scholarly journals Effects of anions on a monomeric and a dimeric arginine kinase

1975 ◽  
Vol 149 (2) ◽  
pp. 387-395 ◽  
Author(s):  
E O Anosike ◽  
D C Watts
Keyword(s):  
Creatine Kinase ◽  
Mixed Type ◽  
Arginine Kinase ◽  
Difference Spectrum ◽  
Ionization State ◽  
Temperature Dependent ◽  
Tyrosine Residues ◽  
Dead End ◽  
Low Concentrations ◽  
The Difference

1. Some effects of anions on the rates of phosphoarginine synthesis by monomeric (lobster) and by dimeric (Holothuria forskali) arginine kinases are reported. 2. As with creatine kinase, acetate ions activate both enzymes: Cl- was also found to activate both although this was an inhibitor of creatine kinase. 3. NO3- inhibits the lobster enzyme. Inhibition is of the mixed type with respect to MgATP. Ki > Ki' and Ks > Ks' indicating that the presence of NO3- promotes the binding of substrate and vice versa. 4. NO3- alone has no effect on the difference spectrum of the lobster enzyme but in the presence of arginine, MgATP, MgADP, MgAMP or MgIDP the difference spectrum is greatly enhanced. A profound effect on the ionization state of tyrosine residues is inferred. 5. With the Holothuria enzyme low concentrations of NO3- activate in a manner that is competitive with arginine. Higher concentrations cause inhibition of the mixed type with respect to arginine in a similar manner to that found with MgATP for the lobster kinase. 6. Of a range of anions tested only NO3- and NO2- enhanced the inhibition of enzyme activity by MgADP, indicating the formation of a pseudo-transition-state dead-end complex, enzyme-arginine-NO3--MgADP. The effect was essentially independent of temperature with the Holothuria enzyme, but with the lobster enzyme was much less marked and temperature dependent. The difference may reflect the different stabilities of the monomer and dimer enzymes, although with neither arginine kinase is the stabilization of the dead-end complex as marked as is found with creatinine kinase.

The interaction of bovine milk caseins with the detergent sodium dodecyl sulphate. II. The effect of detergent binding on spectral properties of caseins

1970 ◽  
Vol 37 (2) ◽  
pp. 259-267 ◽  
Author(s):  
G. C. Cheeseman ◽  
Dorothy J. Knight
Keyword(s):  
Sodium Dodecyl Sulphate ◽  
Sodium Dodecyl ◽  
Bovine Milk ◽  
Difference Spectrum ◽  
Temperature Dependent ◽  
Difference Spectra ◽  
Negative Change ◽  
Tryptophan Residues ◽  
Hydrophobic Binding ◽  
The Difference

SummaryThe dissociation of casein aggregates by the detergent sodium dodecyl sulphate (SDS) gave rise to difference spectra and these spectra were characteristic for each of the different types of casein. Increase in absorption by the chromophore groups, tyrosine and tryptophan, when αs1- and β-casein aggregates were dissociated indicated binding of the detergent at regions of the molecule containing these residues. A decrease in absorption when κ-casein was dissociated indicated that the tyrosine and tryptophan residues were not in the region of the molecule to which the detergent was bound and that in the κ-casein aggregate these residues were in a more hydrophobic environment. Peaks on the difference spectra were obtained at 280 and 288 nm for αs1-casein and 284 and 291 nm for β-casein and troughs at 278 and 286 nm for κ-casein. The difference spectrum reached a maximum value when the αsl- and β-casein aggregates were dissociated and the further binding of SDS did not alter this value. The large negative change in the difference spectrum of κ-casein did not occur until after most of the aggregates were dissociated and did not reach a maximum until binding with SDS was complete. The value obtained for ΔOD was found to be temperature-dependent for β-casein-SDS interaction, but not for αs1- and κ-casein. Changes in spectra were also observed when αs1- and κ-casein interacted to form aggregates. The data obtained confirmed the importance of hydrophobic binding in casein aggregate formation and indicated the possible involvement of tyrosine and tryptophan residues in this binding.

scholarly journals Location of aromatic amino acids and helix content in Escherichia coli ribonucleic acid polymerase

1971 ◽  
Vol 123 (1) ◽  
pp. 117-122 ◽  
Author(s):  
B. H. Nicholson
Keyword(s):  
Escherichia Coli ◽  
Aromatic Amino Acids ◽  
Difference Spectrum ◽  
Optical Rotatory Dispersion ◽  
Intact Protein ◽  
Model Compounds ◽  
Tyrosine Residues ◽  
Tryptophan Residues ◽  
Direct Spectrum ◽  
The Difference

1. The perturbing effect of glycerol on the direct spectrum of Escherichia coli DNA-dependent RNA polymerase has been studied. 2. By comparison with model compounds and with the unfolded polymerase in 3.8m-urea it was possible to determine the ratio of tyrosine and tryptophan residues present. On reduction of the urea-treated enzyme with 2-mercaptoethanol, no further change in the difference spectrum occurred. 3. The amino acid composition of the enzyme is given. 4. In the intact protein approx. 30% of the tryptophan and 54% of the tyrosine residues were exposed. In conjunction with the extinction value and molecular weight this corresponded to 7 tryptophan residues and 57 tyrosine residues on the surface and 16 tryptophan residues and 48 tyrosine residues ‘buried’. 5. The optical rotatory dispersion of the enzyme was unaffected by 20% glycerol. 6. The helix content calculated from Moffit plots over 560–300nm was 13%, and from the 233nm trough 13%.

Near Infrared Spectroscopy and Chemometrics Studies of Temperature-Dependent Spectral Variations of Water: Relationship between Spectral Changes and Hydrogen Bonds

1995 ◽  
Vol 3 (4) ◽  
pp. 191-201 ◽  
Author(s):  
Hisashi Maeda ◽  
Yukihiro Ozaki ◽  
Munehiro Tanaka ◽  
Nobuyuki Hayashi ◽  
Takayuki Kojima
Keyword(s):  
Hydrogen Bonds ◽  
Curve Fitting ◽  
Near Infrared ◽  
Difference Spectrum ◽  
Second Derivative ◽  
Pls Regression ◽  
Temperature Dependent ◽  
Multilinear Regression ◽  
Spectral Changes ◽  
The Difference

The present study aims to provide new insights into the temperature-dependent spectral variations in the near infrared (NIR) region of the spectrum of water by comparing chemometrics with spectroscopic analysis. Fourier transform (FT)-NIR spectra of water in the 9000–5500 cm−1 region have been measured over a temperature range of 5–85°C. The observed spectral changes have been analysed by both chemometrics, such as multilinear regression (MLR), principal component regression (PCR) and partial least squares (PLS) regression, and spectroscopic data analyses, such as second derivative, difference spectra and curve fitting. The second derivative of the NIR spectra of water suggests that an intense feature around 6900 cm−1, due to the combination of antisymmetric and symmetric stretching modes of water, consists of at least five component spectra. Each component spectrum may be ascribed to the water species with no, one, two, three and four hydrogen bonds. Curve fitting has been performed for the 6900 cm−1 band and it has been found that the species with no hydrogen bonds increase largely with temperature, while those with more than two hydrogen bonds decrease. The temperature of water has been predicted by use of MLR, PCR and PLS regression. PCR and PLS regression loadings plots for Factor 1 of the models for the prediction of the temperature of water are almost identical with the difference spectrum of water between 5 and 85°C; both the loadings plots and the difference spectrum reflect strongly the changes in the hydrogen bonds of water. Loadings plots of Factor 1 of the PCR and PLS regression models are very similar to each other. It is very likely that since the temperature-dependent spectral variations of water in the NIR region are very regular, and the spectra have only very small noise and baseline changes, PCR and PLS regression select nearly identical factors.

scholarly journals Subunit interactions in horse spleen apoferritin. Dissociation by extremes of pH

1973 ◽  
Vol 133 (2) ◽  
pp. 289-299 ◽  
Author(s):  
R. R. Crichton ◽  
Charles F. A. Bryce
Keyword(s):  
Conformational Changes ◽  
Difference Spectrum ◽  
Low Ph ◽  
Tryptophan Residue ◽  
Tyrosine Residues ◽  
Ph Values ◽  
Lysine Residues ◽  
Arginine Residues ◽  
The Difference ◽  
Ph Range

1. The dissociation of horse spleen apoferritin as a function of pH was analysed by sedimentation-velocity techniques. The oligomer is stable in the range pH2.8–10.6. Between pH2.8 and 1.6 and 10.6 and 13.0 both oligomer and subunits can be detected. At pH values between 1.6 and 1.0 the subunit is the only species observed, although below pH1.0 aggregation of the subunits to a particle sedimenting much faster than the oligomer occurs. 2. When apoferritin is first dissociated into subunits at low pH values and then dialysed into buffers of pH1.5–5.0, the subunit reassociates to oligomer in the pH range 3.1–4.3. 3. U.v.-difference spectroscopy was used to study conformational changes occurring during the dissociation process. The difference spectrum in acid can be accounted for by the transfer of four to five tyrosine residues/subunit from the interior of the protein into the solvent. This process is reversed on reassociation, but shows the same hysteresis as found by sedimentation techniques. The difference spectrum in alkali is more complex, but is consistent with the deprotonation of tyrosine residues, which appear to have rather high pK values. 4. In addition to the involvement of tyrosine residues in the conformational change at low pH values, spectral evidence is presented that one tryptophan residue/subunit also changes its environment before dissociation and subsequent to reassociation. 5. Analysis of the dissociation and reassociation of apoferritin at low pH values suggests that this is a co-operative process involving protonation and deprotonation of at least two carboxyl functions of rather low intrinsic pK. The dissociation at alkaline pH values does not appear to be co-operative. 6. Of the five tyrosine residues/subunit only one can be nitrated with tetranitromethane. Guanidination of lysine residues results in the modification of seven out of a total of nine residues/subunit. Nine out of the ten arginine residues/subunit react with cyclohexanedione.

Temperature-Dependent Logic Failure in a GaAs Power Amplifier-Duplexer Module Caused by a Subtle Parasitic Schottky Diode

2014 ◽  
Author(s):  
Rose Emergo ◽  
Steve Brockett ◽  
Pat Hamilton
Keyword(s):  
Power Amplifier ◽  
Schottky Diode ◽  
Production Test ◽  
Temperature Dependent ◽  
Cold Temperatures ◽  
Collector Junction ◽  
Power Mode ◽  
The Difference ◽  
Base Contact ◽  
Single Power

Abstract A single power amplifier-duplexer device was submitted by a customer for analysis. The device was initially considered passing when tested against the production test. However, further electrical testing suggested that the device was stuck in a single power mode for a particular frequency band at cold temperatures only. This paper outlines the systematic isolation of a parasitic Schottky diode formed by a base contactcollector punch through process defect that pulled down the input of a NOR gate leading to the incorrect logic state. Note that this parasitic Schottky diode is parallel to the basecollector junction. It was observed that the logic failure only manifested at colder temperatures because the base contact only slightly diffused into the collector layer. Since the difference in the turn-on voltages between the base-collector junction and the parasitic Schottky diode increases with decreasing temperature, the effect of the parasitic diode is only noticeable at lower temperatures.

scholarly journals Potential Pitfalls in Membrane Fouling Evaluation: Merits of Data Representation as Resistance Instead of Flux Decline in Membrane Filtration

Membranes ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 460
Author(s):  
Bastiaan Blankert ◽  
Bart Van der Bruggen ◽  
Amy E. Childress ◽  
Noreddine Ghaffour ◽  
Johannes S. Vrouwenvelder
Keyword(s):  
Membrane Fouling ◽  
Membrane Filtration ◽  
Data Representation ◽  
Strong Impact ◽  
Experimental Conditions ◽  
Permeable Membrane ◽  
Dead End ◽  
Flux Decline ◽  
The Difference ◽  
Filtration Flux

The manner in which membrane-fouling experiments are conducted and how fouling performance data are represented have a strong impact on both how the data are interpreted and on the conclusions that may be drawn. We provide a couple of examples to prove that it is possible to obtain misleading conclusions from commonly used representations of fouling data. Although the illustrative example revolves around dead-end ultrafiltration, the underlying principles are applicable to a wider range of membrane processes. When choosing the experimental conditions and how to represent fouling data, there are three main factors that should be considered: (I) the foulant mass is principally related to the filtered volume; (II) the filtration flux can exacerbate fouling effects (e.g., concentration polarization and cake compression); and (III) the practice of normalization, as in dividing by an initial value, disregards the difference in driving force and divides the fouling effect by different numbers. Thus, a bias may occur that favors the experimental condition with the lower filtration flux and the less-permeable membrane. It is recommended to: (I) avoid relative fouling performance indicators, such as relative flux decline (J/J0); (II) use resistance vs. specific volume; and (III) use flux-controlled experiments for fouling performance evaluation.

scholarly journals Action and Entropy in Heat Engines: An Action Revision of the Carnot Cycle

Entropy ◽  
2021 ◽  
Vol 23 (7) ◽  
pp. 860
Author(s):  
Ivan R. Kennedy ◽  
Migdat Hodzic
Keyword(s):  
Heat Engine ◽  
Working Fluid ◽  
Field Energy ◽  
Carnot Cycle ◽  
Gibbs Potential ◽  
Atmospheric Gases ◽  
Temperature Dependent ◽  
Expansion Phase ◽  
Heat Engines ◽  
The Difference

Despite the remarkable success of Carnot’s heat engine cycle in founding the discipline of thermodynamics two centuries ago, false viewpoints of his use of the caloric theory in the cycle linger, limiting his legacy. An action revision of the Carnot cycle can correct this, showing that the heat flow powering external mechanical work is compensated internally with configurational changes in the thermodynamic or Gibbs potential of the working fluid, differing in each stage of the cycle quantified by Carnot as caloric. Action (@) is a property of state having the same physical dimensions as angular momentum (mrv = mr2ω). However, this property is scalar rather than vectorial, including a dimensionless phase angle (@ = mr2ωδφ). We have recently confirmed with atmospheric gases that their entropy is a logarithmic function of the relative vibrational, rotational, and translational action ratios with Planck’s quantum of action ħ. The Carnot principle shows that the maximum rate of work (puissance motrice) possible from the reversible cycle is controlled by the difference in temperature of the hot source and the cold sink: the colder the better. This temperature difference between the source and the sink also controls the isothermal variations of the Gibbs potential of the working fluid, which Carnot identified as reversible temperature-dependent but unequal caloric exchanges. Importantly, the engine’s inertia ensures that heat from work performed adiabatically in the expansion phase is all restored to the working fluid during the adiabatic recompression, less the net work performed. This allows both the energy and the thermodynamic potential to return to the same values at the beginning of each cycle, which is a point strongly emphasized by Carnot. Our action revision equates Carnot’s calorique, or the non-sensible heat later described by Clausius as ‘work-heat’, exclusively to negative Gibbs energy (−G) or quantum field energy. This action field complements the sensible energy or vis-viva heat as molecular kinetic motion, and its recognition should have significance for designing more efficient heat engines or better understanding of the heat engine powering the Earth’s climates.

Difference Spectrophotometric Estimation of Santonin

1984 ◽  
Vol 67 (5) ◽  
pp. 939-941
Author(s):  
Abdel-Azim M Habib ◽  
Abdalla A Omar ◽  
Taha M Sarg
Keyword(s):  
Difference Spectrum ◽  
Crude Drug ◽  
The Difference

Abstract Santonin gives a characteristic alkaline vs acidic difference spectrum. This was used for its estimation in pharmaceuticals and in the crude drug. Santonin was first extracted and purified through a specific partition procedure; then the difference absorbance was measured either at the maximum, 285 nm, or the minimum, 242 nm. The percentage of santonin can be calculated either by reference to the difference absorbance of a reference santonin sample, treated similarly, or by making use of the determined absorptivity. Measurement at the maximum is advisable, especially when the crude drug is assayed, because natural contaminants may interfere with the difference absorbance at the minimum.

scholarly journals Effects of the Translocation Status of Human Immunodeficiency Virus Type 1 Reverse Transcriptase on the Efficiency of Excision of Tenofovir

2007 ◽  
Vol 51 (8) ◽  
pp. 2911-2919 ◽  
Author(s):  
Bruno Marchand ◽  
Kirsten L. White ◽  
John K. Ly ◽  
Nicolas A. Margot ◽  
Ruth Wang ◽  
...  
Keyword(s):  
Human Immunodeficiency Virus ◽  
Complex Formation ◽  
Reverse Transcriptase ◽  
High Rate ◽  
Human Immunodeficiency Virus Replication ◽  
Degree Of Protection ◽  
Cellular Environment ◽  
Dead End ◽  
Low Concentrations ◽  
Immunodeficiency Virus

ABSTRACT The ATP-dependent phosphorolytic excision of nucleoside analogue reverse transcriptase inhibitors can diminish their inhibitory effects on human immunodeficiency virus replication. Previous studies have shown that excision can occur only when the reverse transcriptase complex exists in its pretranslocational state. Binding of the next complementary nucleotide causes the formation of a stable dead-end complex in the posttranslocational state, which blocks the excision reaction. To provide mechanistic insight into the excision of the acyclic phosphonate nucleotide analog tenofovir, we compared the efficiencies of the reaction in response to changes in the translocation status of the enzyme. We found that rates of excision of tenofovir with wild-type reverse transcriptase can be as high as those seen with 3′-azido-3′-deoxythymidine monophosphate (AZT-MP). Thymidine-associated mutations, which confer >100-fold and 3-fold decreased susceptibility to AZT and tenofovir, respectively, caused substantial increases in the efficiency of excision of both inhibitors. However, in contrast to the case for AZT-MP, the removal of tenofovir was highly sensitive to dead-end complex formation. Site-specific footprinting experiments revealed that complexes with AZT-terminated primers exist predominantly pretranslocation. In contrast, complexes with tenofovir-terminated primers are seen in both configurations. Low concentrations of the next nucleotide are sufficient to trap the complex posttranslocation despite the flexible, acyclic character of the compound. Thus, the relatively high rate of excision of tenofovir is partially neutralized by the facile switch to the posttranslocational state and by dead-end complex formation, which provides a degree of protection from excision in the cellular environment.

Theory of ultrasonic attenuation in one and two dimensional metals

1976 ◽  
Vol 54 (14) ◽  
pp. 1454-1460 ◽  
Author(s):  
T. Tiedje ◽  
R. R. Haering
Keyword(s):  
Ultrasonic Attenuation ◽  
Three Dimensional ◽  
Electronic Systems ◽  
Two Dimensional ◽  
Temperature Dependent ◽  
One Dimensional ◽  
The Difference

The theory of ultrasonic attenuation in metals is extended so that it applies to quasi one and two dimensional electronic systems. It is shown that the attenuation in such systems differs significantly from the well-known results for three dimensional systems. The difference is particularly marked for one dimensional systems, for which the attenuation is shown to be strongly temperature dependent.

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