is extremely dependent on the lipid bilayer phase (DAS), the latter with time resolved fluorescence. Our data (gel or fluid), the maximum of the spectrum shifting around show that the intensity of the lower energy emission band of 50 nm from one phase to the other [4, 6, 10]. Prodan and Laurdan (attributed, in the literature, to the decay Although Prodan and Laurdan have been extensively used, of a solvent relaxed state) is higher in cyclohexane than in their structure and electronic distribution, in different solvents, water, showing a decrease as the polarity of the medium in- are still a matter of discussion [11–13].
    [Show full text]
  • A New Interpretation of the Absorption and the Dual Fluorescence of Prodan in Solution
    A new interpretation of the absorption and the dual fluorescence of Prodan in solution Cíntia C. Vequi-Suplicy1,2, Yoelvis Orozco-Gonzalez1,3, M. Teresa Lamy1, Sylvio Canuto1, Kaline Coutinho1* 1. Instituto de Física, Universidade de São Paulo, Rua do Matão,1371, 05508-090, São Paulo, SP, Brazil. 2. Fundacion IMDEA-Nanociencia Cantoblanco, 28049, Madrid, Spain. 3. Department of Chemistry, Georgia State University, Atlanta, GA 30302, United States. Abstract Remarkable interest is associated to the interpretation of Prodan fluorescent spectrum. A sequential hybrid Quantum Mechanics/Molecular Mechanics (S-QM/MM) method was used to establish that the fluorescent emission occurs from two different excited states, resulting in a broad asymmetric emission spectrum. The absorption spectra in several solvents were measured and calculated using different theoretical models presenting excellent agreement. All theoretical models (INDO-CIS, TD- B3LYP and CASPT2) agree that the first observed band at the absorption spectrum in solution is composed of three electronic excitations very close in energy. Then, the electronic excitation around 340-360 nm may populate the first three excited states (π-π*Lb, n-π* and π-π*La). The ground state S0 and the first three excited states were analyzed using multi-configurational calculations (CASSCF) and second-order multi-configurational perturbation theory (CASPT2). The corresponding equilibrium geometries are all planar in vacuum. Considering the solvent effects in the electronic structure of the solute and in the solvent relaxation around the solute, it was identified that these three excited states can change the relative order depending on the solvent polarity and following the minimum path energy, internal conversions may occur.
    [Show full text]
  • Internally Hydrogen-Bonded PRODAN Derivatives
    W&M ScholarWorks Dissertations, Theses, and Masters Projects Theses, Dissertations, & Master Projects 2015 Internally Hydrogen-Bonded PRODAN Derivatives Douglas William Cheek College of William & Mary - Arts & Sciences Follow this and additional works at: https://scholarworks.wm.edu/etd Part of the Chemistry Commons Recommended Citation Cheek, Douglas William, "Internally Hydrogen-Bonded PRODAN Derivatives" (2015). Dissertations, Theses, and Masters Projects. Paper 1539626962. https://dx.doi.org/doi:10.21220/s2-2ehp-5r55 This Thesis is brought to you for free and open access by the Theses, Dissertations, & Master Projects at W&M ScholarWorks. It has been accepted for inclusion in Dissertations, Theses, and Masters Projects by an authorized administrator of W&M ScholarWorks. For more information, please contact [email protected]. Internally Hydrogen-Bonded PRODAN Derivatives Douglas William Cheek Fairfax, VA Bachelor of Science, College of William & Mary, 2014 A Thesis presented to the Graduate Faculty of the College of William and Mary in Candidacy for the Degree of Master of Science Department of Chemistry The College of William and Mary August 2015 APPROVAL PAGE This Thesis is submitted in partial fulfillment of the requirements for the degree of ster of Science Douglas Willt ieek Approver by the Committee, July >201 ^o^imitteo^ Cjnair Chancellor Professor and Department CKair Christopher Abelt, Chemistry College of William & Mary Associate Professor Elizabeth Harbron, Chemistry College of William & Mary Associate Professor Jonathan Scheerer, Chemistry College of William & Mary ARTS# SCIENCES Institutional Compliance Committee Form Every A&S graduate student must answer all questions below by checking either the “yes” o' the “no” box for each question.
    [Show full text]
  • 2,5-PRODAN Derivatives As Highly Sensitive Sensors of Low Solvent Acidity
    Molecules 2014, 19, 6415-6427; doi:10.3390/molecules19056415 OPEN ACCESS molecules ISSN 1420-3049 www.mdpi.com/journal/molecules Article 2,5-PRODAN Derivatives as Highly Sensitive Sensors of Low Solvent Acidity Alexandra H. Yoon, Laura C. Whitworth, Joel D. Wagner and Christopher J. Abelt * Department of Chemistry, College of William and Mary, Williamsburg, VA 23187-8795, USA * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +1-757-221-2677; Fax: +1-757-221-2715. Received: 2 April 2014; in revised form: 8 May 2014 / Accepted: 12 May 2014 / Published: 20 May 2014 Abstract: Two 5-acyl-2-dimethylaminonaphthalene derivatives, one with a propionyl group and the other with a fused cyclohexanone ring, are investigated as sensors of H-bond-donating ability in protic solvents of low solvent acidity. Their fluorescence is highly quenched in protic solvents, and the quenching order of magnitude is linearly related to the H-bond-donating ability of the solvent as quantified by the solvent acidity (SA) scale. As the solvent acidity increases from 0.15 to 0.40, the fluorescence for both is quenched by more than a factor of ten; thus, they are extremely sensitive sensors of the hydrogen-bond-donating ability in this weakly acidic range. Preferential solvation studies suggest that quenching occurs from a doubly H-bonded excited state. Keywords: H-bonding; sensor; fluorescence; quenching 1. Introduction The development of molecular sensors is an active field of research. Molecules can act as sensors when they have a measurable physical quantity that is responsive to some external stimulus [1].
    [Show full text]
  • Aquatic Pesticides Monitoring Program Literature Review
    SAN FRANCISCO ESTUARY INSTITUTE AQUATIC PESTICIDES MONITORING PROGRAM Aquatic Pesticides Monitoring Program Literature Review Geoff Siemering, Nicole David, Jennifer Hayworth and Amy Franz San Francisco Estuary Institute, Oakland, California Karl Malamud-Roam Contra Costa Mosquito Vector Control CONTRIBUTION NO. 71 APRIL 2003 REVISED FEB 2005 Contact Information San Francisco Estuary Institute 7770 Pardee Lane, 2nd Floor Oakland, CA 94621 Phone: 510-746-SFEI Website: www.sfei.org Contra Costa Mosquito Vector Control District 155 Mason Circle Concord, CA 94520 Phone: 925-685-9301 Website: www.ccmvcd.dst.ca.us/index.html This report should be cited as: Siemering, Geoff, N. David, J. Hayworth, A. Franz and K. Malamud-Roam. October 2003. Revised, February 2005. Aquatics Pesticides Monitoring Program Literature Review. SFEI Contribution 71. San Francisco Estuary Institute, Oakland, CA. San Francisco Estuary Institute Contents Executive Summary ......................................................................................................................................................9 Section I. Evaluation of Health and Environmental Risks Associated with Pesticides and other Chemicals in the Environment ..............................................................................................................................................10 A. Chemical Identification and Characterization ....................................................................................................11 I. Chemical Description and Type .............................................................................................................11
    [Show full text]
  • Blue Fluorescent Amino Acid for Biological Spectroscopy and Microscopy
    Blue fluorescent amino acid for biological spectroscopy and microscopy Mary Rose Hilairea,1, Ismail A. Ahmedb,1, Chun-Wei Lina, Hyunil Joc, William F. DeGradoc,2, and Feng Gaia,d,2 aDepartment of Chemistry, University of Pennsylvania, Philadelphia, PA 19104; bDepartment of Biochemistry and Molecular Biophysics, University of Pennsylvania, Philadelphia, PA 19104; cDepartment of Pharmaceutical Chemistry, University of California, San Francisco, CA 94158; and dUltrafast Optical Processes Laboratory, University of Pennsylvania, Philadelphia, PA 19104 Contributed by William F. DeGrado, April 20, 2017 (sent for review February 20, 2017; reviewed by Jacob W. Petrich and Dongping Zhong) Many fluorescent proteins are currently available for biological are potential candidates that meet the aforementioned require- spectroscopy and imaging measurements, allowing a wide range ments. However, the emission maxima of 6CN-Trp and 7CN-Trp of biochemical and biophysical processes and interactions to be in methanol are centered at 370 and 390 nm, respectively, studied at various length scales. However, in applications where a making them less attractive as visible fluorophores. As shown small fluorescence reporter is required or desirable, the choice of (Fig. 1), the absorption and emission spectra of 4-cyano-indole fluorophores is rather limited. As such, continued effort has been (4CNI), the sidechain of 4CN-Trp, are significantly shifted from devoted to the development of amino acid-based fluorophores those of indole (or Trp) and, in particular, an emission maximum that do not require a specific environment and additional time to of 405 nm suggests that 4CN-Trp could be a viable candidate for mature and have a large fluorescence quantum yield, long fluores- the aforementioned amino acid-based fluorophores.
    [Show full text]
  • Influence of DPPC Liposome Concentration on the Fluorescence
    Influence of DPPC Liposome Concentration on the Fluorescence Properties of PRODAN and LAURDAN K. A. Kozyra, J. R. Heldt, G. Gondek, P. Kwiek, and J. Heldt a Institute of Experimental Physics, University of Gda´nsk, ul. Wita Stwosza 57, 80-952 Gda´nsk, Poland a Institute of Physics, Pomeranian Pedagogical Academy, ul. Arciszewskiego 22B, 76-200 Słupsk, Poland Reprint requests to Dr. K. A. K.; E-mail: [email protected] Z. Naturforsch. 59a, 809 – 818 (2004); received July 21, 2004 Fluorescence spectral features of PRODAN and LAURDAN in phospholipid vesicles of different phase states were investigated. The results indicate that in the liquid crystalline phase the dominant emission results from the charge transfer (CT) excited state, whereas in the gel state of the mem- brane the emission from the locally excited (LE) state dominates. The fluorescence time studies point out that there are two radiation modes, one starting from only vibrationally relaxed excited states S1(LE)ν ((S1(CT)ν ) and the other from a totally thermally equilibrated state S1(LE)EQ (S1(CT)EQ). In accordance with the obtained decay time dependencies, the fluorescence emission from total non- equilibrated excited states consists of a dominant or minor radiation process in the LE or CT band emission. Key words: PRODAN, LAURDAN; Locally Excited and Charge Transfer States; Fluorescence Decay Time. 1. Introduction PRODAN (6-propionyl-2-dimethylaminonaphtal- ene) and LAURDAN (6-dodecanoyl-2-dimethylami- nonaphtalene) have been widely used to study the structure and dynamics of biological systems, e. g. membrane constituents, surfaces, large biological molecules, cells, etc. [1 – 5].
    [Show full text]
  • First Line of Title
    TIME RESOLVED AND STEADY STATE EXPERIMENTS WITH PRODAN AND LAURDAN SOLUTIONS by Matthew J. Phillips A thesis submitted to the Faculty of the University of Delaware in partial fulfillment of the requirements for the degree of Master of Science in Chemistry and Biochemistry Spring 2019 © 2019 Phillips All Rights Reserved TIME RESOLVED AND STEADY STATE EXPERIMENTS WITH PRODAN AND LAURDAN SOLUTIONS by Matthew J. Phillips Approved: __________________________________________________________ Lars Gundlach, Ph.D. Professor in charge of thesis on behalf of the Advisory Committee Approved: __________________________________________________________ Brian Bahnson, Ph.D. Chair of the Department of Chemistry and Biochemistry Approved: __________________________________________________________ John Pelesko, Ph.D. Interim Dean of the College of Arts and Sciences Approved: __________________________________________________________ Douglas J. Doren, Ph.D. Interim Vice Provost for Graduate and Professional Education ACKNOWLEDGMENTS A huge thank you to Dr. Lars Gundlach, whose mentorship and guidance made this work and my professional development possible. My colleagues Samantha Doble, Joseph Avenoso, Han Yan, Mercury Li, Meng Jia, who are always willing to share their knowledge and expertise, and make lab awesome. The support and love of my friends and family iii TABLE OF CONTENTS LIST OF TABLES ......................................................................................................... v LIST OF FIGURES ......................................................................................................
    [Show full text]
  • And Excited-State Dipole Moments of 6-Propionyl-2-(Dimethylamino)Naphthalene Determined from Solvatochromic Shifts*
    Ground- and Excited-State Dipole Moments of 6-Propionyl-2-(dimethylamino)naphthalene Determined from Solvatochromic Shifts* A. Kawski Luminescence Research Group, Institute of Experimental Physics, University of Gdansk, ul. Wita Stwosza 57, 80-952 Gdansk, Poland Reprint requests to Prof. A. K„ Fax: +48 58 3413 175 Z. Naturforsch. 54a, 379-381 (1999); received April 30, 1999 The dipole moments in the ground- and excited-state of the fluorescence probe 6-propionyl-2-(dim- ethylamino)naphthalene (PRODAN) are determined from solvatochromic shifts to be = 2.1 D and tje = 6.4 D. These values concern the free molecule. In the first excited singlet state the dipole moment is only 3 times greater than in the ground state. 1. Introduction the increments in the dipole moments, A/J, determined for different fluorescent molecules, based on the Lippert- The hydrophobic fluorescent probe 6-propionyl-2- Mataga solvent polarity parameter are much overrated in (dimethylamino)naphthalene (PRODAN), is highly sen- comparison to the values /ue obtained by electrooptical sitive to the solvent polarity and can potentially reveal methods [7-10], the polarity of its immediate environment. The spectral In the present paper we determine the dipole moments properties of PRODAN (Figure 1) are of interest in bio- ,ug and yue of PRODAN by the "solvent perturbation chemistry and are described by Weber and Farris [1] and method" [8, 11], utilizing the absorption and fluores- by Lakowicz [2]. cence shifts in different solvents measured by Catalan et al. [4]. CH, I " N "CH. 2. Basic Equations of the Analysis jOOT of Dipole Moments CH3-CH2-C V The following equations are based on the quantum- mechanical perturbation theory [8, 11] of the absorp- PRODAN tion (vA) and fluorescence (vF) band shifts (in wave- Fig.
    [Show full text]
  • Effect of Pressure on the Prodan Fluorescence in Bilayer Membrane of Ether-Linked Lipid, Dihexadecylphosphatidylcholine
    High Pressure Bioscience and Biotechnology 61 Proceedings of the 4th International Conference on High Pressure Bioscience and Biotechnology, Vol. 1, 61–67, 2007 Effect of Pressure on the Prodan Fluorescence in Bilayer Membrane of Ether-Linked Lipid, Dihexadecylphosphatidylcholine Masataka Kusube1, Masaki Goto2, Nobutake Tamai2, Hitoshi Matsuki2 and Shoji Kaneshina*2 1Department of Material Science, Wakayama National College of Technology, 77 Noshima, Nada, Gobo, Wakayama 644-0023, Japan 2Department of Biological Science and Technology, Graduate School of Advanced Technology and Science, and Department of Life System, Institute of Technology and Science, The University of Tokushima, 2-1 Minamijosanjima-cho, Tokushima 770- 8506, Japan *E-mail: [email protected] Received 8 December 2006/Accepted 15 December 2006 Abstract The fluorescence spectra of 6-propionyl-2-(dimethyamino)-naphthalene (Prodan) in the bilayer membrane of an ether-linked phospholipid, dihexadecylphosphatidylcholine (DHPC), were observed as a function of temperature and pressure. Previous results for Prodan in the bilayer membrane of an ester-linked lipid, dipalmitoylphosphatidyl- choline (DPPC), were compared with the present results. A great difference in the fluorescence spectrum shape was found in the ripple gel phase of the DHPC and DPPC bilayers. The location of the Prodan molecule in the bilayer was speculated on the basis of the maximum emission wavelength. The ratio of fluorescence intensity of Prodan at two wavelengths was useful for the determination of bilayer phase transition, especially the pressure-induced interdigitation. Keywords: bilayer membrane, ether-linked lipid, pressure-induced interdigitation, phase transition, Prodan-fluorescence 1. Introduction Dipalmitoyl-(DPPC) and dihexadecylphosphatidylcholine (DHPC) are representative phospholipids with ester- and ether-linkage, respectively.
    [Show full text]
  • Laurdan and Prodan As Polarity-Sensitive Fluorescent Membrane Probes
    UC Irvine UC Irvine Previously Published Works Title Laurdan and Prodan as Polarity-Sensitive Fluorescent Membrane Probes Permalink https://escholarship.org/uc/item/12x671xw Journal Journal of Fluorescence, 8(4) ISSN 1053-0509 Authors Parasassi, T Krasnowska, EK Bagatolli, L et al. Publication Date 1998 DOI 10.1023/A:1020528716621 License https://creativecommons.org/licenses/by/4.0/ 4.0 Peer reviewed eScholarship.org Powered by the California Digital Library University of California Journal of Fluorescence, Vol. 8, No. 4, 1998 Laurdan and Prodan as Polarity-Sensitive Fluorescent Membrane Probes Tiziana Parasassi,1,3 Ewa K. Krasnowska,1 Luis Bagatolli,2 and Enrico Gratton2 Received February 25, 1998; Accepted July 13, 1998 The steady-state and dynamic fluorescence spectral properties of 2-dimethylamino-6-lauroylna- phthalene (LAURDAN) and several other naphthalene derivatives are summarized to illustrate their sensitivity to the polarity of the environment. Results obtained both in solvents of different polarity and in phospholipid vesicles in two phase states are presented. The emission red shift observed in polar solvents and in the phospholipid liquid–crystalline phase is explained on the basis of dipolar relaxation of solvent molecules surrounding the fluorescent naphthalene moiety of these probes. In phospholipid environments, experimental evidence is shown that excludes the intramolecular relative reorientation of the dimethylamino and carbonyl groups in the naphthalene and the reo- rientation of the entire fluorescent moiety. The solvent dipolar relaxation observed for LAURDAN and PRODAN in phospholipid bilayers has been attributed to a small number of water molecules present at the membrane interface. A comparison between LAURDAN emission in phospholipid vesicles prepared in D2O and in H2O is also presented.
    [Show full text]