Neutron activation and the JFK assassination, Part I. Data and interpretation

Five lead fragments from bullet cores from the assassination of American President John F. Kennedy in 1963 were analyzed twice by NAA, first by the FBI in 1964 and then by Vincent P. Guinn in 1977. Their concentrations of Sb have provided invaluable information about the number and origin of bullets that hit Kennedy and Texas Governor John B. Connally. While both analyses appeared to group the fragments into a body shot and a head shot, the FBI set contained a systematic error and Guinn's results from quarters of test bullets showed that the indicator element Sb varied enough over quarters to potentially merge the groups. The latter problem was resolved by the FBI replicate analyses, which showed that antimony was nearly homogeneos on the small scales of the fragments, and by the mechanism by which jacketed bullets break when hitting bone, which generates tiny fragments from a single break near the middle of the lead core. They collectively meant that the fragments within each group were formed on the scale of subfragments. The two groups were just as they appear because the larger quarter-bullet heterogeneities did not apply. This result substantiates Guinn's original conclusion that two and only two bullets from Lee Harvey Oswald's rifle struck the two men. This revised version was published online in July 2006 with corrections to the Cover Date.     

Z/E-photoisomerizations of olefins with 4npi- or (4n + 2)pi-electron substituents: zigzag variations in olefin properties along the T(1) state energy surfaces

[Figure: see text]. A quantum chemical study has been performed to assess changes in aromaticity along the T1 state Z/E-isomerization pathways of annulenyl-substituted olefins. It is argued that the point on the T1 energy surface with highest substituent aromaticity corresponds to the minimum. According to Baird (J. Am. Chem. Soc. 1972, 94, 4941), aromaticity and antiaromaticity are interchanged when going from S0 to T1. Thus, olefins with S0 aromatic substituents (set A olefins) will be partially antiaromatic in T1 and vice versa for olefins with S0 antiaromatic substituents (set B olefins). Twist of the C=C bond to a structure with a perpendicular orientation of the 2p(C) orbitals (3p*) in T1 should lead to regaining substituent aromaticity in set A and loss of aromaticity in set B olefins. This hypothesis is verified through quantum chemical calculations of T1 energies, geometries (bond lengths and harmonic oscillator measure of aromaticity), spin densities, and nucleus independent chemical shifts whose differences along the T1 PES display zigzag dependencies on the number of -electrons in the annulenyl substituent of the olefin. Aromaticity changes are reflected in the profiles of the T1 potential energy surfaces (T1 PESs) for Z/E-isomerizations because olefins in set A have minima at 3p* whereas those in set B have maxima at such structures. The proper combination (fusion) of the substituents of set A and B olefins could allow for design of novel optical switch compounds that isomerize adiabatically with high isomerization quantum yields.     

Potassium Iodide as a Chemical Actinometer for 254 nm Radiation: Use of lodate as an Electron Scavenger

Abstract— A solution of 0.6 M iodide and 0.1 M iodate in 0.01 M borate buffer (pH 9.25) can be used as a chemical actinometer to measure the incident fluence from a low-pressure mercury lamp that puts out more than 85% of its energy at 254 nm. The actinometric solution is optically opaque to light below 290 nm and is optically transparent to wavelengths greater than 330 nm. Hence, the solution absorbs all of the germicidal wavelengths but little if any of the ambient light normally present in the laboratory. Iodate acts as an electron scavenger and prevents the back reaction of the free electron with the iodine atom following UV excitation of KI. Irradiation results in the linear formation of triiodide, which is quantitated by measuring its absorbance at 352 nm. The quantum yield for this system is approximately 0.75 0.03 at 20.7A_oC or approximately three times greater than that obtained previously using nitrous oxide as an electron scavenger. A model is proposed to account for this difference. A precise expression to account for the concentration and temperature dependence of the quantum yield is given by pH = 0.75(1 + 0.23[C - 0.577])(1 + 0.02[T - 20.7]) where C is the concentration of iodide and T is the temperature. The concentration of iodide can be obtained from the absorbance at 300 nm prior to irradiation using 1.061 MJ cm⁻¹ as the molar extinction coefficient. This actinometric system meets the quality criteria established by the International Union of Pure and Applied Chemistry with the caveat that it is designed to measure only germicidal radiation (i.e. wavelengths less than 290 nm).     

Participation d'un groupe amide a la formation de sels de dioxolanne-1,3 ylium-2; Modele biomimetique de reaction de peptidation

An amide group is shown to be capable of intramolecular participation in the formation of an 1,3-dioxolan 2-ylium cation giving a tricyclic organic cation of a new type $\text{5a}$,$\text{b}$. This cation may be considered as a model of an electrophilic intermediate which might be formed from a peptidyl t-RNA during protein biosynthesis.The tricyclic salt $\text{5a}$,$\text{b}$ reacts with water and methanol like a classical dioxolenium salt. An amide acetal $\text{18}$ can be obtained from dimethylamine and 5a; hydrolysis of $\text{18}$ does not lead to the corresponding amide $\text{20}$ but to the cleavage of the CN. bond.     

ACTION SPECTRA FOR THE PHOTOLYSIS OF 5-IODODEOXYURIDINE IN DNA AND RELATED MODEL SYSTEMS: EVIDENCE FOR SHORT-RANGE ENERGY TRANSFER*

Abstract— A variety of polynucleotides containing 5-iodouracil residues were irradiated in aqueous solution with wavelengths between 240 and 313 nm. From the rate of deiodination the photochemical cross sections (a_B) were determined as a function of the irradiation wavelength (A). The expression was used to relate the observed values of _B to the intrinsic quantum yield, φ_INT, and to the absorption cross sections, and for the iodinated and noniodinated residues, respectively. φ_INT is the probability an excited iodouracil residue will deiodinate, while the parameter b is a measure of the number of noniodinated bases which contribute their excitation energy to the deiodination process. For IdUrd and poly(5-iodouridylic acid), the average values of φ_INT calculated from the experimental _B values were 0.0202 and 0.0188, respectively, for irradiation in air. In native, denatured, and depurinated DNA in which IdUrd was substituted for 10% of the Thd, the average φ_INT values were 0.0069, 0.0088, and 0.0153, respectively, indicating an enhancement in φ_INT upon decreasing the order of the polynucleotide. In contrast, the average values of b bor the same set of compounds were found to be 4 , 2 and 0.4, respectively, indicating a decrease in b with decreasing polynucleotide order, i.e. a loss of base stacking decreases the extent of energy transfer. A value of b= 4 for native DNA is assumed to mean that the extent of energy transfer in native DNA is limited to four base donors per iodouracil residue serving as an energy trap.     

PHOTOCHEMISTRY OF DNA CONTAINING IODINATED CYTOSINE*

Abstract— –Irradiation at 313 nm of compounds containing iodinated cytosine moieties results in the photolysis of iodine. Photolysis occurs with a quantum yield of 0·0224·024 for 5-iododeoxycytidine and 5-iododeoxycytidine monophosphate, and 0·004–0·008 for iodinated DNA as well as for iodinated polycytidylate. Photodegradation of the cytosine moiety occurs when air is present during irradiation, presumably due to the reaction of oxygen with the cytosyl radical formed when iodine is lost. This oxygen promoted photodegradation destroys the cytosine chromophore and is complete in the monomers but occurs to only a limited extent in the polymers. In the absence of oxygen or in the presence of ethanol, photodegradation is prevented and the loss of iodine leads exclusively to the formation of the cytosine chromophore. In DNA, the loss of iodine is accompanied by the formation of sugar damage and/or chain breaks. As measured by sedimentation in alkaline sucrose gradients, approximately one break is made for every six iodinqs lost in denatured DNA. The frequency of chain breakage per iodine photolyzed is reduced 2-fold in renatured DNA. Analysis in neutral gradients suggests that half of the breaks observed in alkali are alkali-labile bonds. Both ethanol and cysteamine reduce the number of chain breaks observed in alkali by ˜ 3-fold.     

QUANTUM YIELD OF PHOTOHYDRATION FOR DIMETHYLURACIL. CONCENTRATION AND WAVELENGTH DEPENDENCE*

Abstract— The quantum yields for the photohydration of dimethyluracil were determined for concentrations in the range 5 × 10^--¹-^-1 × 10^--³M by use of 240–280 nm irradiation. The average quantum yield (0.0139 f 0.0005) was independent of both concentration and irradiation wavelength.     

USE OF POTASSIUM IODIDE AS A CHEMICAL ACTINOMETER

Abstract Aqueous solutions of KI were examined for use as chemical actinometers to measure 254 nm (germicidal) radiation. Irradiation results in electron ejection from iodide such that aqueous electrons and iodine atoms are formed. In the presence of N₂0, an electron scavenger, recombination of these two reactive species is eliminated and stoi-chiometric formation of triiodide occurs. The absorbance increase due to triiodide was followed and the quantum yield determined using either a radiometer or ferrioxalate actinometry to estimate the amount of energy absorbed by the KI solution. The quantum yield ( ø ) at 25°C was determined to be 0.26 using radiometry, and 0.224–0.233 using actinometry, depending on the radiation conditions. The following expression was used to measure the incident Huence rate for 254 radiation at a given temperature T for irradiation over a time interval Δt (s) fluence rate (W/m²) = 4. 96 × 10⁶ΔOD(λ)/ e(λ) [0.23+0.004(T-25)] δ t cm⁻¹
At temperatures other than 25°C, the temperature dependence of the quantum yield (0.004/°C) is taken into account by the term shown in the denominator. Because KI remains relatively blind to longer wavelengths such as those found in normal room light, measurements can be made in the presence of room light without having to work in a darkened room.     

Molecular fluorescence excitation-emission matrices relevant to tissue spectroscopy

In vivo and ex vivo studies of fluorescence from endogenous and exogenous molecules in tissues and cells are common for applications such as detection or characterization of early disease. A systematic determination of the excitation-emission matrices (EEM) of known and putative endogenous fluorophores and a number of exogenous fluorescent photodynamic therapy drugs has been performed in solution. The excitation wavelength range was 250-520 nm, with fluorescence emission spectra collected in the range 260-750 nm. In addition, EEM of intact normal and adenomatous human colon tissues are presented as an example of the relationship to the EEM of constituent fluorophores and illustrating the effects of tissue chromophore absorption. As a means to make this large quantity of spectral data generally available, an interactive database has been developed. This currently includes EEM and also absorption spectra of 35 different endogenous and exogenous fluorophores and chromophores and six photosensitizing agents. It is intended to maintain and extend this database in the public domain, accessible through the Photochemistry and Photobiology website (http://www.aspjournal. com/).     

Quantum yield of the iodide-iodate chemical actinometer: dependence on wavelength and concentrations

The quantum yield (QY) of the iodide-iodate chemical actinometer (0.6 M KI-0.1 M KIO3) was determined for irradiation between 214 and 330 nm. The photoproduct, triiodide, was determined from the increase in absorbance at 352 nm, which together with a concomitant measurement of the UV fluence enabled the QY to be calculated. The QY at 254 nm was determined to be 0.73 +/- 0.02 when calibration was carried out against a National Institute of Standards and Technology traceable radiometer or photometric device. At wavelengths below 254 nm the QY increased slightly, leveling off at -0.80 +/- 0.05, whereas above 254 nm the QY decreases linearly with wavelength, reaching a value of 0.30 at 284 nm. In addition, the QY was measured at different iodide concentrations. There is a slight decrease in QY going from 0.6 to 0.15 M KI, whereas below 0.15 M KI the QY drops off sharply, decreasing to 0.23 by 0.006 M KI. Calibration of the QY was also done using potassium ferrioxalate actinometry to measure the irradiance. These results showed a 20% reduction in QY between 240 and 280 nm as compared with radiometry. This discrepancy suggests that the QY of the ferrioxalate actinometer in this region of the spectrum needs reexamination.