Equilibrium Conditions in Laser-Desorbed Plumes: Thermodynamic Properties of α-Cyano-4-Hydroxycinnamic Acid and Protonation of Amino Acids

2006 ◽  
Vol 12 (6) ◽  
pp. 359-367 ◽  
Author(s):  
Gary R. Kinsel ◽  
Daqing Yao ◽  
Faten H. Yassin ◽  
Dennis S. Marynick
1942 ◽  
Vol 144 (3) ◽  
pp. 737-745
Author(s):  
Paul K. Smith ◽  
Alice T. Gorham ◽  
Elizabeth R.B. Smith

2005 ◽  
Vol 2 (5) ◽  
pp. 1515-1615 ◽  
Author(s):  
J. M. Dick ◽  
D. E. LaRowe ◽  
H. C. Helgeson

Abstract. Thermodynamic calculation of the chemical speciation of proteins and the limits of protein metastability affords a quantitative understanding of the biogeochemical constraints on the distribution of proteins within and among different organisms and chemical environments. These calculations depend on accurate determination of the ionization states and standard molal Gibbs free energies of proteins as a function of temperature and pressure, which are not generally available. Hence, to aid predictions of the standard molal thermodynamic properties of ionized proteins as a function of temperature and pressure, calculated values are given below of the standard molal thermodynamic properties at 25°C and 1 bar and the revised Helgeson-Kirkham-Flowers equations of state parameters of the structural groups comprising amino acids, polypeptides and unfolded proteins. Group additivity and correlation algorithms were used to calculate contributions by ionized and neutral sidechain and backbone groups to the standard molal Gibbs free energy (Δ G°), enthalpy (Δ H°), entropy (S°), isobaric heat capacity (C°P), volume (V°) and isothermal compressibility (κ°T) of multiple reference model compounds. Experimental values of C°P, V° and κ°T at high temperature were taken from the recent literature, which ensures an internally consistent revision of the thermodynamic properties and equations of state parameters of the sidechain and backbone groups of proteins, as well as organic groups. As a result, Δ G°, Δ H°, S° C°P, V° and κ°T of unfolded proteins in any ionization state can be calculated up to T~-300°C and P~-5000 bars. In addition, the ionization states of unfolded proteins as a function of not only pH, but also temperature and pressure can be calculated by taking account of the degree of ionization of the sidechain and backbone groups present in the sequence. Calculations of this kind represent a first step in the prediction of chemical affinities of many biogeochemical reactions, as well as of the relative stabilities of proteins as a function of temperature, pressure, composition and intra- and extracellular chemical potentials of O2 and H2, NH3, H2PO4 and CO2.


1963 ◽  
Vol 41 (1) ◽  
pp. 621-628 ◽  
Author(s):  
Takayoshi Higuchi ◽  
Stewart A. Brown

Techniques of isotope competition and trapping were used to study the phenylpropanoid biosynthetic pathway in lignifying wheat plants. The results in general confirm earlier findings that phenyllactic acid (PLA), p-hydroxyphenyllactic acid (HPLA), phenylpyruvic, cinnamic, caffeic, ferulic, and sinapic acids can participate in lignification. L-Phenylalanine and L-tyrosine were converted to PLA and HPLA, respectively, but there was much less conversion of cinnamic acid to PLA, or p-hydroxycinnamic acid to HPLA. A pathway from phenylalanine to cinnamic acid via PLA, and an analogous pathway involving tyrosine thus remain as possible alternatives to the established routes involving deamination of these amino acids by phenylalanine deaminase or tyrase. Feeding of non-radioactive coniferyl alcohol with ferulic acid-C14 results in the formation of both coniferyl- and sinapyl-type lignin residues having lower specific radioactivities than were obtained after the feeding of ferulic acid-C14 alone. After a 5-hour metabolic period in the presence of ferulic acid-C14, both coniferyl aldehyde and coniferyl alcohol became labelled, and the radioactivity of the aldehyde was much higher than that of the alcohol. There was no evidence of coniferin formation. These findings indicate that coniferyl alcohol is formed from ferulic acid through coniferyl aldehyde, and that coniferin is probably unnecessary for lignification, at least in species other than conifers.


1963 ◽  
Vol 41 (3) ◽  
pp. 621-628 ◽  
Author(s):  
Takayoshi Higuchi ◽  
Stewart A. Brown

Techniques of isotope competition and trapping were used to study the phenylpropanoid biosynthetic pathway in lignifying wheat plants. The results in general confirm earlier findings that phenyllactic acid (PLA), p-hydroxyphenyllactic acid (HPLA), phenylpyruvic, cinnamic, caffeic, ferulic, and sinapic acids can participate in lignification. L-Phenylalanine and L-tyrosine were converted to PLA and HPLA, respectively, but there was much less conversion of cinnamic acid to PLA, or p-hydroxycinnamic acid to HPLA. A pathway from phenylalanine to cinnamic acid via PLA, and an analogous pathway involving tyrosine thus remain as possible alternatives to the established routes involving deamination of these amino acids by phenylalanine deaminase or tyrase. Feeding of non-radioactive coniferyl alcohol with ferulic acid-C14 results in the formation of both coniferyl- and sinapyl-type lignin residues having lower specific radioactivities than were obtained after the feeding of ferulic acid-C14 alone. After a 5-hour metabolic period in the presence of ferulic acid-C14, both coniferyl aldehyde and coniferyl alcohol became labelled, and the radioactivity of the aldehyde was much higher than that of the alcohol. There was no evidence of coniferin formation. These findings indicate that coniferyl alcohol is formed from ferulic acid through coniferyl aldehyde, and that coniferin is probably unnecessary for lignification, at least in species other than conifers.


2015 ◽  
Vol 45 (1-2) ◽  
pp. 77-83 ◽  
Author(s):  
Marco V. José ◽  
Gabriel S. Zamudio ◽  
Miryam Palacios-Pérez ◽  
Juan R. Bobadilla ◽  
Sávio Torres de Farías

2011 ◽  
Vol 133 (2) ◽  
Author(s):  
Kian Eisazadeh-Far ◽  
Hameed Metghalchi ◽  
James C. Keck

Thermodynamic properties of ionized gases at high temperatures have been calculated by a new model based on local equilibrium conditions. Calculations have been done for nitrogen, oxygen, air, argon, and helium. The temperature range is 300–100,000 K. Thermodynamic properties include specific heat capacity, density, mole fraction of particles, and enthalpy. The model has been developed using statistical thermodynamics methods. Results have been compared with other researchers and the agreement is good.


1966 ◽  
Vol 44 (4) ◽  
pp. 403-413 ◽  
Author(s):  
P. Chandra ◽  
G. Read ◽  
L. C. Vining

DL-Phenyllactic acid-α-14C, DL-phenylserine-α-14C, L-phenylalanine-carboxyl-14C, and shikimic acid-U-14C were incorporated into phenylalanine and tyrosine isolated from mycelial hydrolysates of Volucrispora aurantiaca as well as into volucrisporin. DL-m-Tyrosine-carboxyl-14C was incorporated into volucrisporin but not into the aromatic amino acids. L-Tyrosine-β-14C, cinnamic acid-α-14C, and m-hydroxycinnamic acid-α-14C were metabolized by the fungus but did not serve as precursors of volucrisporin or of mycelial phenylalanine. The results are consistent with the concept of a biosynthetic pathway to volucrisporin via phenylpyruvic and m-hydroxyphenylpyruvic acids. Substantial amounts of each radioactive substrate fed to V. aurantiaca PRL 1952 were incorporated into a brown melanoid pigment.


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