Thermodynamic profile for urea photo-release from a N-(2-nitrobenzyl) caged urea compound

被引:0
|
作者
Gangadhar Dhulipala
Marisa Rubio
Katja Michael
Jaroslava Mikšovská
机构
[1] Florida International University,Department of Chemistry and Biochemistry
[2] Marshall University,Department of Chemistry and Biochemistry, Department of Chemistry
[3] University of Texas at El Paso,Department of Chemistry
关键词
D O I
暂无
中图分类号
学科分类号
摘要
Photoactivable bioactive molecules, often termed “caged” compounds, have attracted significant attention as useful tools for photo-regulating enzymatic activity. Here we examine the mechanism associated with photo-release of urea from a caged urea compound, N-(2-nitrobenzyl)urea, using photothermal beam deflection and time-resolved absorption spectroscopy. Photodissociation of the caged urea results in the prompt formation of an aci-nitro intermediate that decays to nitrosobenzaldehyde by releasing urea with the rate constant of 4.5 × 103 s−1. Appearance of the aci-nitro intermediate is associated with a volume contraction of −13 ± 1 mL mol−1 and a negligible change in enthalpy (ΔH = 6 ± 4 kcal mol−1). On the microsecond time-scale, the conversion of the aci-nitro intermediate and concomitant release of urea result in a volume expansion of 6 ± 2 mL mol−1 and a negative enthalpy change of −25 ± 5 kcal mol−1. No additional processes were observed on the timescale up to 100 ms suggesting that the breakdown of the aci-nitro intermediate is the rate-limiting step for urea photo-release. These results suggest a similar mechanism for caged urea photo release as determined previously for the caged ATP compound.
引用
收藏
页码:1157 / 1163
页数:6
相关论文
共 15 条
  • [1] Thermodynamic profile for urea photo-release from a N-(2-nitrobenzyl) caged urea compound
    Dhulipala, Gangadhar
    Rubio, Marisa
    Michael, Katja
    Miksovska, Jaroslava
    PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES, 2009, 8 (08) : 1157 - 1163
  • [2] N-(2-CYANETHYLENE-)UREA - ASPARAGINE ANALOGOUS CYTOSTATIC COMPOUND
    BICKER, U
    EXPERIMENTELLE PATHOLOGIE, 1975, 10 (1-2): : 106 - 108
  • [3] Caged mPEG-poly(S-(2-nitrobenzyl)-L-cysteine) for photo-triggered drug release and thiol-ene functionalization
    Wu, Yanjuan
    Yan, Lesan
    He, Hongyan
    Li, Bin
    Xie, Zhigang
    Huang, Yubin
    Jing, Xiabin
    JOURNAL OF CONTROLLED RELEASE, 2013, 172 (01) : E83 - E84
  • [4] N2O and NO emissions from a field of Chinese cabbage as influenced by band application of urea or controlled-release urea fertilizers
    Cheng, W
    Nakajima, Y
    Sudo, S
    Akiyama, H
    Tsuruta, H
    NUTRIENT CYCLING IN AGROECOSYSTEMS, 2002, 63 (2-3) : 231 - 238
  • [5] N2O and NO emissions from a field of Chinese cabbage as influenced by band application of urea or controlled-release urea fertilizers
    W. Cheng
    Y. Nakajima
    S. Sudo
    H. Akiyama
    H. Tsuruta
    Nutrient Cycling in Agroecosystems, 2002, 63 : 231 - 238
  • [6] Biased photo cleavage of N1-/N6-nitrobenzyl from 2'-hydroxyethyl-adenosine and their DNA/RNA Caged-analogues
    Bollu, Amarnath
    Sharma, Nagendra K.
    JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 2021, 404
  • [7] 13C-urea and 15N2-urea: elegant markers to define location and kinetics of in vivo release from a colon-targeted delivery device in men
    Schellekens, R. C. A.
    Olsder, G.
    Maurer, M.
    Kosterink, J.
    Woerdenbach, H. J.
    Wutzke, K. D.
    Frijlink, H. W.
    Stellaard, F.
    EUROPEAN JOURNAL OF CLINICAL INVESTIGATION, 2010, 40 : 66 - 66
  • [8] ON EXTRACTION OF INORGANIC IONS .2. N-(DI-N-BUTYLPHOSPHORO) UREA, (N-DBPU) AS AN EXTRACTANT OF INORGANIC IONS FROM NITRIC ACID SOLUTIONS
    TSOLIS, AK
    BELKAS, EP
    PERRICOS, DC
    RADIOCHIMICA ACTA, 1969, 11 (02) : 117 - &
  • [9] Adsorption of CO2 on KOH activated, N-enriched carbon derived from urea formaldehyde resin: kinetics, isotherm and thermodynamic studies
    Tiwari, Deepak
    Bhunia, Haripada
    Bajpai, Pramod K.
    APPLIED SURFACE SCIENCE, 2018, 439 : 760 - 771
  • [10] Effect of organic, inorganic and slow-release urea fertilisers on CH4 and N2O emissions from rice paddy fields
    Mai Van Trinh
    Tesfai, Mehreteab
    Borrell, Andrew
    Nagothu, Udaya Sekhar
    Thi Phuong Loan Bui
    Vu Duong Quynh
    Le Quoc Thanh
    PADDY AND WATER ENVIRONMENT, 2017, 15 (02) : 317 - 330