Molecular vibrations and conformation of primary dithiocarbamate ester. Infrared and NMR studies on S-methyl dithiocarbamate

The i.r. spectra of a primary dithiocarbamate ester namely, S-methyl dithiocarbamate (SMDTC) and its N-dideuterated compound have been measured between 4000 and 30 cm−1. Spectra in solution and at liquid nitrogen temperature have also been obtained. Assignment of all the fundamentals has been proposed and supported from a full normal coordinate analysis. The band assignments for SMDTC have been compared with those of related molecules and the characteristic bands of primary thioamides are derived. Conformational flexibility of SMDTC has been examined by i.r. and proton NMR spectroscopy. The hindered rotation around the C---N bond has been studied by a complete line shape analysis. The magnitude of ---NH2 and ---CH3 torsional barriers is also estimated from vibrational frequencies and force constants.

Sequence effects in structures of the dinucleotides d-pApT AND d-pTpA

The H1',H2' and H2″ regions of the 270-MHz PMR spectra of two deoxydinucleotides, d-pTpA and d-pApT, have been analyzed. The coupling constants in the sugar ring indicate that both A and T sugars have a tendency to acquire 2E conformations. There is also a marginal difference in the 2E populations of the T sugar in the two dinucleotides. The trends in the chemical shifts of base protons indicate different stacking of the bases in d-pApT and d-pTpA. The sequence effects on base stacking and pentose conformation are discussed.

A note on the analysis of the dispersion equation for surface magnetoplasmons in the Faraday configuration

The analysis of the dispersion equation for surface magnetoplasmons in the Faraday configuration for the degenerate case of decaying constants being equal is given from the point of view of understanding the non-existence of the “degenerate modes”. This analysis also shows that there exist well defined “degenerate points” on the dispersion curve with electromagnetic fields varying linearly over small distances taken away from the interface.

Charge transfer complexes of crown ethers with neutral organic gyama-acceptor, 2-dicyanoethylene 1,3-indane dione

The interaction of benzo-15-crown-5, dibenzo-18-crown-6 and dibenzo-24-crown-8 with 2-dicyanoethylene 1,3-indane dione in CH2Cl2 has been described in terms of the formation of 1 : 1 molecular complexes. The magnitude of association constants and thermodynamic parameters indicate cooperative interactions of oxygens with the acceptors. The 1H and 13C NMR spectra of the complexes show that gyama-gyama interactions are a major source of ground state stabilization in these complexes.

Soil N availability, rather than N deposition, controls indirect N2O emissions

Ammonia volatilised and re-deposited to the landscape is an indirect N2O emission source. This study established a relationship between N2O emissions, low magnitude NH4 deposition (0–30  kg N ha − 1 ), and soil moisture content in two soils using in-vessel incubations. Emissions from the clay soil peaked ( < 0.002 g N [ g soil ] − 1 min − 1 ) from 85 to 93% WFPS (water filled pore space), increasing to a plateau as remaining mineral-N increased. Peak N2O emissions for the sandy soil were much lower ( < 5 × 10 − 5 μg N [ g soil ] − 1 min − 1 ) and occurred at about 60% WFPS, with an indistinct relationship with increasing resident mineral N due to the low rate of nitrification in that soil. Microbial community and respiration data indicated that the clay soil was dominated by denitrifiers and was more biologically active than the sandy soil. However, the clay soil also had substantial nitrifier communities even under peak emission conditions. A process-based mathematical denitrification model was well suited to the clay soil data where all mineral-N was assumed to be nitrified ( R 2 = 90 % ), providing a substrate for denitrification. This function was not well suited to the sandy soil where nitrification was much less complete. A prototype relationship representing mineral-N pool conversions (NO3− and NH4+) was proposed based on time, pool concentrations, moisture relationships, and soil rate constants (preliminary testing only). A threshold for mineral-N was observed: emission of N2O did not occur from the clay soil for mineral-N <70 mg ( kg of soil ) − 1 , suggesting that soil N availability controls indirect N2O emissions. This laboratory process investigation challenges the IPCC approach which predicts indirect emissions from atmospheric N deposition alone.

f Gravity and gravitational singularities

TRAUTMAN has postulated1 that the usual space−time singularity occurring in classical cosmological models and in the gravitational collapse of massive objects could be averted if intrinsic spin effects are incorporated into general relativity by adding torsion terms to the usual Einstein field equations, that is through the Einstein−Cartan theory. Invoking a primordial magnetic field for aligning all the individual nuclear spins he shows that his universe consisting of 1080 aligned neutrons collapses to a minimum radius of the order of 1 cm with a corresponding matter density of 1055 g cm-3.

ESR study of copper diethyldithiophosphate

ESR investigations are reported in single crystals of copper diethyldithiophosphate, magnetically diluted with the corresponding diamagnetic nickel complex. The spectrum at normal gain shows hyperfine components from 63Cu, 65Cu, and 31P nuclei. At much higher gain, hyperfine interaction from 33S nuclei in the ligand is detected. The spin Hamiltonian parameters relating to copper show tetragonal symmetry. The measured parameters are g = 2.085, g =2.025, A63Cu = 149.6 × 10−4 cm−1, A65Cu = 160.8 × 10−4 cm−1, BCu = 32.5 × 10−4 cm−1 and QCu 5.5 × 10−4cm−1. The 31P interaction is isotropic with a coupling constant AP = 9.6 × 10−4 cm−1. Angular variation of the 33S lines shows two different hyperfine tensors indicating the presence of two chemically inequivalent Cu S bonds. The experimentally determined hyperfine constants are A =34.9×10−4 cm−1, B =26.1×10−4 cm−1, A =60.4×10−4 cm−1, B =55.5×10−4 cm−1. The hyperfine parameters show that the hybridization of the ligand orbitals is very sensitive to the symmetry around the ligand. The g values and Cu hyperfine parameters are not much affected by the distortions occurring in the ligand. The energies of the d-d transitions are determined by optical absorption measurements on Cu diethyldithiophosphate in solution. Using the spin Hamiltonian parameters together with optical absorption results, the MO parameters for the complex are calculated. It is found that in addition to the bond, the bonds are also strongly covalent. ©1973 The American Institute of Physics

An inhomogeneity problem in couple stress theory

Using Hilbert theory and Mindlin's couple stress theory, the problem of two-dimensional circular inhomogeneity (when the inserted material is of different size than the size of the cavity and having different elastic constants) is studiedin this paper. Stress could be bounded at infinity. The formulation is valid also for regions other then the circular ones when the matrix is finite has also been tackled. Numerical results are in conformity with the fact that the effect of couple stresses is negligible when the ratio of the smallest dimension of the body to the cahracteristic length is large.

Optical and magnetic resonance studies of the interaction of metallo tetraphenylporphyrins with nitrobenzofuroxan

Metallo tetraphenylporphyrins form I : I molecular complexes with 4,6-dinitrobenzofuroxan. The molecular association is described in terms of T-n. interaction with porphyrins functioning as donors. The association constants and thermodynamic parameters have been evaluated using optical absorption and 'H nmr spectral methods. Based on the binding constants, the donor ability of various metalloporphyrins can be arranged in the following order: Pd(I1) > Co(I1) > Cu(I1) > Ni(I1) - VO(1V) - 2H > Zn(l1). Electron paramagnetic resonance studies of the complexes reveal that the IT-complexation results in changes in the electronic structure of the central metal ions which are reflected in the changes in the M-N 5 bonding. The dipolar contribution to the acceptor proton chemical shifts in the CoTPP complex has been partitioned from ring current contributions using the shifts observed in the ZnTPP complex. The shifts, along with the line broadening ratios observed for the CoTPP complex, are used to arrive at the possible solution structures of the complexes.

Mode of action of antitumour antibiotics: Spectrophotometric studies on the interaction of chromomycin A3 with DNA and chromatin of normal and neoplastic tissue

The binding of chromomycin A3, an antitumour antibiotic, to various DNA and chromatin isolated from mouse and rat liver, mouse fibrosarcoma and Yoshida ascites sarcoma cells was studied spectrophotometrically at 29°C in 10−2 M Tris-HCl buffer, pH 8.0, containing small amounts of MgCl2 (4.5 · 10−5−25 · 10−5 M). An isobestic point at 415 nm was observed when chromomycin A3 was gradually titrated with Image and its spectrum shifted towards higher wavelength. The rates and extent of these spectral changes were found to be dependent on the concentration of Mg2+. The change in absorbance at 440 nm was used to calculate apparent binding constant (Ka p M−1) and sites per nucleotide (n) from Scatchard plots for various DNA and chromatins. As expected, values of n for chromatin (0.06–0.10) were found to be lower than that found for corresponding DNA (0.10–0.15). Apparently no such correlation exists between binding constants (Ka p M−1 · 10−4) of DNA (6.4–11.2) and of chromatin (3.1–8.3), but Ka p M−1 of chromatin isolated from mouse fibrosarcoma and Yoshida ascites sarcoma are 1.5–3 times higher than that found for mouse and rat liver chromatin. These differences may be taken to indicate structural difference in nucleoprotein complexes caused by neoplasia. The relevance of this finding to tumour suppressive action of chromomycin A3 is discussed.

Molecular complexes of macrocyclic polyethers with 1, 3, 5-trinitrobenzene

The interaction of six macrocyclic polyethers with 1, 3, 5-trinitrobenzene has been studied by spectroscopic methods. The association constants have been evaluated by1HMR chemical shift method. There is evidence that major contribution to the interaction isvia n andπ electrons. The donor strengths of the polyethers have been evaluated.

On the Specificity of Carbohydrate-Lectin Recognition The Interaction of a Lectin from Ricinus communis Beans with Simple Saccharides and Concanavalin A

A galactose-specific protein (RC1) isolated from Ricinus communis beans was found to give a precipitin reaction with concanavalin A. Its carbohydrate content amounted to 8–9% of the total protein and was found to be rich in mannose. The interaction of RC1 with galactose and lactose was measured in 0.05 M phosphate buffer containing 0.2 M NaCl (pH 6.8) by the method of conventional equilibrium dialysis. From the analysis of the binding data according to Scatchard method the association constant (Ka) at 5°C was calculated as 3.8 mM−1 and 1.2 mM−1 for lactose and galactose, respectively. In both cases the number of binding sites per molecule of RC1 with molecular weight of 120000 was found to be 2. From the temperature-dependent Ka values for the binding of lactose, the values of –5.7 kcal/mol and –4.3 cal × mol−1× K−1 were calculated for ΔH and ΔS, respectively. The addition of concanavalin A to RC1 or vice versa led to the formation of the insoluble complex RC1· ConA4 containing one molecule of RC1 and one molecule of tetrameric concanavalin A (ConA4) which could be dissociated upon addition of concanavalin A-specific sugars. The complex formation results in a time-dependent appearance of turbidity in the time range from 10s to 10 min. From the measurement of the time-dependent appearance and disappearance of the turbidity the formation (kf) and dissociation (kd) rate constants were calculated as 3 mM−1× s−1 and 0.07 ks−1 respectively. The ratio kf/kd (43μM −1), that corresponds to the association constant of complex RC1· ConA4, is higher than that of mannoside · ConA4 and thereby suggests that protein-protein interaction contributes significantly in stabilising glycoprotein · lectin complexes. The relevance of this finding to the understanding of the chemical specificities that are involved in a model cell-lectin interaction is discussed.

Conformal invariance and scalar-tensor theories

A new generalisation of Einstein’s theory is proposed which is invariant under conformal mappings. Two scalar fields are introduced in addition to the metric tensor field, so that two special choices of gauge are available for physical interpretation, the ‘Einstein gauge’ and the ‘atomic gauge’. The theory is not unique but contains two adjustable parameters ζ anda. Witha=1 the theory viewed from the atomic gauge is Brans-Dicke theory (ω=−3/2+ζ/4). Any other choice ofa leads to a creation-field theory. In particular the theory given by the choicea=−3 possesses a cosmological solution satisfying Dirac’s ‘large numbers’ hypothesis.

Axisymmetric stress distribution in a transversely isotropic thick plate with a circular hole

An exact solution for the stresses in a transversely isotropic infinite thick plate having a circular hole and subjected to axisymmetric uniformly distributed load on the plane surfaces has been given. The solution is in the form of Fourier-Bessel series and integrals. Numerical results for the stresses are given using the elastic constants for magnesium, and are compared with the isotropic case.

A Reinvestigation of the Normal Vibrations of Thioacetamide

The normal coordinate treatments of thioacetamide and its seven isotopic molecules have been carried out using Urey-Bradley force constants refined by a least-squares procedure. The laser Raman spectrum of thioacetamide has also been recorded.