Due to recent interest in the role of heavy metals in enzymes. oxygen-carrying molecules. and anticarcinogenic compounds, the study of metal-protein bonding has assumed a new importance. Studies have been made utilizing platinum compounds as anticarcinogenic agents in several different types of cancerous activity. No study of the mechanism by which Pd(II) and Pt(II) compounds exhibit anticarcinogenic properties has been made to date. The purpose of this research was to investigate the nature of bonding of Pd(II) and Pt(II) with various dipeptides, which were chosen in this study as a basic unit of protein-like material. These compounds have the advantage of having the bonding sites of larger peptides. An amino group, peptide-linkage carbonyl and amide group, and carboxyl group are available for bonding with metal ions to form complexes. The position of the donor atoms on dipeptides allow sterically for the formation of two five-membered rings in a complex when other conditions are suitable. When PdBr2 was refluxed in acetone with a dipeptide, PdBr2 (XX)2 (where XX is a dipeptide) resulted. Bonding of the dipeptide to Pd(II) was through the amino nitrogen atom. Analogous compounds were found to result when PtCl2 was refluxed in acetone with a dipeptide. K2PdCl4afforded a source of Pd(II) in which the dipeptide could function as a bidentate or tridentate ligand. At a pH near 13.0 the dipeptide was bound to Pd(II) through the amino and deprotonated nitrogen atoms. At a pH near 7.0 the carboxylate oxygen of the dipeptide was also bonded to Pd(II). Infrared measurement showed that the Amide I band of the dipeptide had shifted at least 50 c-1 to lower energy upon coordination of the peptide nitogen to Pd(II). Electronic studies indicated that the λ (max) was at a minimum when the dipeptide was acting in a tridentate mode. There was a red shift when the hydroxide ion replaced the carboxylate group in the coordination sphere at pH values near 13.0. Nuclear magnetic resonance spectra indicated tridentate behavior of glycylvaline with Pd(II) at pD 7.11 but showed detachment of the carboxylate group from the coordination sphere at pD 13.06. Infrared analysis showed that there was no reaction of Pt(Il) with the peptide linkage when K2PtCl4 was used at the Pt(II) source. Zeise's salt was used as a third source of Pt(II). Infrared analysis, molecular weight determination, and elemental analysis indicated fission of the peptide bond and formation of compounds of the formula (C2H4PtClX)2, where X is an amino acid residue from the dipeptide reacted with Zeise's salt. Both residues of each dipeptide, ValVal, ValLeu, and LeuVal, were incorporated in the product of Zeise's salt and the dipeptide. Infrared analysis indicated N-trans--O-trans of the donor atoms of the amino acid residues with respect to ethylene in the VaVal and LeuVal products, whereas ValLeu gave an N-trans--N-trans product.

The measurement of viscosity is a common and useful technique for investigating the mechanical behavior of many real fluids. Theoretical interpretations of viscosity measurements have been important in attempts to elucidate fundamental properties of the liquid state. Brush (6) and Bondi (3) give reviews of the current status of attempts to construct theories of liquid viscosity, and it is quite apparent from these reviews that the molecular theory of rheological phenomena is in its infancy. In addition to the fundamental aspects of viscometry, there are many practical applications to which viscosity measurements are directed (25). One has only to scan the contents of the series edited by Eirich (10) to gain an appreciation of the voluminous aspects of practical rheology. Among the rheological topics discussed in the Eirich series are the spinning of synthetic fibers, lubrication and lubricants, extrusion molding, and biological fluid transport. Most of the articles in applied rheology are concerned with commercially available instruments for measurement of viscosity and flow and the general phenomenological theory for flow with emphasis on non- Newtonian flow.

The strained cyclic allene intermediates of 1,2-cyclohexadiene, 1,2-cycloheptadiene and 1,2-cyclooctadiene have been successfully generated by the debromination of their corresponding 2,3-dibromocycloalkenes. Evidence for their intermediate existence was obtained by trapping them with the Diels-Alder trapping agent 2,5-diphenyl 1-3,4-benzofuran and by isolating the corresponding addition products. The goal of this study was to generate the transitory cyclic allenes 1,2-cyclooctadiene, 1,2-cycloheptadiene and 1,2-cyclohexadiene and to investigate some aspects of their chemistry. Evidence for the intermediate existence of these strained cyclic allenes has been found by generating them by the debromination of their corresponding 2,3-dibromocycloalkenes and by trapping the generated cycloallene intermediates with the Diels-Alder trapping agent 2,5-diphenyl-3,4-benzofuran. In order to carry out this study, it became necessary to synthesize 2,3-dibromocyclooctene and 2,3-dibromocycloheptene. 2,3-Dibromocyclohexene had been previously prepared. The synthetic sequence employed to obtain these compounds is summarized by Equations 2 and 3.

Part of this investigation was undertaken to determine the effects of functional group substitution on the ring - as well as on the -NH2 radical - on the formation of metal complexes with the first transition series in the periodic classification of the elements. The outline of the investigation in this report is as follows: (1) To mind methods for the preparation of the complexes.; (2) To examine the relative ease of formation, and the relative solubility of such chelates in common laboratory reagents.; (3) To determine the relative stabilities by relative molar conductance measurements.; (4) To discover relative stabilities by infrared and ultraviolet spectral studies.; and (5) To elucidate the structure of the complexes by (a) Elemental analysis examinations, (b) Infrared and ultraviolet spectral studies.

A major problem confronting every investigator who works with synthetic organic chemistry is that of the crystallization of the products obtained. This problem necessitates extensive attention both on the experimental and on the theoretical level. In order to gain an understanding of the behavior of substances in the liquid state, so as to be better able to manipulate them in procedures intended to induce crystallization from complex mixtures, considerable attention has been given to various models of the liquid state. An understanding of the nature of pure liquids would seem to be an essential prelude to any attempt to understand the behavior of complex mixtures from which one component is to be separated. Since viscous liquids are sometimes in a state of incipient crystallization, or else represent systems which especially resist crystallization (e.g., sirups, glasses, etc.), a study of the capillary behavior of such liquids is of theoretical as well as practical interest. Aside from the insight into the microscopic structure of liquids which may be gained from theoretical interpretations of viscosity measurements, knowledge of viscous flow properties is important in many hydrodynamic problems. The viscosities of solutions of high polymers depend upon the sizes and shapes of the molecules in solution and thus provide a useful method for the study of polymer configurations.

The electrochemical technique of polarography was used to study the complexions formed by Ni(II) ion and pyridine compounds. It was of interest to vary the substituent group on the pyridine ring in order to observe the effects on the nickel - nitrogen coordinate bonds.

It has been found that there exist certain crystalline aluminosilicates which provide regular net-works of channels with diameters no bigger than those of molecules. Such crystals can act as sieves (thus the name "molecular sieves" now marketed by the Linde Air Products Company) and bring about a separation of molecular species by occluding small molecules while not adsorbing larger molecules or molecules with shapes that do not "fit." The aluminosilicates were termed zeolites first by Baron Cronstedt (1) some 200 years ago. He observed that certain mineral crystals, when heated, appeared to melt and to boil at the same time. Thus, from the Greek "zeo," to boil, and "lithos," stone, Cronstedt coined the term "zeolite." The use of zeolite (molecular sieves) has increased during the past several years. The earlier work (1930- 1950) involved the study of the naturally occurring zeolites. During the last ten years the activity has been concerned with the use of synthetic crystalline zeolites in separating both gaseous and liquid components by the molecular sieve action,

It is surprising that no one has considered that coordination might have some effect on the strength of the acid group. It is the intent of this study to fill this gap in the knowledge of amino-acid chemistry. At about the time this study began on the effect of chelation on the strength of the uncomplexed acid group, the next two higher homologs of these dicarboxylic amino acids became commercially available. It was, therefore, decided that the problem of this research should be expanded to include all four of the acidic amino acids. The research problem was also defined to include the systematic synthesis of the platinum and palladium (II) complexes of the four available alpha amino dicarboxylic acids, [see PDF]. Platinum and palladium were chosen since in the +2 oxidation state they were known to form only square planar compounds.

The purpose of this research was to measure fluorescence decay-times of several biologically significant compounds. Although various equations are available which permit one to calculate fluorescence lifetimes from spectral data, ample evidence exists which indicates such calculations are at considerable variance with experimental results.

The initial program of study for consideration was the extension of cyclooctatetraene complexation to other metals of the transition group. Compounds of (COT) with iron, cobalt, chromium, molybdenum, and tungsten which have been reported in the literature involve carbonyl ligands simultaneously as (COT)M(CO)x with x = 2,3----; only Ag(I) as AgN03 adducts are known. Rhodium (I) is said to form an unstable dimer while ruthenium (I) forms a polymer. (COT)Pt(II) chloride, bromide and iodide have been reported but only the iodide has been studied; only (COT)PdCl2 has been reported recently. It was further conceived that substituted (COT) would present a good comparison a ligand especially if steric inhibition of pi-bonding were to be observed. The second phase of the study was limited to platinum (II) and palladium (II) chloride and bromide, owing to the known greater stability of the platinum and palladium complexes; attempted investigation with other metals proved fruitless. The following olefins were chosen for their availability and for the fact that each of these is an eight carbon olefinic system and hence can be considered as an extension of the (COT) system. a. 1,5-cyclooctadiene 1,5-(COD) b. 1,3-cyclooctadiene 1,3-(COD) c. 4-vinylcyclohexene 4-(VCR) d. cyclooctene (COC) Though 1,5-(COD) had been reported as a ligand, the literature records few data on its complexes. The choice of 1,3-(COD)--the isomer of 1 ,5-(COD)--as a ligand posed interesting stereochemical problems in that if both double bonds of this system were employed in pi-bonding to the same metal atom it would produce a distortion of the perpendicularity requirement. On the other hand, 1,3-(COD) offers a conjugated system which might conceivably enhance stability of an over-all pi-bonded system. The other possibilities, of course, would be the use of only one ring olefin per metal atom as: [see PDF file for the chemical bond] Finally, each ring might form a bridge system between two metal atoms. This would be possible if the -MX2 planes were perpendicular rather than coplanar [see PDF file for the chemical bond] In any event there is no mention in the literature on the use of 1,3-(COD) as a ligand except by Cope, Stevens and Hochstein (1950) who prepared a silver nitrate adduct 1 ,3-(COD)· 2AgNO.3 4-vinylcyclohexene provides two olefin systems. Would this hydrocarbon behave as a diolefin or would there be exhibited a preference in pi-bonding of one olefin site over the other? Many possible combinations could be conceived; some of which are shown below. [see PDF file for the chemical bond] The inclusion of cyclooctene in the study was made because the only other cycloalkene reported in the earlier literature was cyclohexene. Only an unstable adduct AgNO3• (C8H14)2 was reported by Jones (1954). Recently a compound with the trans form of cyclooctene was made by Cope (1963). [See PDF file for the chemical bond] This compound exists as diastereoisomers and subsequently was resolved into two optically active forms. In the program of study carried out in this research ciscyclooctene was used exclusively. Not only was it the object of this research to attempt the preparation of the olefin complexes, but also to determine something of their chemistry, such as, thermal stability, displacement reactions and the character of their absorption spectra in the visible, ultraviolet and infrared regions. It was intended to extend the often made comparison of platinum chemistry with that of palladium. Toward the end of this research, one other olefin 1,5,9-cyclododecatriene was employed in a limited investigation because of its triple unsaturation; inspection reveals its relation to 1,5-(COD) by the appearance of two condensed rings with 4 fewer carbon atoms. Yet, the olefins are each 4 carbons removed from the other as in the case of 1,5-(COD).