Chemistry of low-valent platinum dimers

Physical and chemical properties of low-valent platinum dimers, namely [Pt_2(P_2O_5H_2)4]^(4-) and Pt_2(µ-dppm)_2Cl_2, have been investigated using a variety of structural and spectroscopic techniques.

Platinum(II) d^8-d^8 dimers have been shown to exhibit much thermal and photochemical reactivity. Chapter 2 describes studies aimed at elucidating the excited state reduction potenetial of [Pt_2(P_2O_5H_2)4]^(4-), Pt_2, in organic media. By conducting excited state electron transfer studies using derivatized pyridiniums and benzophenones, the excited state reduction potential has been estimated to be ~2 V. The Pt_2 complex undergoes partial oxidation to form Pt(II,III) linear chains. Chapter 3 describes the structural and spectroscopic techniques used to determine the translational symmetries of these [Pt_2(P_2O_5H_2)4]^(4-) (X = Cl, Br), Pt_2X, chains. Pt_2Br has been found to be intermediate between (AAB)_n and (AABCCB)_n, while, Pt_2Cl is of (AABCCB)_n translational symmetry. Investigations into the electronic transitions of Pt_2Cl and Pt_2Br were conducted using high pressure techniques and are presented in Chapter 4. The Pt_2X electronic spectrum exhibits bands attributable to the reduced Pt2 complex and the oxidized Pt_2X_2 complex [Pt_2(P_2O_5H_2)4]^(4-) along with an intervalence charge-tranfer band characteristic of a mixed-valence solid.

Photophysical investigations of a new luminescent chromophore, Pt_2(µ-dppm)_2Cl_2, a d^9-d^9 dimer, and its analogs are described in Chapter 5. The absorption band directly responsible for the observed emission is believed to be very weak and, as of yet, unobserved. Attempts to determine the spin multiplicty and approximate energy of this unobserved transition are described in Chapter 6. Excited-state energy transfer studies indicate that this absorption band is a triplet transition at -13,000 cm^(-1). Although, the Pt_2(µ-dppm)_2Cl_2 excited state is non-luminescent in fluid solution, it has been shown to undergo thermal electron transfer to tetracyanoethylene and photoinduced electron transfer to methylviologen. These experiments are presented in Chapter 7. Preliminary studies, described in Chapter 8, of non-bridged d^9-d^9 platinum(I) dimers have shown that [Pt_2(CNCH_3)_6]^(2+) serves as a versatile precursor in the synthesis of new d^8-d^8 A-frame complexes.

Part I: The abortive infection of bacteriophage øx174 at low temperatures. Part II: The early stages in the process of infection by bacteriophage øx174

Part I

The infection of E. coli by ΦX174 at 15°C is abortive; the cells are killed by the infection but neither mature phage nor SS (single-stranded) DNA are synthesized. Parental RF (replicative form) is formed and subsequently replicated at 15°C. The RF made at 15°C shows normal infectivity and full competence to act as precursor to progeny SS DNA after an increase in temperature to 37°C. The investigations suggest that all of the proteins required for SS DNA synthesis and phage maturation are present in the abortive infection at 15°C.

Three possible causes are suggested for the abortive infection at 15°C: (a) A virus-coded protein whose role is essential to the infection is made at 15°C and assumes its native conformation, but its rate of activity is too low at this temperature to sustain the infection process. (b) Virus maturation may involve the formation of a DNA-protein complex and conformational changes which have an energy threshold infrequently reached at 15°C. (c) A host-coded protein present in uninfected cells, and whose activity is essential to the infection at all temperatures, but not to the host at 15°C, is inactive at 15°C. An hypothesis of this type is offered which proposes that the temperature-limiting factor in SS DNA synthesis in vivo may reflect a temperature-dependent property of the host DNA polymerase.

Part II

Three distinct stages are demonstrated in the process whereby ΦX174 invades its host: (1) Attachment: The phage attach to the cell in a manner that does not irreversibly alter the phage particle and which exhibits "single-hit" kinetics. The total charge on the phage particle is demonstrated to be important in determining the rate at which stable attachment is effected. The proteins specified by ΦX cistrons II, III and VII play roles, which may be indirect, in the attachment reaction. (2) Eclipse: 'The attached phage undergo a conformational change. Some of the altered phage particles spontaneously detach from the cell (in a non-infective form) while the remainder are more tightly bound to the cell. The altered phage particles detached (spontaneously or chemically) from such complexes have at least 40% of their DNA extruded from the phage coat. It is proposed that this particle is, or derives from, a direct intermediate in the penetration of the viral DNA.

The kinetics for the eclipse of attached phage particles are first-order with respect to phage concentration and biphasic; about 85% of the phage eclipse at one rate (k = 0.86 min^-1) and the remainder do so at a distinctly lesser rate (k = 0.21 min^-1).

The eclipse event is very temperature-dependent and has the relatively high Arrhenius activation energy of 36.6 kcal/mole, indicating the cooperative nature of the process. The temperature threshold for eclipse is 17 to 18°C.

At present no specific ΦX cistron is identified as affecting the eclipse process. (3) DNA penetration: A fraction of the attached, eclipsed phage particles corresponding in number to the plaque-forming units complete DNA penetration. The penetrated DNA is found in the cell as RF, and the empty phage protein coat remains firmly attached to the exterior of the cell. This step is inhibited by prior irradiation of the phage with relatively high doses of UV light and is insensitive to the presence of KCN and NaN₃. Temporally excluded superinfecting phages do not achieve DNA penetration.

Both eclipsed phage particles and empty phage protein coats may be dissociated from infected cells; some of their properties are described.

Invariants, Lie-Bäcklund operators and Bäcklund transformations

This thesis is mainly concerned with the application of groups of transformations to differential equations and in particular with the connection between the group structure of a given equation and the existence of exact solutions and conservation laws. In this respect the Lie-Bäcklund groups of tangent transformations, particular cases of which are the Lie tangent and the Lie point groups, are extensively used.

In Chapter I we first review the classical results of Lie, Bäcklund and Bianchi as well as the more recent ones due mainly to Ovsjannikov. We then concentrate on the Lie-Bäcklund groups (or more precisely on the corresponding Lie-Bäcklund operators), as introduced by Ibragimov and Anderson, and prove some lemmas about them which are useful for the following chapters. Finally we introduce the concept of a conditionally admissible operator (as opposed to an admissible one) and show how this can be used to generate exact solutions.

In Chapter II we establish the group nature of all separable solutions and conserved quantities in classical mechanics by analyzing the group structure of the Hamilton-Jacobi equation. It is shown that consideration of only Lie point groups is insufficient. For this purpose a special type of Lie-Bäcklund groups, those equivalent to Lie tangent groups, is used. It is also shown how these generalized groups induce Lie point groups on Hamilton's equations. The generalization of the above results to any first order equation, where the dependent variable does not appear explicitly, is obvious. In the second part of this chapter we investigate admissible operators (or equivalently constants of motion) of the Hamilton-Jacobi equation with polynornial dependence on the momenta. The form of the most general constant of motion linear, quadratic and cubic in the momenta is explicitly found. Emphasis is given to the quadratic case, where the particular case of a fixed (say zero) energy state is also considered; it is shown that in the latter case additional symmetries may appear. Finally, some potentials of physical interest admitting higher symmetries are considered. These include potentials due to two centers and limiting cases thereof. The most general two-center potential admitting a quadratic constant of motion is obtained, as well as the corresponding invariant. Also some new cubic invariants are found.

In Chapter III we first establish the group nature of all separable solutions of any linear, homogeneous equation. We then concentrate on the Schrodinger equation and look for an algorithm which generates a quantum invariant from a classical one. The problem of an isomorphism between functions in classical observables and quantum observables is studied concretely and constructively. For functions at most quadratic in the momenta an isomorphism is possible which agrees with Weyl' s transform and which takes invariants into invariants. It is not possible to extend the isomorphism indefinitely. The requirement that an invariant goes into an invariant may necessitate variants of Weyl' s transform. This is illustrated for the case of cubic invariants. Finally, the case of a specific value of energy is considered; in this case Weyl's transform does not yield an isomorphism even for the quadratic case. However, for this case a correspondence mapping a classical invariant to a quantum orie is explicitly found.

Chapters IV and V are concerned with the general group structure of evolution equations. In Chapter IV we establish a one to one correspondence between admissible Lie-Bäcklund operators of evolution equations (derivable from a variational principle) and conservation laws of these equations. This correspondence takes the form of a simple algorithm.

In Chapter V we first establish the group nature of all Bäcklund transformations (BT) by proving that any solution generated by a BT is invariant under the action of some conditionally admissible operator. We then use an algorithm based on invariance criteria to rederive many known BT and to derive some new ones. Finally, we propose a generalization of BT which, among other advantages, clarifies the connection between the wave-train solution and a BT in the sense that, a BT may be thought of as a variation of parameters of some. special case of the wave-train solution (usually the solitary wave one). Some open problems are indicated.

Most of the material of Chapters II and III is contained in [I], [II], [III] and [IV] and the first part of Chapter V in [V].

On the Mumford-Tate conjecture for Abelian varieties with reduction conditions

In this thesis we study Galois representations corresponding to abelian varieties with certain reduction conditions. We show that these conditions force the image of the representations to be "big," so that the Mumford-Tate conjecture (:= MT) holds. We also prove that the set of abelian varieties satisfying these conditions is dense in a corresponding moduli space.

The main results of the thesis are the following two theorems.

Theorem A: Let A be an absolutely simple abelian variety, End° (A) = k : imaginary quadratic field, g = dim(A). Assume either dim(A) ≤ 4, or A has bad reduction at some prime ϕ, with the dimension of the toric part of the reduction equal to 2r, and gcd(r,g) = 1, and (r,g) ≠ (15,56) or (m -1, m(m+1)/2). Then MT holds.

Theorem B: Let M be the moduli space of abelian varieties with fixed polarization, level structure and a k-action. It is defined over a number field F. The subset of M(Q) corresponding to absolutely simple abelian varieties with a prescribed stable reduction at a large enough prime ϕ of F is dense in M(C) in the complex topology. In particular, the set of simple abelian varieties having bad reductions with fixed dimension of the toric parts is dense.

Besides this we also established the following results:

(1) MT holds for some other classes of abelian varieties with similar reduction conditions. For example, if A is an abelian variety with End° (A) = Q and the dimension of the toric part of its reduction is prime to dim( A), then MT holds.

(2) MT holds for Ribet-type abelian varieties.

(3) The Hodge and the Tate conjectures are equivalent for abelian 4-folds.

(4) MT holds for abelian 4-folds of type II, III, IV (Theorem 5.0(2)) and some 4-folds of type I.

(5) For some abelian varieties either MT or the Hodge conjecture holds.

Electron tunneling in proteins and water

The subject of this thesis is electronic coupling in donor-bridge-acceptor systems. In Chapter 2, ET properties of cyanide-bridged dinuclear ruthenium complexes were investigated. The strong interaction between the mixed-valent ruthenium centers leads to intense metal-to-metal charge transfer bands (MMCT). Hush analysis of the MMCT absorption bands yields the electronic-coupling strength between the metal centers (H_(AB)) and the total reorganization energy (λ). Comparison of ET kinetics to calculated rates shows that classical ET models fail to account for the observed kinetics and nuclear tunneling must be considered.

In Chapter 3, ET rates were measured in four ruthenium-modified highpotential iron-sulfur proteins (HiPIP), which were modified at position His50, His81, His42 and His18, respectively. ET kinetics for the His50 and His81 mutants are a factor of 300 different, while the donor-acceptor separation is nearly identical. PATHWAY calculations corroborate these measurements and highlight the importance of structural detail of the intervening protein matrix.

In Chapter 4, the distance dependence of ET through water bridges was measured. Photoinduced ET measurements in aqueous glasses at 77 K show that water is a poor medium for ET. Luminescence decay and quantum yield data were analyzed in the context of a quenching model that accounts for the exponential distance dependence of ET, the distance distribution of donors and acceptors embedded in the glass and the excluded volumes generated by the finite sizes of the donors and acceptors.

In Chapter 5, the pH-dependent excited state dynamics of ruthenium-modified amino acids were measured. The [Ru(bpy)_(3)] ^(2+) chromophore was linked to amino acids via an amide linkage. Protonation of the amide oxygen effectively quenches the excited state. In addition. time-resolved and steady-state luminescence data reveal that nonradiative rates are very sensitive to the protonation state and the structure of the amino acid moiety.

Studies on the role of histones in the structure and function of chromatin

Studies on the dissociation of histones from chromatin by increasing concentrations of sodium deoxycholate (DOC) have shown that histrone II is removed at lowest concentrations of DOC, while slightly higher concentrations remove histones III and IV. Still higher concentrations remove histone I.

The complete separation of chromatin and ¹⁴C-DOC by sucrose sedimentation indicated that the binding of DOC to chromatin is readily and completely reversible.

The dissociation of histones from chromatin by increasing concentrations of related cholanic acids and some of their conjugated derivatives were studied. The results suggested that the driving force for the interaction between the cholanic acid anion and histones is the lowering of the activity coefficient of the cholanic acid anion which occurs when it is partially removed from solution by interaction with hydrophobic regions of the positively charged histones.

The role of histones in the structure of chromatin has been studied by comparing the effects of selective removal of histones from chromatin by increasing concentrations of DOC with those caused by NaCl (removes histone I at lowest concentrations, while higher concentrations remove histones II, III, and IV). Properties studied included thermal denaturation, sedimentation velocity, flow dichroism, relaxation times of molecules oriented in a flow field, and the irreversible disruption of a 130 S, cross-linked component of sheared chromatin. The data indicated that none of the structural or chemical parameters with which these properties are correlated show a dependence on the presence of one particular histone fraction.

The template activity (ability to prime a 0.2 M KC1 DNA-dependent RNA synthesis system catalyzed by E. coli RNA polymerase) increases from that of native chromatin (approximately 25 per cent of that pure DNA) to that of pure DNA in a fashion which shows a nearly linear relationship to the amount of histone coverage of the template. The precipitability of partially dehistonized chromatin samples in 0.15 M NaCl shows a large dependence on the presence of histone I.

Crystal Coulomb energies: I. Organic donor-acceptor complexes--a review. II. Classical Ewald calculations of the Coulomb binding energy of four donor-acceptor crystals and Wurster's blue perchlorate. III. A rapid-convergence quantum-mechanical formalism for crystal electronic energies

Chapter I

Theories for organic donor-acceptor (DA) complexes in solution and in the solid state are reviewed, and compared with the available experimental data. As shown by McConnell et al. (Proc. Natl. Acad. Sci. U.S., 53, 46-50 (1965)), the DA crystals fall into two classes, the holoionic class with a fully or almost fully ionic ground state, and the nonionic class with little or no ionic character. If the total lattice binding energy 2ε₁ (per DA pair) gained in ionizing a DA lattice exceeds the cost 2ε_o of ionizing each DA pair, ε₁ + ε_o less than 0, then the lattice is holoionic. The charge-transfer (CT) band in crystals and in solution can be explained, following Mulliken, by a second-order mixing of states, or by any theory that makes the CT transition strongly allowed, and yet due to a small change in the ground state of the non-interacting components D and A (or D⁺ and A^-). The magnetic properties of the DA crystals are discussed.

Chapter II

A computer program, EWALD, was written to calculate by the Ewald fast-convergence method the crystal Coulomb binding energy E_C due to classical monopole-monopole interactions for crystals of any symmetry. The precision of E_C values obtained is high: the uncertainties, estimated by the effect on E_C of changing the Ewald convergence parameter η, ranged from ± 0.00002 eV to ± 0.01 eV in the worst case. The charge distribution for organic ions was idealized as fractional point charges localized at the crystallographic atomic positions: these charges were chosen from available theoretical and experimental estimates. The uncertainty in E_C due to different charge distribution models is typically ± 0.1 eV (± 3%): thus, even the simple Hückel model can give decent results.

E_C for Wurster's Blue Perchl orate is -4.1 eV/molecule: the crystal is stable under the binding provided by direct Coulomb interactions. E_C for N-Methylphenazinium Tetracyanoquino- dimethanide is 0.1 eV: exchange Coulomb interactions, which cannot be estimated classically, must provide the necessary binding.

EWALD was also used to test the McConnell classification of DA crystals. For the holoionic (1:1)-(N,N,N',N'-Tetramethyl-para- phenylenediamine: 7,7,8,8-Tetracyanoquinodimethan) E_C = -4.0 eV while 2ε_o = 4.6₅ eV: clearly, exchange forces must provide the balance. For the holoionic (1:1)-(N,N,N',N'-Tetramethyl-para- phenylenediamine:para-Chloranil) E_C = -4.4 eV, while 2ε_o = 5.0 eV: again EC falls short of 2ε₁. As a Gedankenexperiment, two nonionic crystals were assumed to be ionized: for (1:1)-(Hexamethyl- benzene:para-Chloranil) E_C = -4.5 eV, 2ε_o = 6.6 eV; for (1:1)- (Napthalene:Tetracyanoethylene) E_C = -4.3 eV, 2ε_o = 6.5 eV. Thus, exchange energies in these nonionic crystals must not exceed 1 eV.

Chapter III

A rapid-convergence quantum-mechanical formalism is derived to calculate the electronic energy of an arbitrary molecular (or molecular-ion) crystal: this provides estimates of crystal binding energies which include the exchange Coulomb inter- actions. Previously obtained LCAO-MO wavefunctions for the isolated molecule(s) ("unit cell spin-orbitals") provide the starting-point. Bloch's theorem is used to construct "crystal spin-orbitals". Overlap between the unit cell orbitals localized in different unit cells is neglected, or is eliminated by Löwdin orthogonalization. Then simple formulas for the total kinetic energy Q^(XT)_λ, nuclear attraction [λ/λ]^XT, direct Coulomb [λλ/λ'λ']^XT and exchange Coulomb [λλ'/λ'λ]^XT integrals are obtained, and direct-space brute-force expansions in atomic wavefunctions are given. Fourier series are obtained for [λ/λ]^XT, [λλ/λ'λ']^XT, and [λλ/λ'λ]^XT with the help of the convolution theorem; the Fourier coefficients require the evaluation of Silverstone's two-center Fourier transform integrals. If the short-range interactions are calculated by brute-force integrations in direct space, and the long-range effects are summed in Fourier space, then rapid convergence is possible for [λ/λ]^XT, [λλ/λ'λ']^XT and [λλ'/λ'λ]^XT. This is achieved, as in the Ewald method, by modifying each atomic wavefunction by a "Gaussian convergence acceleration factor", and evaluating separately in direct and in Fourier space appropriate portions of [λ/λ]^XT, etc., where some of the portions contain the Gaussian factor.

I. Spectroscopic evidence for slow vibrational relaxation in excited electronic states of diatomics in rare gas solids. II. Static crystal field effects in the electronic spectra of isotopically mixed benzene crystals

Part I

Studies of vibrational relaxation in excited electronic states of simple diatomic molecules trapped in solid rare-gas matrices at low temperatures are reported. The relaxation is investigated by monitoring the emission intensity from vibrational levels of the excited electronic state to vibrational levels of the ground electronic state. The emission was in all cases excited by bombardment of the doped rare-gas solid with X-rays.

The diatomics studied and the band systems seen are: N₂, Vegard-Kaplan and Second Positive systems; O₂, Herzberg system; OH and OD, A ²Σ⁺ - X²II_i system. The latter has been investigated only in solid Ne, where both emission and absorption spectra were recorded; observed fine structure has been partly interpreted in terms of slightly perturbed rotational motion in the solid. For N₂, OH, and OD emission occurred from v' > 0, establishing a vibrational relaxation time in the excited electronic state of the order, of longer than, the electronic radiative lifetime. The relative emission intensity and decay times for different v' progressions in the Vegard-Kaplan system are found to depend on the rare-gas host and the N₂ concentration, but are independent of temperature in the range 1.7°K to 30°K.

Part II

Static crystal field effects on the absorption, fluorescence, and phosphorescence spectra of isotopically mixed benzene crystals were investigated. Evidence is presented which demonstrate that in the crystal the ground, lowest excited singlet, and lowest triplet states of the guest deviate from hexagonal symmetry. The deviation appears largest in the lowest triplet state and may be due to an intrinsic instability of the ³B_1u state. High resolution absorption and phospho- rescence spectra are reported and analyzed in terms of site-splitting of degenerate vibrations and orientational effects. The guest phosphorescence lifetime for various benzene isotopes in C₆D₆ and sym-C₆H₃D₃ hosts is presented and discussed.

I. Foehn winds of southern California. II. Foehn wind cyclo-genesis. III. Weather conditions associated with the Akron disaster. IV. The Los Angeles storm of December 30, 1933 to January 1, 1934

I. Foehn winds of southern California.
An investigation of the hot, dry and dust laden winds occurring in the late fall and early winter in the Los Angeles Basin and attributed in the past to the influences of the desert regions to the north revealed that these currents were of a foehn nature. Their properties were found to be entirely due to dynamical heating produced in the descent from the high level areas in the interior to the lower Los Angeles Basin. Any dust associated with the phenomenon was found to be acquired from the Los Angeles area rather than transported from the desert. It was found that the frequency of occurrence of a mild type foehn of this nature during this season was sufficient to warrant its classification as a winter monsoon. This results from the topography of the Los Angeles region which allows an easy entrance to the air from the interior by virtue of the low level mountain passes north of the area. This monsoon provides the mild winter climate of southern California since temperatures associated with the foehn currents are far higher than those experienced when maritime air from the adjacent Pacific Ocean occupies the region.

II. Foehn wind cyclo-genesis.
Intense anticyclones frequently build up over the high level regions of the Great Basin and Columbia Plateau which lie between the Sierra Nevada and Cascade Mountains to the west and the Rocky Mountains to the east. The outflow from these anticyclones produce extensive foehns east of the Rockies in the comparatively low level areas of the middle west and the Canadian provinces of Alberta and Saskatchewan. Normally at this season of the year very cold polar continental air masses are present over this territory and with the occurrence of these foehns marked discontinuity surfaces arise between the warm foehn current, which is obliged to slide over a colder mass, and the Pc air to the east. Cyclones are easily produced from this phenomenon and take the form of unstable waves which propagate along the discontinuity surface between the two dissimilar masses. A continual series of such cyclones was found to occur as long as the Great Basin anticyclone is maintained with undiminished intensity.

III. Weather conditions associated with the Akron disaster.
This situation illustrates the speedy development and propagation of young disturbances in the eastern United States during the spring of the year under the influence of the conditionally unstable tropical maritime air masses which characterise the region. It also furnishes an excellent example of the superiority of air mass and frontal methods of weather prediction for aircraft operation over the older methods based upon pressure distribution.

IV. The Los Angeles storm of December 30, 1933 to January 1, 1934.
This discussion points out some of the fundamental interactions occurring between air masses of the North Pacific Ocean in connection with Pacific Coast storms and the value of topographic and aerological considerations in predicting them. Estimates of rainfall intensity and duration from analyses of this type may be made and would prove very valuable in the Los Angeles area in connection with flood control problems.

I. Spectroscopic observation of discrete sites in simple liquids. II. Infrared intensity perturbations of hydrogen halide fundamentals in liquid xenon. III. Rotation of HCl in solid rare gases.

Part I

The spectrum of dissolved mercury atoms in simple liquids has been shown to be capable of revealing information concerning local structures in these liquids.

Part II

Infrared intensity perturbations in simple solutions have been shown to involve more detailed interaction than just dielectric polarization. No correlation has been found between frequency shifts and intensity enhancements.

Part III

Evidence for perturbed rotation of HCl in rare gas matrices has been found. The magnitude of the barrier to rotation is concluded to be of order of 30 cm^(-1).

Magnetic behavior of basic iron(III) compounds. I. Magnetic behavior of the basic iron sulphates and basic iron chromate. II. Magnetic behavior of delta ferric oxide hydroxide

I. The thermomagnetic behavior and infrared spectroscopic features of KFe₃(SO₄)₂(OH)₆ (jarosite), (H₃O)Fe₃(SO₄)₂ (OH)₆ (hydronium jarosite), KFe₃(CrO₄)₂ (OH)₆, Fe(OH)SO₄ (basic iron sulfate), and Fe(OH)CrO₄ (basic iron chromate) are reported. Fe(OH)CrO₄ and KFe₃(CrO₄)₂ (OH)₆ are shown to be weak ferro magnets with Curie temperatures of 73 and 71 °K, respectively. This unusual magnetic behavior is rationalized in terms of the ionic spin configurations of the phases. Exchange coupling through chromate bridging groups is shown to be weak.

II. The magnetic behavior and the influence of preparative history on the magnetic behavior of δFeO(OH) is reported. δFeO(OH) is shown to be a fine-particulate, uniaxial, magnetic species. Magnetization data for this species are shown to be consistent with the existence of magnetically inactive layers surrounding magnetic particles.

I. A study of the dynamics of triplet excitons in molecular crystals. II. An investigation of delayed light emission from Chlorella pyrenoidosa

I. PREAMBLE AND SCOPE

Brief introductory remarks, together with a definition of the scope of the material discussed in the thesis, are given.

II. A STUDY OF THE DYNAMICS OF TRIPLET EXCITONS IN MOLECULAR CRYSTALS

Phosphorescence spectra of pure crystalline naphthalene at room temperature and at 77˚ K are presented. The lifetime of the lowest triplet ³B_1u state of the crystal is determined from measurements of the time-dependence of the phosphorescence decay after termination of the excitation light. The fact that this lifetime is considerably shorter in the pure crystal at room temperature than in isotopic mixed crystals at 4.2˚ K is discussed, with special importance being attached to the mobility of triplet excitons in the pure crystal.

Excitation spectra of the delayed fluorescence and phosphorescence from crystalline naphthalene and anthracene are also presented. The equation governing the time- and spatial-dependence of the triplet exciton concentration in the crystal is discussed, along with several approximate equations obtained from the general equation under certain simplifying assumptions. The influence of triplet exciton diffusion on the observed excitation spectra and the possibility of using the latter to investigate the former is also considered. Calculations of the delayed fluorescence and phosphorescence excitation spectra of crystalline naphthalene are described.

A search for absorption of additional light quanta by triplet excitons in naphthalene and anthracene crystals failed to produce any evidence for the phenomenon. This apparent absence of triplet-triplet absorption in pure crystals is attributed to a low steady-state triplet concentration, due to processes like triplet-triplet annihilation, resulting in an absorption too weak to be detected with the apparatus used in the experiments. A comparison of triplet-triplet absorption by naphthalene in a glass at 77˚ K with that by naphthalene-h₈ in naphthalene-d₈ at 4.2˚ K is given. A broad absorption in the isotopic mixed crystal triplet-triplet spectrum has been tentatively interpreted in terms of coupling between the guest ³B_1u state and the conduction band and charge-transfer states of the host crystal.

III. AN INVESTIGATION OF DELAYED LIGHT EMISSION FROM Chlorella Pyrenoidosa

An apparatus capable of measuring emission lifetimes in the range 5 X 10^-9 sec to 6 X 10^-3 sec is described in detail. A cw argon ion laser beam, interrupted periodically by means of an electro-optic shutter, serves as the excitation source. Rapid sampling techniques coupled with signal averaging and digital data acquisition comprise the sensitive detection and readout portion of the apparatus. The capabilities of the equipment are adequately demonstrated by the results of a determination of the fluorescence lifetime of 5, 6, 11, 12-tetraphenyl-naphthacene in benzene solution at room temperature. Details of numerical methods used in the final data reduction are also described.

The results of preliminary measurements of delayed light emission from Chlorella Pyrenoidosa in the range 10^-3 sec to 1 sec are presented. Effects on the emission of an inhibitor and of variations in the excitation light intensity have been investigated. Kinetic analysis of the emission decay curves obtained under these various experimental conditions indicate that in the millisecond-to-second time interval the decay is adequately described by the sum of two first-order decay processes. The values of the time constants of these processes appear to be sensitive both to added inhibitor and to excitation light intensity.

I. Electronic states of heavily-doped molecular crystals--naphthalene. I. Theoretical. II. Experimental. II. Lowest singlet and triplet excited states of pyrazine

PART I

The energy spectrum of heavily-doped molecular crystals was treated in the Green’s function formulation. The mixed crystal Green’s function was obtained by averaging over all possible impurity distributions. The resulting Green’s function, which takes the form of an infinite perturbation expansion, was further approximated by a closed form suitable for numerical calculations. The density-of-states functions and optical spectra for binary mixtures of normal naphthalene and deuterated naphthalene were calculated using the pure crystal density-of-state functions. The results showed that when the trap depth is large, two separate energy bands persist, but when the trap depth is small only a single band exists. Furthermore, in the former case it was found that the intensities of the outer Davydov bands are enhanced whereas the inner bands are weakened. Comparisons with previous theoretical calculations and experimental results are also made.

PART II

The energy states and optical spectra of heavily-doped mixed crystals are investigated. Studies are made for the following binary systems: (1) naphthalene-h₈ and d₈, (2) naphthalene--h₈ and αd₄, and (3) naphthalene--h₈ and βd₁, corresponding to strong, medium and weak perturbations. In addition to ordinary absorption spectra at 4˚K, band-to-band transitions at both 4˚K and 77˚K are also analyzed with emphasis on their relations to cooperative excitation and overall density-of-states functions for mixed crystals. It is found that the theoretical calculations presented in a previous paper agree generally with experiments except for cluster states observed in system (1) at lower guest concentrations. These features are discussed semi-quantitatively. As to the intermolecular interaction parameters, it is found that experimental results compare favorably with calculations based on experimental density-of-states functions but not with those based on octopole interactions or charge-transfer interactions. Previous experimental results of Sheka and the theoretical model of Broude and Rashba are also compared with present investigations.

PART III

The phosphorescence, fluorescence and absorption spectra of pyrazine-h₄ and d₄ have been obtained at 4˚K in a benzene matrix. For comparison, those of the isotopically mixed crystal pyrazine-h₄ in d₄ were also taken. All these spectra show extremely sharp and well-resolved lines and reveal detailed vibronic structure.

The analysis of the weak fluorescence spectrum resolves the long-disputed question of whether one or two transitions are involved in the near-ultraviolet absorption of pyrazine. The “mirror-image relationship” between absorption and emission shows that the lowest singlet state is an allowed transition, properly designated as ¹B_3u ← ¹A_1g. The forbidden component ¹B_2g, predicted by both “exciton” and MO theories to be below the allowed component, must lie higher. Its exact location still remains uncertain.

The phosphorescence spectrum when compared with the excitation phosphorescence spectra, indicates that the lowest triplet state is also symmetry allowed, showing a strong 0-0 band and a “mirror-image relationship” between absorption and emission. In accordance with previous work, the triplet state is designated as ³B_3u.

The vibronic structure of the phosphorescence spectrum is very complicated. Previous work on the analysis of this spectrum all concluded that a long progression of v_6a exists. Under the high resolution attainable in our work, the supposed v_6a progression proves to have a composite triplet structure, starting from the second member of the progression. Not only is the v_9a hydrogen-bending mode present as shown by the appearance of the C-D bending mode in the d₄ spectrum, but a band of 1207 cm^-1 in the pyrazine in benzene system and 1231 cm^-1 in the mixed crystal system is also observed. This band is assigned as 2v_6b and of a_1g symmetry. Its anonymously strong intensity in the phosphorescence spectrum is interpreted as due to the Fermi resonance with the 2v_6a and v_9a band.

To help resolve the present controversy over the crystal phosphorescence spectrum of pyrazine, detailed vibrational analyses of the emission spectra were made. The fluorescence spectrum has essentially the same vibronic structure as the phosphorescence spectrum.

The structure specificity of alpha-chymotrypsin. I. Polypeptides as substrates. II. N-acylated peptide esters as substrates. III. Some reactive esters of N-acylated amino acids as substrates

The structural specificity of α-chymotrypsin for polypeptides and denatured proteins has been examined. The primary specificity of the enzyme for these natural substrates is shown to closely correspond to that observed for model substrates. A pattern of secondary specificity is proposed.

A series of N-acetylated peptide esters of varying length have been evaluated as substrates of α-chymotrypsin. The results are interpreted in terms of proposed specificity theories.

The α-chymotrypsin-catalyzed hydrolyses of a number of N-acetylated dipeptide methyl esters were studied. The results are interpreted in terms of the available specificity theories and are compared with results obtained in the study of polypeptide substrates. The importance of non-productive binding in determining the kinetic parameters of these substrates is discussed. A partial model of the locus of the active site which interacts with the R’₁CONH- group of a substrate of the form R’₁CONHCHR₂COR’₃ is proposed.

Finally, some reactive esters of N-acetylated amino acids have been evaluated as substrates of α-chymotrypsin. Their reactivity and stereo-chemical behavior are discussed in terms of the specificity theories available. The importance of a binding interaction between the carboxyl function of the substrate and the enzyme is suggested by the results obtained.

I. The crystal structure of potassium bis(tricyanovinyl)amine. II. Nuclear magnetic resonance studies of alkali halide solutions. III. Elucidation of the intramolecular hydrogen bond in acetylacetone by the deuterium isotope effect on the chemical shift of the bridge hydrogen

Part I

Potassium bis-(tricyanovinyl) amine, K⁺N[C(CN)=C(CN)₂]₂^-, crystallizes in the monoclinic system with the space group Cc and lattice constants, a = 13.346 ± 0.003 Å, c = 8.992 ± 0.003 Å, B = 114.42 ± 0.02°, and Z = 4. Three dimensional intensity data were collected by layers perpendicular to b* and c* axes. The crystal structure was refined by the least squares method with anisotropic temperature factor to an R value of 0.064.

The average carbon-carbon and carbon-nitrogen bond distances in –C-CΞN are 1.441 ± 0.016 Å and 1.146 ± 0.014 Å respectively. The bis-(tricyanovinyl) amine anion is approximately planar. The coordination number of the potassium ion is eight with bond distances from 2.890 Å to 3.408 Å. The bond angle C-N-C of the amine nitrogen is 132.4 ± 1.9°. Among six cyano groups in the molecule, two of them are bent by what appear to be significant amounts (5.0° and 7.2°). The remaining four are linear within the experimental error. The bending can probably be explained by molecular packing forces in the crystals.

Part II

The nuclear magnetic resonance of ⁸¹Br and ¹²⁷I in aqueous solutions were studied. The cation-halide ion interactions were studied by studying the effect of the Li⁺, Na⁺, K⁺, Mg⁺⁺, Cs⁺ upon the line width of the halide ions. The solvent-halide ion interactions were studied by studying the effects of methanol, acetonitrile, and acetone upon the line width of ⁸¹Br and ¹²⁷I in the aqueous solutions. It was found that the viscosity plays a very important role upon the halide ions line width. There is no specific cation-halide ion interaction for those ions such as Mg⁺⁺, Di⁺, Na⁺, and K⁺, whereas the Cs⁺ - halide ion interaction is strong. The effect of organic solvents upon the halide ion line width in aqueous solutions is in the order acetone ˃ acetonitrile ˃ methanol. It is suggested that halide ions do form some stable complex with the solvent molecules and the reason Cs⁺ can replace one of the ligands in the solvent-halide ion complex.

Part III

An unusually large isotope effect on the bridge hydrogen chemical shift of the enol form of pentanedione-2, 4(acetylacetone) and 3-methylpentanedione-2, 4 has been observed. An attempt has been made to interpret this effect. It is suggested from the deuterium isotope effect studies, temperature dependence of the bridge hydrogen chemical shift studies, IR studies in the OH, OD, and C=O stretch regions, and the HMO calculations, that there may probably be two structures for the enol form of acetylacetone. The difference between these two structures arises mainly from the electronic structure of the π-system. The relative population of these two structures at various temperatures for normal acetylacetone and at room temperature for the deuterated acetylacetone were calculated.