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K R Thomas

Publications and source records attributed to K R Thomas.

At least 19 recordsLinked to original sources
PubMed2001

Lattice-dictated conformers in bis(pyrazolyl)pyridine-based iron(II) complexes: Mössbauer, NMR, and magnetic studies.

Iron(II) complexes [FeL(2)](ClO(4))(2).CH(3)CN, [FeL(2)](BPh(4))(2).2CH(3)CN, and [FeL(2)](PF(6))(2) with an FeN(6) chromophore of the same ligand L (2,6-bis(3,5-dimethylpyrazol-1-ylmethyl)pyridine) and differing counterions have been made and their crystal and molecular structures determined. The first two crystallized in triclinic space group P(-)1, and the third, with PF(6)(-) anion in Ibca space group. The FeL(2) complex ions in all lattices have similarly distorted octahedral geometry. Variable-temperature Mössbauer spectra of [FeL(2)](ClO(4))(2).CH(3)CN and [FeL(2)](PF(6))(2) measured in the temperature range 1.7-300 K reveal temperature-dependent populations of two different spin states with increased amount of low-spin form at high temperatures, a phenomenon unlike the normal spin crossover behavior; this abnormal behavior is interpreted here as due to the presence of two different conformations. It is very interesting to note that the two different compounds have similar spectra, Mössbauer parameters, and temperature dependence. But the variable-temperature Mössbauer spectra of [FeL(2)](BPh(4))(2).2CH(3)CN in the range 20-300 K do not show the presence of such different species but exhibit a clear phase transition at approximately 200 K. This phase transition is further supported by SQUID measurements. The results of variable-temperature (1)H NMR in CD(3)CN and the solution susceptibility measurement of all complexes also support the presence of high-spin and low-spin forms in solution. Hence, the complex ion [FeL(2)](2+) exhibits a thermally driven interconversion between low-spin and a high-spin structural forms-a phenomenon observed in the solid and solution states due to ligand dynamics. This is not due to the well-known spin crossover phenomenon. These results are compared with the case of normal spin crossover seen in [FeL'(2)](ClO(4))(2) (L' = 2,6-(bis(pyrazol-1-ylmethyl)pyridine)).

Journal Article↗
PubMed2001

Light-emitting carbazole derivatives: potential electroluminescent materials.

Stable carbazole derivatives that contain peripheral diarylamines at the 3- and 6-positions and an ethyl or aryl substituent at the 9-position of the carbazole moiety have been synthesized via palladium-catalyzed C-N bond formation. These new carbazole compounds (carbs) are amorphous with high glass transition temperatures (T(g), 120-194 degrees C) and high thermal decomposition temperatures (T(d) > 450 degrees C). The compounds are weakly to moderately luminescent in nature. The emission wavelength ranges from green to blue and is dependent on the substituent at the peripheral nitrogen atoms. Two types of light-emitting diodes were constructed from carb: (I) ITO/carb/TPBI/Mg:Ag and (II) ITO/carb/Alq(3)/Mg:Ag, where TPBI and Alq(3) are 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene and tris(8-hydroxyquinoline) aluminum, respectively. In type I devices, the carb functions as the hole-transporting as well as emitting material. In type II devices, either carb, or Alq(3) is the light-emitting material. Several green light-emitting devices exhibit exceptional maximum brightness, and the physical performance appears to be better than those of typical green light-emitting devices of the structure ITO/diamine/Alq(3)/Mg:Ag. The relation between the LUMO of the carb and the performance of the light-emitting diode is discussed.

Journal Article↗
PubMed2001

Copper(II) azide complexes of aliphatic and aromatic amine based tridentate ligands: novel structure, spectroscopy, and magnetic properties.

Copper(II) azide complexes of three tridentate ligands namely 2,6-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L), 2,6-(pyrazol-1-ylmethyl)pyridine (L'), and dipropylenetriamine (dpt) yield three kinds of complexes with different azide-binding modes. The ligand L forms two end-on-end (mu-1,3) diazido-bridged binuclear complexes, [CuL(mu-N(3))](2)(ClO(4))(2) (1) and [CuL(mu-N(3))(ClO(4))](2).2CH(3)CN (2), and L' forms a perchlorato-bridged quasi-one-dimensional chain complex, [CuL'(N(3))(ClO(4))](n)() (3) with monodentate azide coordination. The ligation of dipropylenetriamine (dpt) gives a end-on (mu-1,1) diazido-bridged binuclear copper complex [Cu(dpt)(mu-N(3))](2)(ClO(4))(2) (4). The crystal and molecular structures of these complexes have been solved. Variable-temperature EPR results of 1 and 2 are identical and indicate the presence of both ferromagnetic and antiferromagnetic interactions within the dimer, the former dominating at low temperatures and the latter at high temperatures. The unusual temperature-dependent magnetic moment and EPR spectra of this dimer reveal the presence of temperature-dependent population of two triplet states, one being caused by antiferromagnetic and the other by ferromagnetic interaction, the former transforming to the latter on cooling. While the interaction of ground spin doublets of the two metal centers gives rise to a ferromagnetic coupling of J(g) = 90.73 cm(-1), the other coupling of J(e) = -185.64 cm(-1) is suggested to be caused by the interaction between an electron in one metal center and an electron from the azide of the other monomer by excitation of a d-electron to the empty ligand orbital. The ferromagnetic state is energetically favored by 104.39 cm(-1). Compound 3 exhibits axial spectra at room temperature and 77 K, and variable-temperature magnetic susceptibility data indicate that the copper centers form a weakly antiferromagnetic one-dimensional chain with J = -0.11 cm(-1). In the case of 4, the unique presence of two nonidentical dimeric units with different bond lengths and bond angles within the unit cell as inferred by crystal structure is proved by single-crystal EPR spectroscopy.

Journal Article↗
PubMed2001

EPR of Cu(II)-doped seven-coordinate inclusion compounds, M(stpy)3(NO3)2 x 1/2stpy (M = Cd(II) and Zn(II), stpy = trans-4-styrylpyridine): low symmetry effects in admixture of ground states.

Single crystal EPR of Cu(II)-doped low symmetry pentagonal bipyramidal Werner-type clathrate inclusion complexes of Cd(stpy)3(NO3)2 x 1/2stpy(1) and Zn(stpy)3(NO3)2 x 1/2stpy(2) (stpy = trans-4-styrylpyridine) is reported. The spin Hamiltonian parameters are found to be orthorhombic with g33 = 2.298, g22 = 2.108, g11 = 2.066, A33 = 107.3, A22 = 54.4 and A11 = 23.1 x 10(-4) cm(-1) for 1 and g33 = 2.292, g22 = 2.111, g11 = 2.067, A33 = 107.5, A22 = 54.7 and A11 = 22.9 x 10(-4) cm(-1) for 2. Angular variation studies for both 1 and 2 suggest that the Cu(II) ions are substitutionally incorporated in the host lattices. The magnitude of Cu(II) hyperfine coupling constant (A33) in both 1 and 2 are found to be low, in comparison to those of the pure Cu(II) complex, indicative of low symmetry for the substitutional sites in accordance with the crystal data. Such large reductions in Cu(II) hyperfine coupling are explicable in terms of a mixed d(x2 - y2)/dz2 ground state and delocalization of unpaired spin density onto the ligands.

Cadmium↗
PubMed2001

A mouse model of familial porphyria cutanea tarda.

Approximately one-third of patients with porphyria cutanea tarda (PCT), the most common porphyria in humans, inherit a single mutant allele of the uroporphyrinogen decarboxylase (URO-D) gene. PCT associated with URO-D mutations is designated familial PCT. The phenotype is characterized by a photosensitive dermatosis with hepatic accumulation and urinary excretion of uroporphyrin and hepta-carboxylic porphyrins. Most heterozygotes for URO-D mutations do not express a porphyric phenotype unless hepatic siderosis is present. Hemochromatosis gene (HFE) mutations are frequently found when the phenotype is expressed. We used homologous recombination to disrupt one allele of murine URO-D. URO-D(+/-) mice had half-wild type (wt) URO-D protein and enzymatic activity in all tissues but did not accumulate hepatic porphyrins, indicating that half-normal URO-D activity is not rate limiting. When URO-D(+/-) mice were injected with iron-dextran and given drinking water containing delta-aminolevulinic acid for 21 days, hepatic porphyrins accumulated, and hepatic URO-D activity was reduced to 20% of wt. We bred mice homozygous for an HFE gene disruption (HFE(-/-)) to URO-D(+/-) mice, generating mice with the URO-D(+/-)/HFE(-/-) genotype. These animals developed a porphyric phenotype by 14 weeks of age without ALA supplementation, and URO-D activity was reduced to 14% of wt. These data indicate that iron overload alone is sufficient to reduce URO-D activity to rate-limiting levels in URO-D(+/-) mice. The URO-D(+/-) mouse serves as an excellent model of familial PCT and affords the opportunity to define the mechanism by which iron influences URO-D activity.

Aminolevulinic Acid↗
PubMed2001

Psychosocial issues following traumatic brain injury.

The author contends that Dean, Colantonio, Ratcliff, and Chase in 2000 probably underestimated the importance of psychosocial factors in the very long-term adaptation to disability by 166 individuals with traumatic brain injury.

Adaptation, Psychological↗
PubMed2000

Maintenance of functional equivalence during paralogous Hox gene evolution.

Biological diversity is driven mainly by gene duplication followed by mutation and selection. This divergence in either regulatory or protein-coding sequences can result in quite different biological functions for even closely related genes. This concept is exemplified by the mammalian Hox gene complex, a group of 39 genes which are located on 4 linkage groups, dispersed on 4 chromosomes. The evolution of this complex began with amplification in cis of a primordial Hox gene to produce 13 members, followed by duplications in trans of much of the entire unit. As a consequence, Hox genes that occupy the same relative position along the 5' to 3' chromosomal coordinate (trans-paralogous genes) share more similarity in sequence and expression pattern than do adjacent Hox genes on the same chromosome. Studies in mice indicate that although individual family members may have unique biological roles, they also share overlapping functions with their paralogues. Here we show that the proteins encoded by the paralogous genes, Hoxa3 and Hoxd3, can carry out identical biological functions, and that the different roles attributed to these genes are the result of quantitative modulations in gene expression.

Alleles↗
PubMed1999

Targeting genes for self-excision in the germ line.

A procedure is described that directs the self-induced deletion of DNA sequences as they pass through the male germ line of mice. The testes-specific promoter from the angiotensin-converting enzyme gene was used to drive expression of the Cre-recombinase gene. Cre was linked to the selectable marker Neor, and the two genes flanked with loxP elements. This cassette was targeted to the Hoxa3 gene in mouse ES cells that were in turn used to generate chimeric mice. In these chimeras, somatic cells derived from the ES cells retained the cassette, but self-excision occurred in all ES-cell-derived sperm.

Animals↗
PubMed1995

A mouse model for the delta F508 allele of cystic fibrosis.

The most common cause of cystic fibrosis is a mutation that deletes phenylalanine 508 in cystic fibrosis transmembrane conductance regulator (CFTR). The delta F508 protein is misprocessed and degraded rather than traveling to the apical membrane. We used a novel strategy to introduce the delta F508 mutation into the mouse CFTR gene. Affected epithelia from homozygous delta F508 mice lacked CFTR in the apical membrane and were Cl-impermeable. These abnormalities are the same as those observed in patients with delta F508 and suggest that these mice have the same cellular defect. 40% of homozygous delta F508 animals survived into adulthood and displayed several abnormalities found in human disease and in CFTR null mice. These animals should provide an excellent model to investigate pathogenesis and to examine therapies directed at correcting the delta F508 defect.

Alleles↗
PubMed1995

A psychoanalytic study of Alexander the Great.

The purpose of this paper was to demonstrate how Freudian concepts such as the Oedipus complex, castration anxiety, fear of loss of love, the psychosexual stages of development, and the tripartite structure of personality can be used to understand the life and achievements of Alexander the Great. To accomplish this purpose, specific incidents, myths, and relationships in Alexander's life were analyzed from a Freudian psychoanalytic perspective. Green (1991), in his recent biography of Alexander, has questioned the merit of using Freudian concepts to understand Alexander's character. In fact, he stated specifically: If he (Alexander) had any kind of Oedipus complex it came in a poor second to the burning dynastic ambition which Olympias so sedulously fostered in him; those who insist on his psychological motivation would do better to take Adler as their mentor than Freud (p.56). Later, in the concluding section of his book, Green (1991, pp. 486-487) discounted Freudian interpretations of Alexander's distaste for sex, the rumors of his homosexual liaisons, his partiality for middle-aged or elderly ladies, and the systematic domination of his early years by Olympias as little more than the projected fears and desires of the interpreters. And again, an Adlerian power-complex paradigm was suggested as the preferable theoretical framework to use. Green's argument was based primarily on an exchange, reported originally by Plutarch, which took place between Alexander and Philip prior to Alexander's tutorship with Aristotle. Purportedly, Philip enjoined his son to study hard and pay close attention to all Aristotle said "so that you may not do a great many things of the sort that I am sorry I have done." At this point, Alexander "somewhat pertly" took Philip to task "because he was having children by other women besides his wife." Philip's reply was: "Well then, if you have many competitors for the kingdom, prove yourself honorable and good, so that you may obtain the kingdom not because of me, but because of yourself." Green interpreted this exchange as confirming that Alexander was more interested in his succession to the throne (power) than in any sexual relationships Philip might be having with any women other than Olympias. That is, Alexander's concern in this exchange was not about Philip's marital infidelity per se, but rather about the prospect of potential competitors (other children) for the throne. Significantly, by emphasizing the manifest content of the exchange, Green ignored a myriad of other possible fears and wishes on Alexander's part, including the fear of castration, the wish to have sex (like his father) with Olympias and other women, the wish to challenge his father's authority and superiority, the fear of loss of love, and the wish (given Philip's homosexual exploits with other boys) to have sex with Philip. Moreover, one could easily explain what Green has described as "the burning dynastic ambition which Olympias so sedulously fostered in him" (p.56), and Alexander's so called "power-complex" in terms which are perfectly consistent with drive/structure theory (e.g., see Freud, 1900/1953a and Freud, 1914/1957, respectively). In other words, Green's arguments against the possibility of a Freudian solution to the puzzle of Alexander's character are less than compelling. By contrast, as demonstrated in this paper, a plethora of historical data exist to suggest that much of Alexander's personality structure and behavior can be explained by his unresolved Oedipus complex, the ambition and self-confidence instilled in him by Olympias, the anal-sadistic and narcissistic organization of his character, his unconscious wish to please his mother, and his being lapped (from birth) in the myth of the hero. Although it is risky, at best, to attempt to analyze an individual without the benefit of clinical data, and even more risky to base such an analysis on fragmentary and often contradictory data assimilated long

Adult↗
PubMed1994

The Americans with Disabilities Act: social policy and worldwide implications for practice.

The primary purpose of this article is to inform an international audience about the Americans with Disabilities Act, which is considered by some American humanists to be the most significant piece of legislation since the passage of the Civil Rights Act in 1964. A secondary purpose of the article will be to place the Americans with Disabilities Act within the context of a world socio-political climate that demands a framework for the care and empowerment of individuals with disabilities.

Australia↗
PubMed1993

Location of crossovers during gene targeting with insertion and replacement vectors.

Gene targeting was used to introduce nonselectable genetic changes into chromosomal loci in mouse embryo-derived stem cells. The nonselectable markers were linked to a selectable marker in both insertion- and replacement-type vectors, and the transfer of the two elements to the Hprt locus was assayed. When insertion vectors were used as substrates, the frequency of transfer was highly dependent upon the distance between the nonselectable marker and the double-strand break in the vector. A marker located close to the vector ends was frequently lost, suggesting that a double-strand gap repair activity is involved in vector integration. When replacement vectors were used, cotransfer of a selectable marker and a nonselectable marker 3 kb apart was over 50%, suggesting that recombination between vector and target often occurs near the ends of the vector. To illustrate the use of replacement vectors to transfer specific mutations to the genome, we describe targeting of the delta F508 mutation to the CFTR gene in mouse embryo-derived stem cells.

Animals↗
PubMed1992

The Wolf-Man case: classical and self-psychological perspectives.

Freud's description of his analysis and treatment of the Wolf-Man will be forever regarded as an extraordinary clinical and theoretical achievement. What has been attempted in this paper is to demonstrate how selected aspects of the Wolf-Man case could be interpreted using a self-psychology paradigm. The intent was not to demean Freud or to undermine the theoretical and clinical contributions of drive/structure theory. Rather, I have attempted to show how Freud's analysis and treatment of the Wolf-Man might have been enhanced by a familiarity with more recent developments in psychoanalysis.

Adult↗
PubMed1992

High-fidelity gene targeting in embryonic stem cells by using sequence replacement vectors.

Mutations were targeted to the Hprt locus in murine embryonic stem cells by using sequence replacement vectors. When the vector was designed such that the mutated sequences were flanked on both sides by several kilobases of DNA homologous to the target locus, replacement of chromosomal sequences with the exogenous DNA occurred with precision. If, on the other hand, the target-homologous DNA on one arm of the vector was reduced to below 1 kb in length, the fidelity of recombination was diminished.

Animals↗