Aggregation studies in crystals of apolar helical peptides: Boc-Aib-Val-Ala-Leu-Aib-Val-Ala-Leu-Aib-OMe

In the crystal, the backbone of Boc-(Aib-Val-Ala-Leu)2-Aib-OMe adopts a helical form with four alpha-type hydrogen bonds in the middle, flanked by 3(10)-type hydrogen bonds at either end. The helical molecules stack in columns with head-to-tail hydrogen bonds, either directly between NH and CO, or bridged by solvent molecules. The packing of the helices is parallel, even in space group P2(1). Cell parameters are a = 9.837(2) A, b = 15.565(3) A, c = 20.087(5) A, beta = 96.42(2) degrees, dcalc = 1.091 g/cm3 for C46H83N9O12.1.5H2O.0.67CH3OH. There appears to be some hydration of the backbone in this apolar helix.

Studies in terpenoids-XIII. Magnetic anisotropy2 in and stereochemistry of some gem-dimethylcyclobutanoids related to pinonic acid

The chemical shifts of “axial” vs “equatorial” Me protons of some gem-dimethylcyclobutanoids derived from α-pinene, arising from magnetic anisotropy of the ring and as influenced by vicinal substituents, are discussed. Conformational aspects of some cis- and trans-pinonic, pinononic and pinic acids have been elucidated on the basis of NMR evidence.

Studies in bubble formation — III

Bubble formation from single horizontal orifices submerged in Newtonian liquids has been investigated for such chamber volumes that both the pressure inside the chamber and flow rate into the bubble are time dependent. The data collected show that under these conditions the bubble volume decreases exponentially with increase in orifice submergence. The equations for the generalized two stage model of bubble formation, taking the variation of gas flow rate with time into account, have been derived. These equations reduce to the cases of constant gas flow rate and constant pressure when adequate constraints are imposed. The results obtained under intermediate conditions have been quantitatively explained on the basis of these equations.

Studies in bubble formation—II bubble formation under constant pressure conditions

Bubble formation under constant pressure conditions has been investigated for wide range of variation of liquid properties.Air bubbles were formed from single horizontal orifices submerged in liquids whose viscosity varied from 1·0 to 600 cPs and surface tension from 37 to 72 dyn/cm. Air flow rate was varied from 2 to 250 cm3/sec and the orifice diameter from 0·0515 to 0·4050 cm.

Studies in bubble formation—I bubble formation under constant flow conditions

A model based on two step mechanism of bubble formation is proposed. The resulting equations are used to explain the discrepancies existing in the literature. Data have been collected over a wide range of variables to test the model.

Studies in sesquiterpenes—XXIX *1: Structure of himachalenes

α-and β-Himachalenes, the two major sesquiterpene components of the essential oil of Himalayan deodar (Cedrus deodara, Loud.) are shown to represent a new sequiterpenoid carbon framework. Evidence is presented which establishes their gross structures.

Studies in the hydrolysis of metal ions -Part I.Copper

The hydrolysis of cupric ion has been studied at various ionic strengths (0·01, 0·05, 0·1 and 0·5 M). The results are analyzed employing 'core + links' theory, log-log plot, normalization plot, and extrapolation method for obtaining the pure mononuclear curve. The stability constants of Cu2(OH)2++, Cu3(OH)4++, Cu(OH)+ and Cu(OH)2 have been reported.

Studies in sesquiterpenes—XXIV *1: Synthesis of (±)-cadinene dihydrochloride

A total synthesis of (±)-4-isopropyl-trans-decalin-1,6-dione, a key intermediate in the cadinane series, and its conversion into (±)-cadinene dihydrochloride, is reported.

Studies in oxasteroids—I : Synthesis of 3-cyano-3-methyl-7-methoxychroman-4-one and the structure of an “abnormal” product

A synthesis of 3-cyano-3-methyl-7-methoxychroman-4-one is reported. The structure of an “abnormal” product obtained during isomerization (III) with potassium t-butoxide in t-butanol, followed by alkylation with methyl iodide has been proved to be 3-t-butoxy-2-cyano- 2-mehthyl-2′,4′-dimethoxypropiophenone (IVa).

Studies in sesquiterpenes—XXV : A synthesis of α-selinene

The conversion of α-cyperone into α-selinene is described.

Studies in sesquiterpenes—XXVI : Synthesis of 2,2,6-trimethyl-3-oxo-1-carbomethoxybicyclo[0,3,3]octane, a degradation product of patchouli alcohol

The synthesis of the title compound is described and results of some experiments on the degradation of patchouli alcohol are reported.

Drop formation studies in liquid—liquid systems

Benzene drops were formed in continuous media of water and glycerine of varying physical properties. The effect on drop volumes of variables like volumetric flow-rate, interfacial tension, continuous phase viscosity and capillary diameter was studied. An equation has been developed, based on a two stage drop formation mechanism, which predicts drop volumes within an average error of 7 per cent for the range of physical properties employed in this investigation.

ESR and optical absorption studies in copper diethyldithiocarbamate

ESR investigations at X band and optical-absorption measurements have been reported in single crystals of copper (n) diethyldithiocarbamate Cu[S 2CN(C2H5)2]2 diluted to 0.2% with the corresponding zinc complex. The measurements have been made both at room and liquid-oxygen temperatures. ESR measurements gave the following values for the parameters in spin Hamiltonian g11=2.1085, g=2.023(6), A63= 142.4×10-4 cm-1, A65 = 152.0×10-4 cm-1, B = 22.4×10-4 cm-1, Q~3×10-4 cm-1. Polarized optical absorption study has made possible a proper assignment of the absorption bands to their corresponding transitions. This has led to information regarding the ordering of the MO levels of the complex. The coefficients used in the MO description of the complex have been calculated from the observed parameters. The results show that the metal ligand BIσ bond is purely covalent and that the out-of-plane w bonding is appreciably covalent whereas the in-plane Π bonding is ionic. Further, it is noted that the metal ligand binding is more covalent with sulfur as ligand than with oxygen or nitrogen.