DOCSLIB.ORG

Perylene Bisimides: Facile Synthesis and Characterization As Near-Infrared Fluorescent Dyes

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Perylene Bisimides: Facile Synthesis and Characterization As Near-Infrared Fluorescent Dyes Materials 2014, 7, 7548-7565; doi:10.3390/ma7117548 OPEN ACCESS materials ISSN 1996-1944 www.mdpi.com/journal/materials Article 1,7-Bis-(N,N-dialkylamino)perylene Bisimides: Facile Synthesis and Characterization as Near-Infrared Fluorescent Dyes Kew-Yu Chen * and Che-Wei Chang Department of Chemical Engineering, Feng Chia University, Taichung 40724, Taiwan; E-Mail: [email protected] * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +886-4-2451-7250 (ext. 3683); Fax: +886-4-2451-0890. External Editor: Dirk Poelman Received: 20 October 2014; in revised form: 10 November 2014 / Accepted: 13 November 2014 / Published: 24 November 2014 Abstract: Three symmetric alkylamino-substituted perylene bisimides with different n-alkyl chain lengths (n = 6, 12, or 18), 1,7-bis-(N,N-dialkylamino)perylene bisimides (1a–1c), were synthesized under mild condition and were characterized by 1H NMR, 13C NMR and high resolution mass spectroscopy. Their optical and electrochemical properties were measured using UV-Vis and emission spectroscopic techniques as well as cyclic voltammetry (CV). These compounds show deep green color in both solution and solid state, and are highly soluble in dichloromethane and even in nonpolar solvents such as hexane. The shapes of the absorption spectra of 1a–1c in the solution and solid state were found to be almost the same, indicating that the long alkyl chains could efficiently prevent intermolecular contact and aggregation. They show a unique charge transfer emission in the near-infrared region, of which the peak wavelengths exhibit strong solvatochromism. The dipole moments of the molecules have been estimated using the Lippert–Mataga equation, and upon excitation, they show larger dipole moment changes than that of 1,7-diaminoperylene bisimide (2). Moreover, all the dyes exhibit two irreversible one-electron oxidations and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Complementary density functional theory calculations performed on these chromophores are reported in order to rationalize their electronic structure and optical properties. Materials 2014, 7 7549 Keywords: near-infrared fluorescent dyes; 1,7-bis-(N,N-dialkylamino)perylene bisimides; intramolecular charge transfer; solvatochromism; Lippert–Mataga equation; density functional theory calculations 1. Introduction Derivatives of perylene bisimide (PBI) have continuously attracted significant attention due to their applications in molecular electronic devices, such as light-emitting diodes [1–5], LCD color filters [6,7], organic field-effect transistors (OFETs) [8–13], light-harvesting arrays [14,15], photovoltaic cells [16–25], molecular wires [26,27], and photochromic materials [28,29]. PBIs have also been utilized as building blocks to construct supramolecular or artificial photosynthetic systems [30–33]. These organic molecules are advantageous due to their high molar absorptivities, high photochemical and optical stabilities, reversible redox properties, ease of synthetic modification and excellent thermal stability [34–55]. The electronic characteristics of PBIs can also be fine-tuned by introducing different substituents at the bay-positions (1,6,7,12-positions) of the conjugated perylene core. Based on these rules, a number of perylene bisimide derivatives with either electron-withdrawing or electron-donating groups have been reported in the literature, including: (a) perfluoroalkyl-substituted PBIs [56,57]; (b) cyano-substituted PBIs [58,59], (c) nitro-substituted PBIs [60–62]; (d) ferrocenyl-substituted PBIs [63,64], (e) aryl-substituted PBIs [65,66], (f) boryl-substituted PBIs [67]; (g) alkyl-substituted PBIs [68]; (h) piperidinyl-substituted PBIs [69–71], (i) pyrrolidinyl-substituted PBIs [72–74]; (j) amino-substituted PBIs [75,76], (k) alkylamino-substituted PBIs [77–79], (l) alkoxy-substituted PBIs [80–84]; (m) hydroxy-substituted PBIs [85,86], etc. To date, a promising strategy for introducing substituents onto the PBI core is bromination or chlorination of perylene dianhydride. Subsequently, replacement of these halogens is readily executed by traditional substitution reactions or by metal-catalyzed cross-coupling reactions. However, both of these methods are usually accompanied by extensive debromination [77] and stringent reaction conditions such as high temperatures, and absence of oxygen and water. In an effort to expand the scope of PBI-based chromophores available for designing systems for colorful dyes and self-assembly, we synthesized a series of blue dyes based on 1,7-diaminoperylene bisimides [76]. We herein report on the introduction of different long alkyl chains of 1,7-diaminoperylene bisimide (2) affording chromophores (1a–1c) that are deep green in color and that readily undergo two irreversible one-electron oxidations and two quasi-reversible one-electron reductions. 2. Experimental Section 2.1. General The starting materials such as perylene-3,4,9,10-tetracarboxyldianhydride, acetic acid, cyclohexylamine, cerium (IV) ammonium nitrate (CAN), tin (II) chloride dihydrate (SnCl2.2H2O), N-methyl-2-pyrrolidinone (NMP), tetrahydrofuran (THF), sodium hydride (NaH), 1-iodohexane (C6H13I), 1-iodododecane (C12H25I), and 1-iodooctadecane (C18H37I) were purchased from Merck Materials 2014, 7 7550 (Whitehouse Station, NJ, USA), ACROS (Pittsburgh, PA, USA) and Sigma–Aldrich (St. Louis, MO, USA). Solvents were distilled freshly according to standard procedure. Column chromatography was performed using silica gel Merck Kieselgel si 60 (40–63 mesh). 1H and 13C NMR spectra were recorded in CDCl3 on a Bruker 400 MHz NMR spectrometer (Palo Alto, CA, USA). Mass spectra were recorded on a VG70-250S mass spectrometer (Tokyo, Japan). The absorption and emission spectra were measured using a Jasco V-570 UV–Vis spectrophotometer (Tokyo, Japan) and a Hitachi F-7000 fluorescence spectrophotometer (Tokyo, Japan), respectively. Cyclic voltammetry (CV) was performed with a CH instruments (Austin, TX, USA) at a potential rate of 200 mV/s in a 0.1 M solution of tetrabutylammonium hexafluorophosphate (TBAPF6) in dichloromethane. Platinum and Ag/AgNO3 electrodes were used as counter and reference electrodes, respectively. 2.2. Synthesis 2.2.1. Perylene Bisimide (4) A suspension of perylene dianhydride (900 mg, 2.3 mmol), cyclohexylamine (570 mg, 5.8 mmol), and acetic acid (500 mg, 8.3 mmol) in 50 mL of N-methyl-2-pyrrolidinone was stirred at 80 °C under nitrogen for 8 h. After the mixture was cooled to room temperature, the precipitate was isolated by filtration, washed with 200 mL of MeOH, and dried in a vacuum. The crude product was purified by silica gel column chromatography with eluent CH2Cl2 to afford 4 (950 mg, 75%). Characterization 1 data: 4: H NMR (400 MHz, CDCl3) δ 8.64 (d, J = 8.0 Hz, 4H), 8.60 (d, J = 8.0 Hz, 4H), 5.05 (m, 2H), 2.58 (m, 4H), 1.91 (m, 4H), 1.76 (m, 6H), 1.36–1.46 (m, 6H). MS (FAB): m/z (relative intensity) 555 + (M , 100); HRMS calcd. for C36H31N2O4 555.2284, found 555.2290. 2.2.2. Synthesis of 1,7-Dinitroperylene Bisimide (3) A mixture of perylene bisimide 4 (900 mg, 1.6 mmol), cerium (IV) ammonium nitrate (CAN) (2.4 g, 4.4 mmol), nitric acid (0.1 M, 6.0 mL) and dichloromethane (150 mL) was stirred at 25 °C under N2 for 48 h. The mixture was neutralized with 10% KOH and extracted with CH2Cl2. After solvent was removed, the crude product was purified by silica gel column chromatography with eluent 1 CH2Cl2 to afford 3 (837 mg, 80%). Characterization data: 3: H NMR (400 MHz, CDCl3) δ 8.78 (s, 2H), 8.67 (d, J = 8.0 Hz, 2H), 8.28 (d, J = 8.0 Hz, 2H), 4.99 (m, 2H), 2.51 (m, 4H), 1.92 (m, 4H), 1.74 (m, 6H), 1.46 (m, 4H), 1.36 (m, 2H); MS (FAB): m/z (relative intensity) 645 (M+H+, 100); HRMS calcd. for C36H29O8N4 645.1985, found 645.1981. 2.2.3. Synthesis of 1,7-Diaminoperylene Bisimide (2) Tin chloride dihydrate (1.5 g, 7.2 mmol) and 3 (0.8 g, 1.2 mmol) were suspended in 60 mL of THF, and stirred 20 min. The solvent was refluxed with stirring for 6 h at 80 °C. THF was removed at the rotary evaporator, and the residue was dissolved in ethyl acetate and washed with 10% NaOH solution and brine. The organic layer was dried over anhydrous MgSO4 and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with eluent ethyl acetate/n-hexane (2/3) to afford 2 (595 mg, 85%). Characterization data: 2: 1H NMR (400 MHz, CDCl3) δ 8.87 (d, J = 8.4 Hz, 2H), 8.43 (d, J = 8.4 Hz, 2H), 8.14 (s, 2H), 5.04, (m, 2H), 4.94 (s, 4H), Materials 2014, 7 7551 2.61 (m, 4H), 1.93 (m, 4H), 1.74 (m, 6H), 1.36–1.54 (m, 6H); MS (FAB): m/z (relative intensity) 585 + (M+H , 100); HRMS calcd. for C36H33O4N4 585.2502, found 585.2504. 2.2.4. General Procedure for Alkylation (1a–1c) A mixture of solution of 2 (410 mg, 0.70 mmol), sodium hydride (97%, 200 mg, 8.00 mmol) and dry THF (60 mL) was stirred at 0 °C under N2 for 30 min. Alkyl iodide (4.20 mmol) was then added and the resulting mixture was stirred for 8 h. The resulting mixture was diluted with 15 mL of water and extracted with CH2Cl2. The crude product was purified by silica gel column chromatography with eluent ethyl acetate/n-hexane (1/2) to afford 1a (1b or 1c) in 75% yield. Characterization data: 1a: 1 H NMR (400 MHz, CDCl3) δ 9.21 (d, J = 8.0 Hz, 2H), 8.45 (s, 2H), 8.38 (d, J = 8.0 Hz, 2H), 5.03 (m, 2H), 3.45 (m, 4H), 3.15 (m, 4H), 2.57 (m, 4H), 1.87 (m, 4H), 1.15–1.75 (m, 44H), 13 0.82 (t, J = 6.4 Hz, 12H); C NMR (100 MHz, CDCl3) δ 164.51, 164.21, 148.51, 135.42, 130.32, 128.21, 125.31, 124.29, 122.90, 122.74, 122.63, 121.10, 53.77, 52.54, 31.42, 29.17, 27.46, 26.89, 26.60, 25.52, + 22.49, 13.90; MS (FAB): m/z (relative intensity) 921 (M+H , 100); HRMS calcd.
Load more

Recommended publications
  • Mild Synthesis of Perylene Tetracarboxylic Monoanhydrides with Potential Applications in Organic Optoelectronics
    City University of New York (CUNY) CUNY Academic Works All Dissertations, Theses, and Capstone Projects Dissertations, Theses, and Capstone Projects 5-2019 Mild Synthesis of Perylene Tetracarboxylic Monoanhydrides with Potential Applications in Organic Optoelectronics Xizhe Zhao The Graduate Center, City University of New York How does access to this work benefit ou?y Let us know! More information about this work at: https://academicworks.cuny.edu/gc_etds/3258 Discover additional works at: https://academicworks.cuny.edu This work is made publicly available by the City University of New York (CUNY). Contact: [email protected] Mild Synthesis of Perylene Tetracarboxylic Monoanhydrides with Potential Applications in Organic Optoelectronics By Xizhe Zhao A dissertation submitted to the Graduate Faculty in Chemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy The City University of New York. 2019 © 2019 Xizhe Zhao All Rights Reserved ii Mild Synthesis of Perylene Tetracarboxylic Monoanhydrides with Potential Applications in Organic Optoelectronics by Xizhe Zhao This manuscript has been read and accepted for the Graduate Faculty in Chemistry in satisfaction of the dissertation requirement for the degree of Doctor of Philosophy. 04/29/19 Prof. Shi Jin _________________________ __________________________________________________ Date Chair of Examining Committee 04/29/19 Prof. Brian R. Gibney _________________________ __________________________________________________ Date Executive Officer Supervisory Committee: Prof. Krishnaswami Raja Prof. Sanjai Kumar Pathak THE CITY UNIVERSITY OF NEW YORK iii ABSTRACT Mild Synthesis of Perylene Tetracarboxylic Monoanhydrides with Potential Applications in Organic Optoelectronics By Xizhe Zhao Advisor: Professor Shi Jin Perylene tetracarboxylic derivatives are considered good n-type semi-conductors. In past decades, there has been extensive study on their synthesis and electronic properties.
    [Show full text]
  • Highly Soluble Monoamino-Substituted Perylene Tetracarboxylic Dianhydrides: Synthesis, Optical and Electrochemical Properties
    Int. J. Mol. Sci. 2014, 15, 22642-22660; doi:10.3390/ijms151222642 OPEN ACCESS International Journal of Molecular Sciences ISSN 1422-0067 www.mdpi.com/journal/ijms Article Highly Soluble Monoamino-Substituted Perylene Tetracarboxylic Dianhydrides: Synthesis, Optical and Electrochemical Properties Kew-Yu Chen * and Che-Wei Chang Department of Chemical Engineering, Feng Chia University, Taichung 40724, Taiwan; E-Mail: [email protected] * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +886-4-2451-7250 (ext. 3683); Fax: +886-4-2451-0890. External Editor: Dennis N. Kevill Received: 8 November 2014; in revised form: 21 November 2014 / Accepted: 1 December 2014 / Published: 8 December 2014 Abstract: Three dialkylamino-substituted perylene tetracarboxylic dianhydrides with different n-alkyl chain lengths (n = 6, 12 or 18), 1a–1c, were synthesized under mild conditions in high yields and were characterized by 1H NMR, 13C NMR and high resolution mass spectroscopy. Their optical and electrochemical properties were measured using UV-Vis and emission spectroscopic techniques, as well as cyclic voltammetry (CV). This is the first time that the structures and the properties of monoamino-substituted perylene tetracarboxylic dianhydrides have been reported. These molecules show a deep green color in both solution and the solid state and are soluble in most organic solvents. They all show a unique charge transfer emission in the near-infrared region, and the associated peaks exhibit solvatochromism. The dipole moments of the compounds have been estimated using the Lippert-Mataga equation, and upon excitation, they show slightly larger dipole moment changes than those of corresponding perylene diimides, 2a–2c.
    [Show full text]
  • Polycyclic Aromatic Hydrocarbon Structure Index
    United States Department of Commerce Technology Administration National Institute of Standards and Technology NIST Special Publication 922 Polycyclic Aromatic Hydrocarbon Structure Index Lane C. Sander and Stephen A. Wise This publication is available free of charge from: https://doi.org/10.6028/NIST.SP.922e2020 NIST Special Publication 922 Polycyclic Aromatic Hydrocarbon Structure Index Lane C. Sander and Stephen A. Wise Chemical Science and Technology Laboratory National Institute of Standards and Technology Gaithersburg, MD 20899-0001 December 1997 revised August 2020 This publication is available free of charge from: https://doi.org/10.6028/NIST.SP.922e2020 U.S. Department of Commerce Wilbur L. Ross, Jr., Secretary National Institute of Standards and Technology Walter Copan, NIST Director and Under Secretary of Commerce for Standards and Technology Errata for SP 922 (printed document) Corrected entries are listed below 2 1 3 19 Acephenanthrylene CH 9 10 4 201-06-9 16 10 202 1.291 8 5 Cyclopenta[jk]phenanthrene 11.70 7 6 9.067 3.890 10 1 9 2 27208-37-3 226 1.200 33 8 3 Cyclopenta[cd]pyrene CH18 10 7 4 11.52 6 5 Acepyrene Acepyrylene 9.602 3.887 10 9 1 34 Benz[mno]aceanthrylene 203-13-4 CH 226 8 2 18 10 1.222 7 3 Naphtho[1,8,7,6-cdef]fluorene 11.83 6 5 4 9.679 3.884 2 HC2 1 3 41 11 4 1H-Cyclopenta[e]pyrene 109587-09-9 CH19 12 240 10 5 9 8 6 7 11 1 10 2 9 3 52 5H-Benzo[cd]pyrene 191-34-4 CH19 12 240 1.233 8 5 4 7 6 Pyrenindene 11.92 C 9.674 H2 4.207 14 1 13 2 12 3 160 4 Cyclopent[b]indeno[4,5-g]- 72088-81-4 CH24 14 302 10 11 9 phenanthrene 8 5 7 6 2 3 1 4 14 5 Cyclopent[b]indeno[5,6-g]- 72088-82-5 CH 302 161 6 24 14 12 13 phenanthrene 11 10 7 89 Polycyclic Aromatic Hydrocarbon Structure Index Lane C.
    [Show full text]
  • Polycyclic Aromatic Hydrocarbons (Pahs)
    Polycyclic Aromatic Hydrocarbons (PAHs) Factsheet 4th edition Donata Lerda JRC 66955 - 2011 The mission of the JRC-IRMM is to promote a common and reliable European measurement system in support of EU policies. European Commission Joint Research Centre Institute for Reference Materials and Measurements Contact information Address: Retiewseweg 111, 2440 Geel, Belgium E-mail: [email protected] Tel.: +32 (0)14 571 826 Fax: +32 (0)14 571 783 http://irmm.jrc.ec.europa.eu/ http://www.jrc.ec.europa.eu/ Legal Notice Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use which might be made of this publication. Europe Direct is a service to help you find answers to your questions about the European Union Freephone number (*): 00 800 6 7 8 9 10 11 (*) Certain mobile telephone operators do not allow access to 00 800 numbers or these calls may be billed. A great deal of additional information on the European Union is available on the Internet. It can be accessed through the Europa server http://europa.eu/ JRC 66955 © European Union, 2011 Reproduction is authorised provided the source is acknowledged Printed in Belgium Table of contents Chemical structure of PAHs................................................................................................................................. 1 PAHs included in EU legislation.......................................................................................................................... 6 Toxicity of PAHs included in EPA and EU
    [Show full text]
  • Supplemental Comments on EPA's Draft Risk Evaluation for C.I. Pigment Violet 29
    UNITED STATES ENVIRONMENTAL PROTECTION AGENCY Supplemental Comments of Safer Chemicals Healthy Families, Earthjustice, Environmental Health Strategy Center, Natural Resources Defense Council and the Undersigned Groups on EPA’s Draft Risk Evaluation for C.I. Pigment Violet 29 under the Amended Toxic Substances Control Act Submitted via Regulations.gov (May 17, 2019) Docket ID EPA-HQ-OPPT-2018-0604 INTRODUCTION AND SUMMARY Safer Chemicals Healthy Families (SCHF), Earthjustice, Environmental Health Strategy Center, Natural Resources Defense Council, and the undersigned groups submit these supplemental comments on the Environmental Protection Agency (EPA) draft risk evaluation for C.I. Pigment Violet 29 (PV29) under section 6(B) of the Toxic SuBstances Control Act (TSCA).1 Our organizations are committed to assuring the safety of chemicals used in our homes, schools and workplaces and in the many products to which our families and children are exposed each day. During the legislative process to amend TSCA, we worked hard to maximize public health protection and to assure that EPA has the necessary authority to evaluate and eliminate the risks of unsafe chemicals. We strongly support a proactive approach to implementing the new law that uses the improved tools that Congress gave EPA to deliver significant health and environmental benefits to the American public. On April 17, 2019,2 EPA reopened the comment period on the PV29 evaluation for 30 days in order to receive feedback on supplemental materials it had added to the PV29 docket. These materials include portions of 24 studies on PV29 that the Agency had initially withheld as Confidential Business Information (CBI), as well as updated systematic review files and backup scoring sheets.
    [Show full text]
  • Benzo(G,H,I)Perylene Worksheet
    CHEMICAL UPDATE WORKSHEET Chemical Name: Benzo(g,h,i)perylene CAS #: 191-24-2 Revised By: RRD Toxicology Unit Revision Date: September 15, 2015 (A) Chemical-Physical Properties Part 201 Value Updated Value Reference Source Comments Molecular Weight (g/mol) 276.34 276.34 EPI EXP Physical State at ambient temp Solid Solid MDEQ Melting Point (˚C) --- 278.00 EPI EXP Boiling Point (˚C) 500 500.00 EPI EXP Solubility (ug/L) 0.26 0.26 EPI EXP Vapor Pressure (mmHg at 25˚C) 1.0E-10 1.00E-10 EPI EXP HLC (atm-m³/mol at 25˚C) 5.34E-8 3.31E-07 EPI EXP Log Kow (log P; octanol-water) 6.7 6.63 EPI EXP Koc (organic carbon; L/Kg) 3.86E+6 1.951E+06 EPI EST Ionizing Koc (L/kg) NR NA NA Diffusivity in Air (Di; cm2/s) 0.08 2.39E-02 W9 EST Diffusivity in Water (Dw; cm2/s) 8.0E-6 6.0922E-06 W9 EST Soil Water Partition Coefficient NR NR NA NA (Kd; inorganics) CHEMICAL UPDATE WORKSHEET Benzo(g,h,i)perylene (191-24-2) Part 201 Value Updated Value Reference Source Comments Flash Point (˚C) NA NA NA NA Lower Explosivity Level (LEL; NA NA NA NA unit less) Critical Temperature (K) NA NA NA Enthalpy of Vaporization NA NA NA (cal/mol) Density (g/mL, g/cm3) 1.3 PC EXP EMSOFT Flux Residential 2 m NA 4.48E-09 EMSOFT EST (mg/day/cm2) EMSOFT Flux Residential 5 m NA 4.48E-09 EMSOFT EST (mg/day/cm2) EMSOFT Flux Nonresidential 2 m NA 4.88E-09 EMSOFT EST (mg/day/cm2) EMSOFT Flux Nonresidential 5 m NA 4.88E-09 EMSOFT EST (mg/day/cm2) 2 CHEMICAL UPDATE WORKSHEET Benzo(g,h,i)perylene (191-24-2) (B) Toxicity Values/Benchmarks Source*/Reference Comments/Notes Part 201 Value Updated Value /Date /Issues Reference Dose 7.1E-3 2.0E-3 MDEQ, 2015 (RfD) (mg/kg/day) Tier 3 Source: Complete MDEQ: Basis: In the absence of chemical-specific toxicity data for benzo (g, h, i) perylene, NYDEC and TCEQ identify pyrene as an appropriate chemical surrogate and recommend the pyrene IRIS RfD (3.0E-2 mg/kg/d) without modification.
    [Show full text]
  • Rate Constant for Fluorescence Quenching: Anthracene
    The Rate Constant for Fluorescence Quenching1 Purpose This experiment utilizes fluorescence intensity measurements to determine the rate constant for the fluorescence quenching of anthracene or perylene by CCl4 in an ethanol solvent. Introduction The fluorescence intensity of a substance depends on the natural lifetime of its first excited singlet state and on the rate that the first excited state is deactivated by nonradiative processes. Much of the nonradiative deactivation comes about because of collisions of the excited molecule with solvent molecules. However, some substances are particularly efficient at deactivating, or quenching, excited states. These tend to be substances with heavy atoms (for example halogens) or paramagnetic compounds. Oxygen is a particularly good quencher, therefore it is often necessary to remove the oxygen from solution before measuring fluorescence spectra. Fluorescent probes, such as dansyl chloride, are used in biochemistry to study the various binding sites in large macromolecules through the difference of the quenching rates of the bound verses free probe. Theory Aromatic hydrocarbons generally show intense fluorescence but no phosphorescence in fluid solution at room temperature. The fluorescence of most of these compounds is efficiently quenched by halogenated alkanes such as carbon tetrachloride and chloroform (2-5). To a certain extent these quenching events result in photochemical reactions between the aromatic hydrocarbon and the quencher. The object of this experiment is to determine the rate constant for this quenching reaction through measurements of the fluorescence intensity of the aromatic hydrocarbon in ethanol with various amounts of the quencher. The theory will be discussed with reference to the quenching of anthracene fluorescene with CCl4 in ethanol.
    [Show full text]
  • Guidance for Evaluating the Cancer Potency of PAH Mixtures
    Environmental Health Division, Environmental Surveillance and Assessment Section PO Box 64975 St. Paul, MN 55164-0975 651-201-5000 www.health.state.mn.us Guidance for Evaluating the Cancer Potency of Polycyclic Aromatic Hydrocarbon (PAH) Mixtures in Environmental Samples Minnesota Department of Health February 8, 2016 Guidance for Evaluating the Cancer Potency of Polycyclic Aromatic Hydrocarbon (PAH) Mixtures in Environmental Samples February 8, 2016 For more information, contact: Environmental Health Division, Environmental Surveillance and Assessment Section PO Box 64975 St. Paul, MN 55164-0975 Phone: 651-201-5000 Fax: 651-201-4606 This report describes guidance for conducting risk assessments. This work was conducted by the Site Assessment and Consultation Unit, Carl Herbrandson, PhD, senior toxicologist, under the supervision of Rita Messing, PhD, with the collaboration of the Health Risk Assessment Unit, Helen Goeden, PhD, senior toxicologist, and Kate Sande, MS, Research Scientist, under the supervision of Pamela Shubat, PhD. Questions on the content of this report should be directed to the Health Risk Assessment Unit, 651-201- 4899 or by email to [email protected]. Information about this work is also posted on the MDH website at Guidance for PAHs (http://www.health.state.mn.us/divs/eh/risk/guidance/pahmemo.html) Upon request, this material will be made available in an alternative format such as large print, Braille or audio recording. Printed on recycled paper. Guidance for Evaluating the Cancer Potency of Polycyclic Aromatic Hydrocarbon (PAH) Mixtures in Environmental Samples Executive Summary The Minnesota Department of Health (MDH) offers guidance for a wide range of risk assessment needs.
    [Show full text]
  • Dimension Controlled Self-Assembly of Perylene Based Molecules
    RICE UNIVERSITY Dimension Controlled Self-Assembly of Perylene Based Molecules by Arshad S. Sayyad A THESIS SUBMITTED IN PARTIAL FULLFILLMENT OF THE REQUIREMENTS FOR THE DEGREE Doctor of Philosophy Pulick 1 M. Ajayan, Chair, Benjamin M. an Mary Greenwood Anderson Professor in Engineering and Professor of Mechanical Engineering and Materials Science and Chemistry ~ Lon Wilson, Professor of Chemistry Houston, Texas DECEMBER 2010 II ABSTRACT Dimension Controlled SeH-Assembly of Perylene Based Molecules by Arshad S. Sayyad Recent advances in the self-assembly of highly organized structures of organic semiconducting molecules by controlled non-covalent interactions has opened avenues for creating materials with unique optical and electrical properties. The main focus of this thesis lies in the synthesis and self-assembly of n-type perylene based organic semiconducting molecules into highly organized materials. Perylene based molecules used in this study are perylene diimide (PTCDI, two side-chains), perylene mono imide (m-PTCI, one side-chain), perylene tetracarboxylic acid (PTCA, no side-chain) and tetra­ alkali metal salts of PTCA (M4-PTCA, no side-chain), which are synthesized from the parent perylene tetracarboxylic dianhydride (PTCDA). The self-assembly of these molecules have been performed using solution processing methods (dispersion, phase­ transfer, and phase-transfer at high temperature) by taking advantage of the changes in solubility of the molecules, wherein the molecular interactions are maximized to favorably allow for the formation of highly organized structures. Dimension control (lD, 2D and 3D structures) of self-assembly has been obtained for different perylene based molecules by appropriate design of the molecule followed by controlling the conditions of assembly.
    [Show full text]
  • Perylene Diimide-Based Fluorescent and Colorimetric Sensors for Environmental Detection
    sensors Review Perylene Diimide-Based Fluorescent and Colorimetric Sensors for Environmental Detection Shuai Chen 1,2,3, Zexu Xue 1, Nan Gao 1, Xiaomei Yang 2 and Ling Zang 2,3,* 1 Flexible Electronics Innovation Institute and School of Pharmacy, Jiangxi Science & Technology Normal University, Nanchang 330013, Jiangxi, China; [email protected] (S.C.); [email protected] (Z.X.); [email protected] (N.G.) 2 Nano Institute of Utah, University of Utah, Salt Lake City, UT 84112, USA; [email protected] 3 Department of Materials Science and Engineering, University of Utah, Salt Lake City, UT 84112, USA * Correspondence: [email protected] Received: 5 January 2020; Accepted: 7 February 2020; Published: 9 February 2020 Abstract: Perylene tetracarboxylic diimide (PDI) and its derivatives exhibit excellent thermal, chemical and optical stability, strong electron affinity, strong visible-light absorption and unique fluorescence on/off features. The combination of these features makes PDIs ideal molecular frameworks for development in a broad range of sensors for detecting environmental pollutants such as heavy 2+ 2+ 2+ 2+ metal ions (e.g., Cu , Cd , Hg , Pd , etc.), inorganic anions (e.g., F−, ClO4−, PO4−, etc.), as well as poisonous organic compounds such as nitriles, amines, nitroaromatics, benzene homologues, etc. In this review, we provide a comprehensive overview of the recent advance in research and development of PDI-based fluorescent sensors, as well as related colorimetric and multi-mode sensor systems, for environmental detection in aqueous, organic or mixed solutions. The molecular design of PDIs and structural optimization of the sensor system (regarding both sensitivity and selectivity) in response to varying analytes are discussed in detail.
    [Show full text]
  • Creosote 216
    CREOSOTE 216 4. CHEMICAL AND PHYSICAL INFORMATION 4. CHEMICAL AND PHYSICAL INFORMATION 4.1 CHEMICAL IDENTITY The chemical synonyms and identification numbers for wood creosote, coal tar creosote, and coal tar are listed in Tables 4-1 through 4-3. Coal tar pitch is similar in composition to coal tar creosote and is not presented separately. Coal tar pitch volatiles are compounds given off from coal tar pitch when it is heated. The volatile component is not shown separately because it varies with the composition of the pitch. Creosotes and coal tars are complex mixtures of variable composition containing primarily condensed aromatic ring compounds (coal-derived substances) or phenols (wood creosote). Therefore, it is not possible to represent these materials with a single chemical formula and structure. The sources, chemical properties, and composition of coal tar creosote, coal tar pitch, and coal tar justify treating these materials as a whole. Wood creosote is discussed separately because it is different in nature, use, and risk. Information regarding the chemical identity of wood creosote, coal tar creosote, and coal tar is located in Tables 4-1 through 4-3. 4.2 PHYSICAL AND CHEMICAL PROPERTIES Wood creosote, coal tar creosote, coal tar, and coal tar pitch differ from each other with respect to their composition. Descriptions of each mixture are presented below. 4.2.1 Wood Creosote Wood creosotes are derived from beechwood (referred to herein as beechwood creosote) and the resin from leaves of the creosote bush (Larrea, referred to herein as creosote bush resin). Beechwood creosote consists mainly of phenol, cresols, guaiacols, and xylenols.
    [Show full text]
  • Environmental Defense Fund Comments on Draft Risk Evaluation for CI Pigment Violet 29
    Environmental Defense Fund Comments on Draft Risk Evaluation for C.I. Pigment Violet 29 (Anthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline- 1,3,8,10(2H,9H)-tetrone) Docket ID: EPA-HQ-OPPT-2018-0604 Submitted Monday, January 14, 2019 Environmental Defense Fund (EDF) appreciates the opportunity to provide comments to the Environmental Protection Agency (EPA) on the draft risk evaluation for C.I. Pigment Violet 29 (Anthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline- 1,3,8,10(2H,9H)-tetrone) (hereafter PV29) being prepared under section 6(b)(4) of the Toxic Substances Control Act (TSCA) as amended by the Lautenberg Act, enacted on June 22, 2016.1 Executive Summary Under TSCA § 6(b)(4)(A), EPA must determine whether PV29 “presents an unreasonable risk of injury to health or the environment, without consideration of costs or other nonrisk factors, including an unreasonable risk to a potentially exposed or susceptible subpopulation identified as relevant to the risk evaluation by the Administrator, under the conditions of use.” In reaching that determination, TSCA §§ 26(h) and (k) require that EPA use the best available science and consider all reasonably available information. Under its own regulations, EPA has defined “reasonably available information” to include information that EPA “can reasonably generate, obtain, and synthesize for use in risk evaluations.” 40 C.F.R. § 702.33. In its draft risk evaluation, EPA concludes that PV29 does not present an unreasonable risk. As detailed in our comments below, EPA’s draft risk evaluation cannot support that conclusion because EPA lacks sufficient information to characterize the hazards, exposures, and risks presented by PV29.
    [Show full text]