Copper(II) Complexes of l-Arginine as Netropsin Mimics Showing DNA Cleavage Activity in Red Light

Copper(II) complexes [Cu(L-arg)(2)](NO3)(2) (1) and [Cu(L-arg)(B)Cl]Cl (2-5), where B is a heterocyclic base, namely, 2,2'-bipyridine (bpy, 2), 1,10-phenanthroline (phen, 3), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 4), and dipyrido[3,2-a:2',3'-c)phenazine (dppz, 5), are prepared and their DNA binding and photoinduced DNA cleavage activity studied. Ternary complex 3, structurally characterized using X-ray crystallography, shows a square-pyramidal (4 + 1) coordination geometry in which the N,O-donor L-arginine and N,N-donor 1,10-phenanthroline form the basal plane with one chloride at the elongated axial site. The complex has a pendant cationic guanidinium moiety. The one-electron paramagnetic complexes display a metal-centered d-d band in the range of 590-690 nm in aqueous DMF They show quasireversible cyclic voltammetric response due to the Cu(II)/Cu(I) couple in the range of -0.1 to -0.3 V versus a saturated calomel electrode in a DMF-Tris HCl buffer (pH 7.2). The DNA binding propensity of the complexes is studied using various techniques. Copper(II) bis-arginate 1 mimics the minor groove binder netropsin by showing preferential binding to the AT-rich sequence of double-strand (ds) DNA. DNA binding study using calf thymus DNA gives an order: 5 (L-arg-dppz) >= 1 (biS-L-arg) > 4 (L-arg-dpq) > 3 (L-arg-phen) >> 2 (L-arg-bpy). Molecular docking calculations reveal that the complexes bind through extensive hydrogen bonding and electrostatic interactions with ds-DNA. The complexes cleave supercoiled pUC19 DNA in the presence of 3-mercaptopropionic acid as a reducing agent forming hydroxyl ((OH)-O-center dot) radicals. The complexes show oxidative photoinduced DNA cleavage activity in UV-A light of 365 nm and red light of 647.1 nm (Ar-Kr mixed-gas-ion laser) in a metal-assisted photoexcitation process forming singlet oxygen (O-1(2)) species in a type-II pathway. All of the complexes, barring complex 2, show efficient DNA photocleavage activity. Complexes 4 and 5 exhibit significant double-strand breaks of DNA in red light of 647.1 nm due to the presence of two photosensitizers, namely, L-arginine and dpq or dppz in the molecules.

Photoinduced DNA and Protein Cleavage Activity of Ferrocene-Appended L-Methionine Reduced Schiff Base Copper(II) Complexes of Phenanthroline Bases

Ferrocene-appended ternary copper(H) complexes of phenanthroline bases having CuN3OS coordination with an axial Cu-S bond derived from L-methionine reduced Schiff base shows red light induced oxidative DNA cleavage activity following a hydroxyl radical pathway. The dipyridophenazine complex, in addition, displays photoinduced oxidative cleavage of bovine serum albumin protein in UV-A light.

The Origin of Regioselectivity in a-Cleavage Reactions of Cyclopropenethiones: Potential Role of Pseudo-Jahn-Teller Effect in Substituted Cyclopropenyl Systems

Arylalkylcyclopropenethiones undergo highly regioselective photochemical a-cleavage via thioketene carbene intermediates, giving rise to products derived from the less stabilized carbene. UHF MIND0/3 calculations provide an insight into this unexpected regioselectivity. The nx* triplet of cyclopropenethione is calculated to have a highly unsymmetrical geometry with an elongated C-C bond, a delocalized thiaaUyl fragment, and a pyramidal radicaloid carbon (which eventually becomes the carbene center). From this molecular electronic structure, aryl group stabilization is expected to be more effective at the thiaallyl group rather than at the pyramidal radical center. Thus, the stability of the substituted triplet thione rather than that of the thioketene carbene determines the preferred regiochemistry of cleavage. The unusual structure of the cyclopropenethione triplet is suggested to be related to one of the Jahn-Teller distorted forms of the cyclopropenyl radical. An alternative symmetrical structure is adopted by the corresponding triplet of cyclopropenone, partly accounting for its differing photobehavior. A similar structural dichotomy is demonstrated for the corresponding radical anions as well.

Photo-induced double-strand DNA and site-specific protein cleavage activity of L-histidine (mu-oxo)diiron(III) complexes of heterocyclic bases

Three oxo-bridged diiron(III) complexes of L-histidine and heterocyclic bases [Fe-2(mu-O)(L-his)(2)(B)(2)](ClO4)(2) (1-3), where B is 2,2'-bipyridine (bpy),1,10-phenanthroline (phen), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq), were prepared and characterized. The bpy complex 1 was structurally characterized by X-ray crystallography. The molecular structure showed a {Fe-2(mu-O)} core in which iron(III) in a FeN4O2 coordination is bound to tridentate monoanionic L-histidine and bidentate bpy ligands. The Fe center dot center dot center dot Fe distance is similar to 3.5 angstrom. The Fe-O-Fe unit is essentially linear, giving a bond angle of similar to 172 degrees. The complexes showed irreversible cyclic voltammetric cathodic response near -0.1 V vs. SCE in H2O-0.1 M KCl. The binuclear units displayed antiferromagnetic interaction between two high-spin (S = 5/2) iron(III) centers giving a -J value of -110 cm(-1). The complexes showed good DNA binding propensity giving a binding constant value of similar to 10(5) M-1. Isothermal titration calorimetric data indicated single binding mode to the DNA. The binding was found to be driven by negative free energy change and enthalpy. The dpq complex 3 showed oxidative double-strand DNA cleavage on exposure to UV-A and visible light. The phen complex 2 displayed single-strand photocleavage of DNA. The DNA double-strand breaks were rationalized from theoretical molecular docking calculations. Mechanistic investigations showed formation of hydroxyl radicals as the reactive species through photodecarboxylation of the L-histidine ligand. The complexes exhibited good binding propensity to bovine serum albumin (BSA) protein in Tris-HCl/NaCl buffer medium. The dpq complex 3 showed UV-A light-induced site-specific oxidative BSA cleavage forming fragments of similar to 45 kDa and similar to 20 kDa molecular weights via SOH pathway.

Paranormal, superstitious, magical, and religious beliefs

A lack of conceptual clarity and multivariate studies has impeded research on paranormal, superstitious, and magical beliefs. In this series of studies a new conceptual framework of these beliefs was presented. A general belief in the paranormal was shown to lead to specific paranormal, superstitious, and magical beliefs. The beliefs were defined equally as category mistakes where the core attributes of psychological, physical, and biological phenomena are confused with each other. This definition was supported by an empirical examination: Paranormal believers confused more core knowledge than skeptics. A multivariate study revealed that the best predictors of paranormal beliefs were intuitive thinking and a humanistic world view, while low analytical thinking was a less important predictor. Another study showed that women s greater belief in the paranormal compared to men was partially explained by women s higher intuitive and lower analytical thinking. Additionally, it was shown that university students were originally more skeptical than vocational school students, but university studies did not increase skepticism. The finding that paranormal beliefs mainly arise from an intuitive system, instead of a malfunctioning analytical system, explains why the beliefs do not vanish with the increase of education, scientific knowledge, and rational thinking. Religious and paranormal beliefs share important qualities and generally, they were positively related. The most religious people, however, abandoned paranormal beliefs. Religious people and paranormal believers differed from the skeptics similarly by being more intuitive, having experienced more mystical phenomena, and having peers and parents with more positive attitudes toward the supernatural. Religious people had, however, higher conservation and benevolence values than paranormal believers. The new conceptual framework presented in this series of studies integrates research on paranormal, superstitious, magical, and religious beliefs. Hopefully it will enable researchers to develop more elaborated hypotheses and theoretical statements about paranormal beliefs in the future.

Intergenerational Transfer of Sabbath Observance : How is Religious Tradition Transferred to Children among Finnish Seventh-day Adventists?

This study examined religious home education in educational, psychological, and sociological context. Growing up within a religious denomination is a process of learning the rules, norms, opinions, and attitudes, which serve to make the individual an active member of the group. It is a process of transferring the cultural inheritance between generations. Sabbathkeeping can be regarded as a strong indicator of the Seventh-day Adventist value system, which is also why I have concentrated on this specific issue in my study. The purpose of the study was to find out, how the Sabbath is transferred from parents to children among Finnish Adventists. It was also examined how parents could make the day of rest positively exceptional for children, and how the parental authoritativeness affects the process of transference. According to Bull & Lockhart s (1989) theory, the amount of Adventist generations in family history influences the transfer of religious tradition. This study aimed to find out whether or not this theory would apply to the present-day Finland. The nature of religious development among Adventist young people was also one of the interests of the research. The methods used in the study were in-depth interviews (n = 10) and a survey (n = 106). The majority of the interviewees was young adults (age 15-30) grown up in Adventist families. The interviews were taped and transcribed for the study, and survey answers were analysed with SPSS-data analysis program. The amount of survey questionnaires evaluated was 106, whole population of 15-30 year-old Finnish Adventists being about one thousand. Democratic relationship between parents and children, parents' example, encouragement to own thinking, and positive experiences of Sabbath and the whole religion, including the social dimension of the Adventism, seem to be some of the most significant factors in transference of religious tradition. Both too severe and too permissive education were considered to lead to similar results: unsuccessful transfer of values, or even rebellion and adopting a totally opposite way of life than that of the parents. In this study the amount of Adventist generations in family history does not correlate significantly with the end results of value transference. Keywords: Sabbath, intergenerational, value transference, religious home education Avainsanat: sapatti, arvojen siirtyminen vanhemmilta lapsille, uskonnollinen kotikasvatus

Compulsory Voting, Encouraged Tweeting? Australian Elections and Social Media

This chapter examines patterns in social media activity around Australian elections, focusing primarily on the 2013 federal election and supplemented by extended research into social media and Australian politics between 2007 and 2015. The coverage of Australian elections on social media is analysed from three perspectives: the evolution of the use of online platforms during elections; politician and party social media strategies during the 2013 election, focusing on Twitter; and citizen engagement with elections as demonstrated through election day tweeting practices. The specific context of Australian politics, where voting is compulsory, and the popularity of social media platforms like Twitter makes this case notably different from other Western democracies. It also demonstrates the extended mediation of politics through social media, for politicians and citizens alike.

Religious Jew Ordered to East Transport Artworks

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New reagents 3: aluminium iodide - a highly regioselective ether-cleaving reagent with novel cleavage pattern

AlI3 is an easily accessible and versatile ether-cleaving reagent.

Enzymatic cleavage of carotenoids

1. 1.|Carotene 15,15′-dioxygenase (EC 1.13.11.21) has been isolated from the intestine of guinea pig and rabbit and purified 38- and 30-fold, respectively, but subjecting the intestinal homogenate to protamine sulfate treatment, (NH4)2SO4 fractionation and acetone precipitation. 2. 2.|The guinea pig enzyme showed a pH optimum at 8.5, an optimum substrate concentration of 200 nmoles of β,β-carotene per 25 ml of reaction mixture, an apparent Km with β,β-carotene as substrate of 9.5 · 10−6 M and a V 3.3 nmoles of retinal formation/mg protein per h. The reaction was linear upto 3 h and the reaction rate increased linearly with increase in enzyme protein concentration. The enzyme was activated by GSH and Fe2+ and inhibited by sodium dodecylsulfate, sulfhydryl binding and iron chelating agents. 3. 3.|The reaction catalysed by guinea pig enzyme was strictly stoichiometric. 4. 4.|Rabbit enzyme showed a close similarity with guinea pig enzyme with respect to time course, optimum substrate concentration, activation by Fe2+ and GSH, inhibition by sodium dodecylsulfate, iron chelating and sulfhydryl binding agents. However, it showed a slightly lower pH optimum (pH 7.8). 5. 5.|The enzyme from guinea pig and rabbit showed remarkable similarity with respect to cleavage of carotenoids. The enzyme from both the species was more specific for β,β-carotene but could also cleave a number of other carotenoids at the 15,15′-double bond. 6. 6.|10′-Apo-β-carotenal and 10′-apo-β-carotenol were readily cleaved compared with other apo-β-carotenals and apo-β-carotenols tested. 7. 7.|It has been conclusively shown for the first time that mono-ring substituted carotenoids are also cleaved at the 15,15′-double bond.

Effect of vitamin A deprivation on the cholesterol side-chain cleavage enzyme activity of testes and ovaries of rats (Short Communication)

The cholesterol side-chain cleavage enzyme activity is decreased considerably at the mild stage of vitamin A deficiency in rat testes and ovaries and the decrease in activity becomes more pronounced with progress of deficiency. Supplementation of the deficient rats with retinyl acetate, but not retinoic acid, restores the enzyme activity to normal values. The cholesterol side-chain cleavage enzyme of adrenals is not affected by any of the above treatments.

Enzymatic cleavage of carotenoids

1. 1.|Carotene 15,15′-dioxygenase (EC 1.13.11.21) has been isolated from the intestine of guinea pig and rabbit and purified 38- and 30-fold, respectively, but subjecting the intestinal homogenate to protamine sulfate treatment, (NH4)2SO4 fractionation and acetone precipitation. 2. 2.|The guinea pig enzyme showed a pH optimum at 8.5, an optimum substrate concentration of 200 nmoles of β,β-carotene per 25 ml of reaction mixture, an apparent Km with β,β-carotene as substrate of 9.5 · 10−6 M and a V 3.3 nmoles of retinal formation/mg protein per h. The reaction was linear upto 3 h and the reaction rate increased linearly with increase in enzyme protein concentration. The enzyme was activated by GSH and Fe2+ and inhibited by sodium dodecylsulfate, sulfhydryl binding and iron chelating agents. 3. 3.|The reaction catalysed by guinea pig enzyme was strictly stoichiometric. 4. 4.|Rabbit enzyme showed a close similarity with guinea pig enzyme with respect to time course, optimum substrate concentration, activation by Fe2+ and GSH, inhibition by sodium dodecylsulfate, iron chelating and sulfhydryl binding agents. However, it showed a slightly lower pH optimum (pH 7.8). 5. 5.|The enzyme from guinea pig and rabbit showed remarkable similarity with respect to cleavage of carotenoids. The enzyme from both the species was more specific for β,β-carotene but could also cleave a number of other carotenoids at the 15,15′-double bond. 6. 6.|10′-Apo-β-carotenal and 10′-apo-β-carotenol were readily cleaved compared with other apo-β-carotenals and apo-β-carotenols tested. 7. 7.|It has been conclusively shown for the first time that mono-ring substituted carotenoids are also cleaved at the 15,15′-double bond.

Characterization of Mycobacterium leprae RecA intein, a LAGLIDADG homing endonuclease, reveals a unique mode of DNA-binding, helical distortion and cleavage, compared to a canonical LAGLIDADG homing endonuclease

Mycobacterium leprae, which has undergone reductive evolution leaving behind a minimal set of essential genes, has retained intervening sequences in four of its genes implicating a vital role for them in the survival of the leprosy bacillus. A single in-frame intervening sequence has been found embedded within its recA gene. Comparison of M. leprae recA intervening sequence with the known intervening sequences indicated that it has the consensus amino acid sequence necessary for being a LAGLIDADG-type homing endonuclease. In light of massive gene decay and function loss in the leprosy bacillus, we sought to investigate whether its recA intervening sequence encodes a catalytically active homing endonuclease. Here we show that the purified M. leprae RecA intein (PI-MleI) binds to cognate DNA and displays endonuclease activity in the presence of alternative divalent cations, Mg2+ or Mn2+. A combination of approaches including four complementary footprinting assays such as DNase I, Cu/phenanthroline, methylation protection and KMnO4, enhancement of 2-aminopurine fluorescence and mapping of the cleavage site revealed that PI-MleI binds to cognate DNA flanking its insertion site, induces helical distortion at the cleavage site and generates two staggered double-strand breaks. Taken together, these results implicate that PI-MleI possess a modular structure with separate domains for DNA target recognition and cleavage, each with distinct sequence preferences. From a biological standpoint, it is tempting to speculate that our findings have implications for understanding the evolution of LAGLIDADG family of homing endonucleases

Sermons, discourses, and epistolary opinions on religious matters by Gershom Seixas

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