scholarly journals The structure of bacilysin and other products of Bacillus subtillis

1970 ◽  
Vol 118 (4) ◽  
pp. 563-570 ◽  
Author(s):  
J. E. Walker ◽  
E. P. Abraham
Keyword(s):  
Methyl Ester ◽  
Proton Magnetic Resonance Spectrum ◽  
Cotton Effect ◽  
Optical Rotatory Dispersion ◽  
Keto Group ◽  
Spin Splitting ◽  
Unsaturated Ketone ◽  
Epoxide Group ◽  
Group 4 ◽  
Optical Rotatory Dispersion Curve

1. Mass spectra of the trimethylsilyl derivative and the methyl ester of the N-trifluoroacetyl derivative of bacilysin indicated that the antibiotic had a molecular weight of 270. Several peaks in the spectrum of the methyl ester were consistent with the presence of an N-terminal alanine residue in the molecule. 2. The proton-magnetic-resonance spectrum of bacilysin confirmed that the antibiotic contained an epoxide group and the spin–spin splitting of the protons of the epoxide group indicated that the side chain of the epoxycyclohexanone ring was attached at C-4 and was αβ to the keto group. 3. The formation of an αβ-unsaturated ketone on reduction of bacilysin with chromous chloride also showed that the epoxide was αβ to the keto group. 4. The optical-rotatory-dispersion curve of bacilysin showed a positive Cotton effect. On the assumption that the reversed Octant rule for αβ-epoxyketones was applicable this revealed the absolute stereochemistry and enabled a definitive structure to be assigned to the molecule. 5. Similar measurements showed that substance AA1, isolated from culture supernatants, was the C-terminal amino acid of bacilysin. 6. Hydrolysis of substance P2 with leucine aminopeptidase and the mass spectrum of the methyl ester of its N-trifluoroacetyl derivative showed that this substance was l-analyl-l-alanine. 7. These results are discussed in relation to the biogenesis of bacilysin.

scholarly journals DETERMINATION OF THE POLARIZATION OPTICAL PROPERTIES OF THE AMYLOID-CONGO RED COMPLEX BY PHASE MODULATION MICROSPECTROPHOTOMETRY

1974 ◽  
Vol 22 (12) ◽  
pp. 1105-1112 ◽  
Author(s):  
DOUGLASS L. TAYLOR ◽  
ROBERT D. ALLEN ◽  
EARL P. BENDITT
Keyword(s):  
Circular Dichroism ◽  
Congo Red ◽  
Phase Modulation ◽  
Optical Rotation ◽  
Polarized Light ◽  
Visible Spectrum ◽  
Linear Dichroism ◽  
Cotton Effect ◽  
Optical Rotatory Dispersion ◽  
Circular Dichroïsm

The polarization properties responsible for the classical "green birefringence" of the amyloid-Congo red complex have been determined by a new optical method, phase modulation microspectrophotometry. This method now makes possible the measurement of one optical property at a time (birefringence, optical rotation, linear dichroism and circular dichroism throughout the visible spectrum) in complex specimens in which visible contrast in polarized light is the result of a mixture of polarization effects. The green birefringence is explained by a combination of optical effects, the strongest of which are dispersion of birefringence and linear dichroism superimposed on the smaller effects of circular dichroism and optical rotatory dispersion. The interaction of the planar dye molecules with the amyloid protein induces an extrinsic Cotton effect.

Studies in Mass Spectrometry. VII. Triterpenoids: Ifflaionic Acid

1963 ◽  
Vol 16 (4) ◽  
pp. 683 ◽  
Author(s):  
JS Shannon
Keyword(s):  
Mass Spectrometry ◽  
Methyl Ester ◽  
Functional Groups ◽  
Mass Spectra ◽  
Molecular Ions ◽  
Keto Group ◽  
Chemical Derivatives ◽  
Pentacyclic Triterpenoid

The mass spectra of the methyl ester of the new unsaturated pentacyclic triterpenoid ifflaionic acid (urs-12-en-3-on-30-oic acid) and some of its chemical derivatives are presented. These may be used to assign position C-20 to the carbomethoxy and C-3 or C-7 to the keto group. Mechanistic proposals for, and the effect of functional groups on, the main fragmentation of the molecular ions (cleavage through ring C) are discussed.

Some features of the optical rotatory dispersion spectrum of the α-lytic protease of Sorangium sp.

1969 ◽  
Vol 47 (3) ◽  
pp. 317-321 ◽  
Author(s):  
G. M. Paterson ◽  
D. R. Whitaker
Keyword(s):  
Optical Rotation ◽  
Substrate Binding ◽  
Cotton Effect ◽  
Optical Rotatory Dispersion ◽  
Rotatory Dispersion ◽  
Kinetic Properties ◽  
Optical Rotatory ◽  
Cotton Effects ◽  
Ph Dependent

A study of the kinetic properties of the α-lytic protease of Sorangium sp. indicated that substrate-binding by the enzyme was not pH dependent. In agreement with this indication of a pH-insensitive conformation, the optical rotation of the enzyme between pH 5 and 10.5 is not pH dependent. The optical rotatory dispersion spectrum above 220 mμ shows a main Cotton effect with a trough at 230 mμ and small but well-marked Cotton effects between 260 and 300 mμ. The reduced, mean residue rotation at the trough of the main Cotton effect was estimated to be −1650 ± 80° cm2/dmole; the Moffitt–Yang parameter b0 for rotations above 325 mμ is approximately zero. These values suggest that the enzyme has virtually no α-helices.

Some remarks on the interpretation of natural and magnetically induced optical activity data

1967 ◽  
Vol 297 (1448) ◽  
pp. 16-26 ◽  
Keyword(s):  
Optical Activity ◽  
Dipole Transition ◽  
Optically Active ◽  
Optical Rotatory Dispersion ◽  
Perturbation Approach ◽  
Activity Data ◽  
Rotational Strength ◽  
Optical Rotatory Dispersion Curve ◽  
Isotropic Media ◽  
Induced Optical Activity

1. Introduction—A classification for optically active chromophores One of the most useful concepts that emerges from the perturbation approach to the theory of natural optical activity is that of the ‘rotational strength’ of a transition (Condon 1937). This signed quantity conveniently and effectively measures how strongly a particular transition contributes to both the dispersive and absorp­tive aspects of the optical activity of a molecule (Moscowitz 1962); it is obtainable experimentally from either the pertinent partial optical rotatory dispersion curve or the partial circular dichroism curve (Djerassi 1960), and it is amenable to theo­retical calculation for homogeneous isotropic media as the following scalar product (Condon 1937; Moscowitz 1962; Djerassi 1960; Rosenfield 1928). R ba = I {( a | μ e | b ). ( b | μ m | a )}. Here ( a | μ e | b ) and ( b | μ m | a ) are the electric and magnetic dipole transition moments, respectively, connecting the ground state a and the excited state b , and I means imaginary part. Accessible as such to both theory and experiment, the rotational strength provides one of the most suitable foundations on which to build quanti­tative correlations between optical activity data and molecular structure.

Alkaloids of Lycopodiumlucidulum Michx. Structure and properties of alkaloid L.23

1969 ◽  
Vol 47 (3) ◽  
pp. 449-455 ◽  
Author(s):  
W. A. Ayer ◽  
B. Altenkirk ◽  
R. H. Burnell ◽  
M. Moinas
Keyword(s):  
Absolute Configuration ◽  
Cotton Effect ◽  
Ultraviolet Spectrum ◽  
Optical Rotatory Dispersion ◽  
Rotatory Dispersion ◽  
Optical Rotatory ◽  
Structure And Properties ◽  
The Absolute ◽  
Related Compounds ◽  
Circular Dichroic

The minor alkaloids present among the strong bases of Lycopodiumlucidulum have been reinvestigated. Manske and Marion's alkaloid L.23 has been shown to be epimeric with lycodoline at C-12 and the nitrogen. A correlation between the two alkaloids has been achieved. The presence of a σ-coupled p interaction in the ultraviolet spectrum of lycopodine, lycodoline, and related compounds is described. A Cotton effect due to this chromophore has been detected by means of circular dichroism. The optical rotatory dispersion and circular dichroic properties of lycopodine, 12-epilycopodine, lycodoline, and alkaloid L.23 are discussed in terms of the absolute configuration assigned to these alkaloids.

CONFORMATIONAL STUDIES ON SYNTHETIC POLY-α-AMINO ACIDS: THE HELICAL SENSE OF POLY-L-TRYPTOPHAN: OPTICAL ROTATORY DISPERSION STUDIES

1965 ◽  
Vol 43 (5) ◽  
pp. 1588-1598 ◽  
Author(s):  
Gerald D. Fasman ◽  
Margarete Landsberg ◽  
Manuel Buchwald
Keyword(s):  
Wavelength Range ◽  
Cotton Effect ◽  
Optical Rotatory Dispersion ◽  
Rotatory Dispersion ◽  
Helical Conformation ◽  
Optical Rotatory ◽  
Negative Cotton Effect ◽  
Cotton Effects ◽  
The Right ◽  
Tryptophanyl Residue

The synthesis of high molecular weight (100 000 to 200 000) polymers and copolymers of L-tryptophan and γ-benzyl-L-glutamate is reported. The optical rotatory dispersion (o.r.d.) of these polypeptides is recorded in the wavelength range 540–320 mμ and the b0 values of the Moffitt equation, using λ0 = 212ν, are listed. Poly-L-tryptophan has a b0 value of +570 in dimethylformamide (DMF). A linear relationship exists between this value, b0 values of copolymers of various ratios of L-tryptophan and γ-benzyl-L-glutamate, and the value of− 670 found for poly-γ-benzyl-L-glutamate. The o.r.d. curve of a poly-L-tryptophan film, in the 330–200 mμ wavelength range, reveals two positive Cotton effects in the 270–290 mμ region and a large negative Cotton effect at 233 mμ. Thus, despite the positive b0 value, these data prove that poly-L-tryptophan, in DMF, has the right-handed helical conformation. Hypochromicity was found for the tryptophanyl residue in the helical polypeptide. The rotatory contribution of chromophores, such as tryptophan or coenzymes, when bound asymmetrically to a protein, can be very significant, and caution is advised in the interpretation of such o.r.d. curves.

scholarly journals Oligonucleotide studies. Optical rotatory dispersion of five homodinucleotides

1969 ◽  
Vol 113 (5) ◽  
pp. 843-851 ◽  
Author(s):  
Yasuo Inoue ◽  
Kimihiko Satoh
Keyword(s):  
Ionic Strength ◽  
Salt Concentration ◽  
Equilibrium Mixture ◽  
Cotton Effect ◽  
Phosphate Group ◽  
Optical Rotatory Dispersion ◽  
Rotatory Dispersion ◽  
Optical Rotatory ◽  
Ionization State ◽  
Terminal Phosphate Group

1. The optical rotatory dispersion (ORD) of five homodinucleotides, ApAp(3′), CpCp(3′), GpGp(3′), IpIp(3′) and UpUp(3′) (where A, C, G, I and U represent adenosine, cytidine, guanosine, inosine and uridine respectively, and p to the left of a nucleoside symbol indicates a 5′-phosphate and to the right it indicates a 3′-phosphate), were measured as a function of pH, ionic strength and Mg2+ concentration. 2. The ORD titrations of ApAp(3′) and CpCp(3′), which were made by measuring the ORD curves at closely spaced pH intervals, exhibit a maximum at approx. pH5·0 and 5·7 for ApAp(3′) and CpCp(3′) respectively in the profile of the magnitude of the first Cotton effect versus pH. The results indicate that the conformational rigidity of these dinucleotides depends on the ionization state of a 3′-terminal phosphate group. 3. ApAp(3′) was shown to exist as an approximately 1:1 equilibrium mixture of the two major ionic species represented by Ap(−1)Ap(−1) and Ap(−1)Ap(−2) at pH6·16, whereas at pH7·5 it exists exclusively as a form of Ap(−1)Ap(−2). 4. To ascertain the effects of the presence of a terminal phosphate group and of the ionization of the secondary phosphate on the conformation of adenylate dimer, we measured the ORD of ApA, ApAp(3′)CH3 and ApAp(2′). The rotatory power of the first Cotton effect in the above series of dinucleotides decreased at 20° in the order ApA> ApAp(3′)CH3≈ApAp(3′)(−1)> ApAp(2′) at pH7> ApAp(3′) at pH7. 5. The pH–rotation profiles were also obtained for ApAp(2′), CpCp(2′) and UpUp(3′), but no corresponding maximum was observed. Although simple nearest-neighbour calculations based on the ORD data of IpIp(3′) and 5′-IMP account for the observed ORD spectrum of polyinosinic acid at low salt concentration, there were large discrepancies between calculated and experimental results of the polyguanylic acid ORD even at low ionic strength. 6. The extent to which the amplitude of the Cotton effects of IpIp(3′) increases with salt concentration, especially by the addition of Mg2+, was much greater than that observed for ApAp(3′). The implication of such salt effects on the ORD is considered.

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