A stereochemical and positional isotope exchange study of the mechanism of activation of tyrosine by tyrosyl-tRNA synthetase from Bacillus stearothermophilus

Tyrosyl-tRNA synthetase from Bacillus stearothernwphilus catalyses the activation of [¹⁸O₂]-tyrosine by adenosine 5$\text{[}\text{?}$(R)α-¹⁷O]triphosphate with inversion of configuration at P_α. It also catalyses positional isotope exchange in adenosine5$\text{[}\text{?}$(β-¹⁸O₂]triphosphate in the presence of tyrosine, but not in its absence or in the presence of the competitive inhibitor tyrosinol. Together these results imply that the enzyme catalyses an associative “in line” displacement of pyrophosphate from P_α of ATP by tyrosine.     

Two-photon spectra of gases by three-wave mixing

We show that the two-photon resonances in the third-order susceptibility can be exploited to yield two-photon spectra of molecular gases at moderately high spectral resolution. This form of spectroscopy does not depend on the occurrence of processes (such as fluorescence of photoionization) leading to indirect methods of two-photon absorption. The method is direct and leads in principle to values for a two-photon cross section. Comparisons of two-photon and coherent anti-Stokes Raman resonances leads to ratios of Raman and two-proton cross sections independent of the laser powers and spatial characteristics. The technique is documented with rotationally resolved spectra of SO₂ and NO. A value for |α_xxα_yy| of 1.5 × 10^?52 cm⁶ was measured for the O₁₂ (6$\text{built:1}\text{2}$) component of the (A)²Σ ← (X)² Π_{$\text{1}\text{2}$} transition of nitric oxide.     

Optical resolution of tricarbonyl(1-carboxycyclohexa-1,3-diene) iron and the absolute configuration of the products

Resolution of the acid ($\text{1}$) (shown as the (+)-isomer) into its optically pure (+) and (?) isomers and reduction of the CO₂H yields the 2-Me derivative ($\text{2}$) (shown as the (?)-isomer). The absolute configuration of ($\text{2}$) is defined by conversion of the salt ($\text{3}$) of known configuration into ($\text{2}$) and ($\text{4}$). This is the first resolution leading to preparation of pure complexes of known absolute configuration.     

Conformational dependence of pyranoid rings 1,2-cis-fused to dioxolane rings on the configuration of the dioxolane rings in acetylated derivati

X-Ray and ¹H N.M.R. studies on pyranoid rings 1,2-$\text{cis}$-fused to dioxolane rings in acetylated $\text{D}$-gluco- and $\text{D}$--galactopyranose derivatives demonstrate that the configuration of the dioxolane ring influences the conformation of the pyranoid ring in the $\text{D}$-gluco but not in the $\text{D}$-galactopyranose series. The crystal structure of 3,4,6-tri-$\text{O}$-acetyl-1,2-$\text{O}$-(R)--(l-cyano-ethylidene)-α-$\text{D}$-glucopyranose ($\text{1}$) and 3,4,6-tri-$\text{O}$-acetyl-1,2-$\text{O}$-($\text{R}$)-(1-cyano-ethylidene)-α-$\text{D}$-galactopyranose ($\text{2}$)have been determined by X-ray analysis. Lattice parameters for $\text{1}$ are a=20.6021 (11), b=8.0438 (2), c=5.5541 (1) Å and β= 95.588 (3)° for a cell with P21 symmetry. These parameters for $\text{2}$ are a=20.3361 (7), b=10.0907 (2), c=18.9115 (5) Å, β =112.399 (2)°, C2, with two crystallographycally independent molecules. The conformation of the pyranoid ring in both compounds can be described as flattened ⁴C₁ and that of the dioxolane ring as distorted E₁. The importance of the torsion angles for describing problems of configuration is remarked and the use of relative configurational angles is stressed. The ¹H N.M.R. spectra of $\text{1}$ and $\text{2}$ and 3,4,6-tri-$\text{O}$-acetyl-1,2-O-(S)- and (R)-ethylidene-α-$\text{D}$-glucopyranose ($\text{5}$ and $\text{7}$), 3,4,6-tri-O-acetyl--1,2-O-(S)- and ($\text{R}$)-ethylidene-α-$\text{D}$-galactopyranose ($\text{6}$ and $\text{8}$), and 3,4,6-tri-$\text{O}$-acetyl-1,2-$\text{O}$-($\text{S}$)-and ($\text{R}$)-benzylidene-α-$\text{D}$-glucopyranose ($\text{9}$ and $\text{10}$) have been analyzed by using iterative computer methods and N.O.E. measurements. The results indicate that the major solution conformation of the pyranoid ring of the derivatives in the $\text{D}$-gluco series $\text{1}$, $\text{5}$ and $\text{9}$ may be described as flattened ⁴C₁ and that of $\text{7}$ and $\text{10}$ as ²$\text{S}$₅. The major solution conformation of the pyranoid ring in all compounds in the $\text{D}$-galacto series ($\text{2}$,$\text{4}$,$\text{6}$,$\text{8}$) may be described as flattened ⁴$\text{C}$₁.     

An estimation of the temperature dependence of the excluded-volume integral

Lower critical solution temperatures (LCST) of trans-decalin solutions of polystyrene were measured on a newly built electric thermostat, the theta point Θ_L associated with the LCST being determined as 662 K. By use of this result together with the literature data for the ordinary theta point (Θ_U) and the entropy of dilution parameter, the excluded-volume integral B(T) was estimated in terms of the Eichinger method over the temperature range Θ_U to Θ_L. This enabled us to calculate the excluded-volume variable $\text{z}\text{as}\text{0.770 C}{}_{\mathrm{<mtext>M</mtext>}}\text{′ B(T)}\text{M}{}_{\mathrm{<mtext>w</mtext>}}{}^{0.5}$. Here, C_M′ is a numerical factor specific for a given polymer-solvent system and $\text{M}$_w is the weight-average molecular weight. Using the z values calculated from the above expression, we analysed the data on dilute solution properties of polystyrene reported by Berry and by Inagaki et al. It was found that the Domb-Barrett and the Suzuki equations for α_s (the linear expansion factor for the radius of gyration) were in good agreement with Berry's data of light scattering. The first coefficient k₁ in the series α_ν³ = 1 + k₁z + … (α_ν: the hydrodynamic expansion factor) was experimentally evaluated as 1.70. Furthermore, a conversion of the Suzuki equation for α₅ into that for α_ν with this k₁ value was found to account quite satisfactorily for the viscosity behaviour observed by Inagaki et al.     

X ray crystallography of (+)-(R)p methyl phenyl phosphoramidate of ethyl L-phenylalaninate

The absolute configuration of (+)-(R)_p methyl phenyl phosphoramidate of ethyl L-phenylalaninate $\text{1}$ was determined by X ray crystallography.     

A novel synthesis of carbacyclin analogs via a stereoselective introduction of 15α-hydroxy group

(+/-)-6,9α-Methanoprostaglandin I₃, ($\text{2}$) and (+/-)-5,6-dihydro-6,9α-methano-6β-prostaglandin I₃, ($\text{4a}$) have been synthesized using a new method for the stereoselective introduction of the 15α-hydroxy group via a stereoselective electrophilic addition of phenyl-sulfenyl chloride to the enol ether ($\text{6}$) and ($\text{23}$) respectively.     

Shape analysis of the velocity distribution in supersonic Ar beams: Comparison between experiment and theory

The shape parameters of the velocity distribution for beam densityF(v) = C($\text{v}\text{α}$)² exp[?($\text{v}\text{?}\text{u}\text{α}$)²]

from a supersonic expansion of Ar are determined both experimentally via time-of-light(TOF) analysis and computationally by solving the Boltzmann equation for a radial flow field via the method of moments. TOF spectra are recorded by means of the detection of metastable Ar atoms. This technique eliminates velocity discrimination in the detection process. Significance test and a sensitivity analysis for the experimental and theoretical results are included. The agreement of measured and calculated shape parameters is very good. Small-angle scattering of particles, travelling with small relative velocity along the same stream line, is still effective beyond the transition region to free molecular flow and continues to modify the distribution function. A primitive model that correlates the shape parameters c₃ and c₄ with the terminal speed ratio and describes their variation with the distance from the nozzlee is developed.     

Alkylation de l'acetylacetate de methyle par le α(p-nitrophenyl)-ethanol chiral par deshydratation intermoleculaire

Mitsunobu's method of acetoacetic ester alkylation by $\text{p}$-nitrophenyl-ethanol avoid the S_RN1 reaction and is well appropriate for the correlation of absolute configuration and $\text{ee}$ of the O and C alkylation products.     

The preperation and coordination properties of 1,4-diaza-3-methylbutadiene-2-ylpalladium(II) complexes with different substituents on the imino nitrogen atoms

The complexes trans-[PdCl{$\text{C(=NR)C}$(ME)=NR'} (PPh₃)₂] (R=C₆H₁₁,p-C₆H₄OMe; R$\text{.}\text{?}$=p-C₆H₄OMe, Me) containing a σ-bonded 1,4-diaza-3-menthyl-butadiene-2-yl group with different substituents on the nitrogen atoms have been prepared by two routes. The first involves initial methylation of the mixed isonitrile complex [PdCl₂(CNR)(CNR')]by HgMe₂, followed by reaction with PPh₃ ($\text{Pd}\text{PPh}{}_3$molar ratio $\text{1}\text{2}$). The second method involves condensation of primary aliphatic amines with the carbonyl group of the 1-azabut-1-en-3-one-2-yl moiety of the complex trans-[PdCl{$\text{C(=NR)C}$(Me) = 0} (PPh₃)₂]. The 1,4-diaza-3-methylbutadiene-2-yl derivatives act through their imino nitrogen atoms as chelating ligands towards anhydrous metal chlorides MCl₂ (M = Co, Ni, Cu, Zn). Magnetic moment measurements and the far-infrared and electronic spectra of these adducts indicate an essentially pseudo-tetrahedral configuration at M in the solid and in solution. With the ZnCl₂ adducts, the ¹H NMR pattern for the phenyl protons of the p-methoxyphenyl N-substituents dependss upon the position of the substituent i the 1,4-diazabutadiene chain.     

The crystal structure of α-SrMnO3

α-SrMnO₃ crystallizes in the hexagonal system with unit-cell dimensions a = 5.454(1) Å, c = 9.092(2)Å, space group $\text{P6}{}_3\text{mmc}\text{, Z = 4}$. The structure was solved by the heavy-atom method; of 404 unique reflections measured by counter method, 203 that obeyed the condition |F₀| ≥ 3σ (|F₀|) were used in the refinement to a conventional R value of 0.043. The structure consists of four close-packed SrO₃ layers in an ABAC stacking sequence along the hexagonal c axis. Oxygen octahedra containing Mn⁴⁺ are grouped into face-sharing pairs linked by corner sharing within the cubically stacked “A” layer.     

The structure and absolute configuration of heterophylloidine

The structure and absolute configuration of heterophylloidine, a new C₂₀-diterpenoid alkaloid isolated from $\text{Aconitum heterophylloides}$ Stapf, have been determined with the aid of ¹³C NMR spectral data and single-crystall X-ray analysis of the product obtained by treatment of heterophylloidine with aqueous hydrobromic acid.     

Extended hopane derivatives in sediments: identification by 1H NMR

The sedimentary C₃₂ hopanoic acid $\text{3a}$, one of the most abundant in nature and of probable bacterial origin, has been isolated for the first time as a single component and characterised by ¹H NMR. The 17αH,21βH configuration of the C₃₁ alkane has been similarly confirmed.     

Structure cristalline du phosphatoantimonate K3Sb3P2O14

K₃Sb₃P₂O₁₄ crystallizes in the rhombohedral system, space group $\text{R}\text{3}\text{m}$ with a = 7.147(1) Å, c = 30.936(6) Å, Z = 3. The structure was determined from 701 reflections collected on a Nonius CAD4 automatic diffractometer with $\text{Mo}\text{K}\text{α}$ radiation. The final R index and the weighted R_w index are 0.033 and 0.042, respectively. The structure is built up from layers of SbO₆ octahedra and PO₄ tetrahedra sharing corners. The potassium ions are situated between the (Sb₃P₂O₁₄)^3? covalent layers.     

A new determination of the absolute configuration of the chiral amine

A new method for assignment of the absolute configuration of the asymmetric carbon atom attached to an amino or imino group using rac.-3-hexadecanoyl-4-methoxycarbonyl-1,3-thiazolidine-2-thione (rac.-HDMTT) ($\text{4}$) is described.     

Action of tert-butyl azidoformate on the conjugate bases of 1,2,3,4-tetrahydro-9H-carbazole and other indole derivatives

tert-Butyl azidoformate ($\text{2}$) reacts with the conjugate bases of $\text{3a}$, $\text{7a}$, $\text{9}$ (R¹ = R² = CH₃), and $\text{9}$ (R¹ = CH₃, R² = H) to give products [$\text{4}$, $\text{8}$, $\text{12}$, and $\text{14}$, respectively] in addition to the expected N-(tert-butoxycarbonyl)indole derivatives.     

Fluorescence spectra of laser-excited YO molecules in a H2O2Ar flame

CW dye laser induced fluorescence emission and thermal emission spectra of YO-molecules in a 1 atm H₂O₂Ar flame of 2430 K were recorded simultaneously. Narrow band laser excitation was applied to four rotational lines in the (1, 1) Q-branch of the A²Π_{$\text{3}\text{2}$}→X²Σ⁺ transition and broadband excitation was applied to several separate Q-branches of the A²Π_{$\text{1}\text{2}$,$\text{3}\text{2}$}→X²Σ⁺ transitions. From the differences between the fluorescence emission spectra and thermal emission spectra, we conclude that collisional de-excitation of an excited vibronic level takes place by vibrational relaxation, decay to the electronic ground state and by intermultiplet transfer in order of increasing probability.     

Ichthyotoxic sesterterpenoids from the neo guinean sponge carteriospongia foliascens

Six 20,24-dimethylscalarane derivatives ($\text{5}$, $\text{12}$, $\text{15}$, $\text{17}$, $\text{19}$, and $\text{21}$) have been isolated from the Neo Guinean sponge Carteriospongia foliascens. Compound $\text{12}$ is identical with a C₂₇ tetracyclic terpene previously isolated from an Australian specimen of the same sponge. The five other derivatives are new and their structures have been established on the basis of their spectral data. The structure of $\text{5}$ was confirmed by single-crystal X-ray diffraction and that of $\text{15}$ by chemical correlation with $\text{12}$. The configuration at C-4 for all these compounds has been determined through ¹³C NMR data. Evidence leading to reverse the configuration at this centre in previously reported C₂₇ tetracyclic terpenes is discussed. An ecological function is suggested for these molecules.     

Study of the pyrolysis of polystyrenes: I. Kinetics of thermal decomposition

The pyrolysis of polystyrene, studied by isothermal thermogravimetry in the temperature range 300–400°C, obeys the kinetic law dα/dτ = k(1 - α)[1 - α)^2b]^{$\text{1}\text{2}$} or dα/dτ = k(1 - α)tanh β, expressions in which b depends on temperature and (cosh β)^{$\text{1}\text{3}$} = 1 - α.In order to establish the validity of this law in the very large range 0.10 < α < 0.95, it was assumed that the pyrolysis is carried out in three steps: random initiation, depolymerization and termination by disproportionation or combination. In the kinetic expression the term tanh β is proportional to the concentration of radicals and represents the setting up of the steady state. The activation energies obtained for every step agree very well with those given in the literature, whereas the apparent activation energy of the global mechanism was found to be about 43 kcal mol^?1.