• Title/Summary/Keyword: T-bond

Search Result 469, Processing Time 0.032 seconds

The Crystal Structure of Bis(1,2-diaminopropane)palladium(Ⅱ) Bis(oxalato)palladate(Ⅱ) (Bis(1,2-diaminopropane)palladium(Ⅱ) Bis(oxalato)palladate(Ⅱ)의 결정구조)

  • Kim Sei Hwan;NagGung Hae;Jeon, Ho Jung
    • Journal of the Korean Chemical Society
    • /
    • v.37 no.6
    • /
    • pp.599-603
    • /
    • 1993
  • Crystal structure of bis(1,2-diaminopropane)palladium(II) bis(oxalato)palladate(II) has been determined by X-ray crystallography. Crystal data: $Pd_2C_{10}H_{10}N_{4}O_{8}$, $M_W$ = 573.09, orthorhombic, space group $P_{ccn}$ (No = 56), a = 16.178(5), b = 16.381(6), c = 6.685(2)$\{AA}$, V = 1771.6 $\{AA}^3$, $M_W$W = 573.09, $D_c$ = 2.014 g${\cdot}c\;m^{-3}$, Z = 4, T = 294K, F(000) = 1056.0 and $\mu$ = 20.466 c$m^{-1}$. The intensity data were collected with $Mo-K\alpha$ radiation (${\lambda}$ = 0.7107 $\AA)$ on an automatic four-circle diffractometer with a graphite monochromater. The structure was solved by Patterson method and refined by full matrix least-squares methods using Pivot weights. The final R and S values were R = 0.065, $R_W = 0.059, R_{all}$ = 0.065 and S = 4.315 for 605 observed reflections. Both cation and anion complexes are essentially planar and have dihedral angle of $18(l)^{\circ}$ between thier planes. In the crystal structure, they do not have the Magnus's salt type mixed stacks; instead, the complex anions form regular stacks along the c-axis with the M-M bond length of $3.343(5)\AA$ and their stacks are surrounded by the complex cations through hydrogen bonds with the nitrogen-oxygen distances of 2.94(3) and $3.31(4)\AA.$

  • PDF

Evaluation of effect of galvanic corrosion between nickel-chromium metal and titanium on ion release and cell toxicity

  • Lee, Jung-Jin;Song, Kwang-Yeob;Ahn, Seung-Geun;Choi, Jung-Yun;Seo, Jae-Min;Park, Ju-Mi
    • The Journal of Advanced Prosthodontics
    • /
    • v.7 no.2
    • /
    • pp.172-177
    • /
    • 2015
  • PURPOSE. The purpose of this study was to evaluate cell toxicity due to ion release caused by galvanic corrosion as a result of contact between base metal and titanium. MATERIALS AND METHODS. It was hypothesized that Nickel (Ni)-Chromium (Cr) alloys with different compositions possess different corrosion resistances when contacted with titanium abutment, and therefore in this study, specimens ($10{\times}10{\times}1.5mm$) were fabricated using commercial pure titanium and 3 different types of Ni-Cr alloys (T3, Tilite, Bella bond plus) commonly used for metal ceramic restorations. The specimens were divided into 6 groups according to the composition of Ni-Cr alloy and contact with titanium. The experimental groups were in direct contact with titanium and the control groups were not. After the samples were immersed in the culture medium - Dulbecco's modified Eagle's medium[DMEM] for 48 hours, the released metal ions were detected using inductively coupled plasma mass spectrometer (ICP-MS) and analyzed by the Kruskal-Wallis and Mann-Whitney test (P<.05). Mouse L-929 fibroblast cells were used for cell toxicity evaluation. The cell toxicity of specimens was measured by the 3-{4,5-dimethylthiazol-2yl}-2,5-diphenyltetrazolium bromide (MTT) test. Results of MTT assay were statistically analyzed by the two-way ANOVA test (P<.05). Post-hoc multiple comparisons were conducted using Tukey's tests. RESULTS. The amount of metal ions released by galvanic corrosion due to contact between the base metal alloy and titanium was increased in all of the specimens. In the cytotoxicity test, the two-way ANOVA showed a significant effect of the alloy type and galvanic corrosion for cytotoxicity (P<.001). The relative cell growth rate (RGR) was decreased further on the groups in contact with titanium (P<.05). CONCLUSION. The release of metal ions was increased by galvanic corrosion due to contact between base metal and titanium, and it can cause adverse effects on the tissue around the implant by inducing cytotoxicity.

Determination of Free 4-hydroxyproline with Dansylchloride by HPLC in Human Urine (소변 중 4-hydroxyproline 분석에 관한 연구)

  • Lee, Keou-Weon;Cho, Young-Bong;Lee, Kyung-Jong
    • Journal of Preventive Medicine and Public Health
    • /
    • v.35 no.4
    • /
    • pp.282-286
    • /
    • 2002
  • Objectives : The level of 4-hydroxyproline (4-Hyp) in human urine was measured using high performance liquid chromatography (HPLC) with a fluorescence detector. This method is useful for medical examinations and investigating the radicals induced by physical, chemical, mental stresses. This method is superior to many published several methods in terms of its low cost and ability to analyze many samples. Methods : The urine from workers in a tire manufacturing company (22 male pre- and post-shift workers) and 18 office-workers as controls were analyzed. Data concerning age, the cumulative drinking amount and the cumulative smoking amount was collected with a questionnaire. The optimum applied amount of dansyl-Cl, the optimum reaction temperature and time, the recoveries and the optimum pH of the eluent and buffer were determined.4-Hyp from human urine was derivatized with dansyl-Cl (dimethylamino-naphthalene-1-sulfonyl chloride) after removing the a-amino acid by a treatment with phthalic dicarboxaldehyde (OPA) and cleaned with Bond Elut C18 column. The 4-Hyp derivatives were separated on a reversed phase column by gradient elution with a phosphate buffer (5 mmol, pH 8.0) and acetonitrile, and detected by fluorescence measurements at 340 nm (excitation) and 538 nm (emission). Results : The detection limit for the urinary free 4-Hyp was $0.364{\mu}mol/l$. The recovery rate of 4-Hyp was 99.7%, and the effective pH of the phosphate buffer and borate buffer were 3.0 and 8.0, respectively. From statistical analysis, age, drinking and smoking did not affect the urinary free 4-Hyp in both the controls and workers. The range of urinary 4-Hyp in the controls, pre-shift, and post-shift workers were 0.33-16.44, N.D-49.06, and $0.32-56.27{\mu}mol/l$. From the pared-sample t-test, the urinary 4-Hyp levels in post-shift workers ($11.82{\pm}6.73\;nmmol/mg\;Cre$) were 2-fold higher than in pre-shift workers ($5.36{\pm}5.53\;nmol;/mg\;Cre$) and controls ($4.91{\pm}4.89\;nmol;/mg\;Cre$). Conclusions : This method was developed with high sensitivity, accuracy, and precision. The present method was effectively applied to analyze the urinary free 4-Hyp in both controls and workers.

Study on Synthesis of 68GeO2 and Behavior of 68Ga3+ for Generator Column (Generator 컬럼용 68GeO2 합성 및 68Ga3+의 거동에 관한 연구)

  • Kim, Gun Gyun;Lee, Jun Young;Kim, Sang Wook;Hur, Min Gu;Yang, Seung Dae;Park, Jeong Hoon
    • Journal of Radiation Industry
    • /
    • v.10 no.4
    • /
    • pp.189-192
    • /
    • 2016
  • $^{68}Ga$ has emerged as a promising candidate for non-invasive diagnostic imaging within Positron Emission Tomography (PET) because of its advantageous radiochemical characteristics ($t_{1/2}=68min$, ${\beta}^+$ yield ~89%). $^{68}Ga$ forms a stable chelation with various ligands and it is possible to be quickly and easily study using a $^{68}Ge/^{68}Ga$ generator. Commercial $^{68}Ge/^{68}Ga$ generators are chromatographic system using the inorganic materials such as alumina and tin dioxide which are employed as column matrixes for $^{68}Ge$. In this study, we tried out to make $^{68}Ge/^{68}Ga$ generator system with the $^{68}GeO_2$ microstructures for column matrix. $^{68}Ge$ tends to have stable bond with oxide as $^{68}GeO_2$ microstructures. The $^{68}GeO_2$ has been synthesized by hydrolysis of $GeCl_4$ (sol-gel method) and characterized by X-ray diffraction and scanning electron microscope for geometrical analysis. The stability of $GeO_2$ was tested using eluents with diverse solvents(water, ethanol and 0.1 N HCl). The radioactivity of $^{68}Ga^{3+}$ in eluate through $GeO_2$ was measured to prove a function as column material for a generator.

qEEG Measures of Attentional and Memory Network Functions in Medical Students: Novel Targets for Pharmacopuncture to Improve Cognition and Academic Performance

  • Gorantla, Vasavi R.;Bond, Vernon Jr.;Dorsey, James;Tedesco, Sarah;Kaur, Tanisha;Simpson, Matthew;Pemminati, Sudhakar;Millis, Richard M.
    • Journal of Pharmacopuncture
    • /
    • v.22 no.3
    • /
    • pp.166-170
    • /
    • 2019
  • Objectives: Attentional and memory functions are important aspects of neural plasticity that, theoretically, should be amenable to pharmacopuncture treatments. A previous study from our laboratory suggested that quantitative electroencephalographic (qEEG) measurements of theta/beta ratio (TBR), an index of attentional control, may be indicative of academic performance in a first-semester medical school course. The present study expands our prior report by extracting and analyzing data on frontal theta and beta asymmetries. We test the hypothesis that the amount of frontal theta and beta asymmetries (fTA, fBA), are correlated with TBR and academic performance, thereby providing novel targets for pharmacopuncture treatments to improve cognitive performance. Methods: Ten healthy male volunteers were subjected to 5-10 min of qEEG measurements under eyes-closed conditions. The qEEG measurements were performed 3 days before each of first two block examinations in anatomy-physiology, separated by five weeks. Amplitudes of the theta and beta waveforms, expressed in ${\mu}V$, were used to compute TBR, fTA and fBA. Significance of changes in theta and beta EEG wave amplitude was assessed by ANOVA with post-hoc t-testing. Correlations between TBR, fTA, fBA and the raw examination scores were evaluated by Pearson's product-moment coefficients and linear regression analysis. Results: fTA and fBA were found to be negatively correlated with TBR (P<0.03, P<0.05, respectively) and were positively correlated with the second examination score (P<0.03, P=0.1, respectively). Conclusion: Smaller fTA and fBA were associated with lower academic performance in the second of two first-semester medical school anatomy-physiology block examination. Future studies should determine whether these qEEG metrics are useful for monitoring changes associated with the brain's cognitive adaptations to academic challenges, for predicting academic performance and for targeting phamacopuncture treatments to improve cognitive performance.

Relationship between maximum bite force and facial skeletal pattern (최대 교합력과 안면 골격 형태에 관한 연구)

  • Choi, Won-Cheul;Kim, Tae-Woo
    • The korean journal of orthodontics
    • /
    • v.33 no.6 s.101
    • /
    • pp.437-451
    • /
    • 2003
  • The purpose of this study was to measure maximum bite force and to investigate its relationship with anteroposterior, vertical, and transverse facial skeletal measurements. From among the dental students at the College of Dentistry, forty subjects (26 male and 14 female) were selected. With two sets of strain gauge, maximum bite force at the right and left first molars and anterior teeth was measured in the morning and afternoon. After taking lateral and posteroanterior cephalograms, fifty and nineteen variables were evaluated, respectively Paired t-tests and an independent t-test were done and correlation coefficients were obtained. 1. The maximum bite force at the first molars was $68.0\pm13.9kg$. in males and $55.6\pm10.5kg$ in females (p<0.05) while the force at the anterior teeth was $8.4\pm4.9kg\;and\;1.1\pm3.4kg$ respectively (p<0.05). 2. Some tendency for a greater value of maximum bite force at the preferred side was observed but not statistically significant (p>0.05). 3. Significant difference was observed between the strong bite force group and the weak bite force group in some cephalometric and other measurements (p<0.05). N-S-Ar, S-Ar-Go, FH-Hl, IMPA and MMO showed a significant difference in posterior maximum bite force (P). N-S-Ar and FH-H1 also showed a significant difference in anterior maximum bite force (A). 4. Several cephalometric variables showed some correlation with maximum bite force (p<0.05). N-S-Ar, S-Ar-Go, UGA, FH-H6, FH-H1, body weight and MMO were significantly correlated with posterior maximum bite force (P). Go-Me, P-1 and IMPA were significantly correlated with anterior maximum bite force (A).

Further Studies on the Specificity of the N- and C-terminal Antigenic Determinant of Hen Egg-white Lysozyme (계난백(鷄卵白) Lysozyme의 N-말단(末端)과 C-말단(末端) 항원결정기(抗原決定基)에 대한 연구(硏究))

  • Ha, Youn-Mun
    • The Journal of the Korean Society for Microbiology
    • /
    • v.12 no.1
    • /
    • pp.19-32
    • /
    • 1977
  • The specificity of the N- and C-terminal antigenic determinant($P_{17}$: sequence $Lys^1-{cys-}^6-Asn^{27},\;{Trp^{12}}_2-Cys^{127}-Leu^{129}$) of hen egg-white lysozyme(HL) was studied in more detail. In a Scatchard plot of the binding of $^{14}C$-acetyl HL with guinea pig purified anti-$P_{17}$ antibody experimental values bent sharply aear r=1. This suggests of two antibody populations with different affinities for HL or possible steric hindrance in the binding of a second HL molecule to the second binding site of the antibody molecule. The antigenic activities of various peptides were tested by measuring their inhibition of the binding of $^{14}C-acetyl-P_{17}$ with the antibody, Only $P_{17}$ and $P_{17}t$(sequence $Lys^1-cys^6-Homoser^{12},\;Trp^{123}-Cys^{127}-Leu^{128})$) were inhibitory, with $K_1$ values of $2.0{\times}10^4$ and $8.1{\times}10^3$, respectively. These results indicate that the direct binding site of $P_{17}$ to anti-$P_{17}$ antibody may be located in the terminal portion of $P_{17}$ (sequence $Lys^1-Cys^6-Homoser^{12},\;Trp^{123}-Cys^{127}-Leu^{129})$) while the rest of $P_{17}$ may be important in maintaining the conformation of this determinant. The single disulphide bond involved in this determinant is essential for manifestation of immunological activity.

  • PDF

The Role of DNA Binding Domain in hHSF1 through Redox State (산화환원에 따른 hHSF1의 DNA binding domain의 역할)

  • Kim, Sol;Hwang, Yun-Jeong;Kim, Hee-Eun;Lu, Ming;Kim, An-D-Re;Moon, Ji-Young;Kang, Ho-Sung;Park, Jang-Su
    • Journal of Life Science
    • /
    • v.16 no.6
    • /
    • pp.1052-1059
    • /
    • 2006
  • The heat shock response is induced by environmental stress, pathophysiological state and non-stress conditions and wide spread from bacteria to human. Although translations of most proteins are stopped under a heat shock response, heat shock proteins (HSPs) are produced to protect cell from stress. When heat shock response is induced, conformation of HSF1 was changed from monomer to trimer and HSF1 specifically binds to DNA, which was called a heat shock element(HSE) within the promoter of the heat shock genes. Human HSF1(hHSFl) contains five cysteine(Cys) residues. A thiol group(R-SH) of Cys is a strong nucleophile, the most readily oxidized and nitrosylated in amino acid chain. This consideration suggests that Cys residues may regulate the change of conformation and the activity of hHSF1 through a redox-dependent thiol/disulfide exchange reaction. We want to construct role of five Cys residues of hHSF by redox reagents. According to two studies, Cys residues are related to trimer formation of hHSF1. In this study, we want to demonstrate the correlation between structural change and DNA-binding activity of HSF1 through forming disulfide bond and trimerization. In this results, we could deduce that DNA binding activity of DNA binding domain wasn't affected by redox for always expose outside to easily bind to DNA. DNA binding activity of wild-type HSF's DNA binding domain was affected by conformational change, as conformational structure change (trimerization) caused DNA binding domain.

Sesquiterpenoids Bioconversion Analysis by Wood Rot Fungi

  • Lee, Su-Yeon;Ryu, Sun-Hwa;Choi, In-Gyu;Kim, Myungkil
    • 한국균학회소식:학술대회논문집
    • /
    • 2016.05a
    • /
    • pp.19-20
    • /
    • 2016
  • Sesquiterpenoids are defined as $C_{15}$ compounds derived from farnesyl pyrophosphate (FPP), and their complex structures are found in the tissue of many diverse plants (Degenhardt et al. 2009). FPP's long chain length and additional double bond enables its conversion to a huge range of mono-, di-, and tri-cyclic structures. A number of cyclic sesquiterpenes with alcohol, aldehyde, and ketone derivatives have key biological and medicinal properties (Fraga 1999). Fungi, such as the wood-rotting Polyporus brumalis, are excellent sources of pharmaceutically interesting natural products such as sesquiterpenoids. In this study, we investigated the biosynthesis of P. brumalis sesquiterpenoids on modified medium. Fungal suspensions of 11 white rot species were inoculated in modified medium containing $C_6H_{12}O_6$, $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ for 20 days. Cultivation was stopped by solvent extraction via separation of the mycelium. The metabolites were identified as follows: propionic acid (1), mevalonic acid lactone (2), ${\beta}$-eudesmane (3), and ${\beta}$-eudesmol (4), respectively (Figure 1). The main peaks of ${\beta}$-eudesmane and ${\beta}$-eudesmol, which were indicative of sesquiterpene structures, were consistently detected for 5, 7, 12, and 15 days These results demonstrated the existence of terpene metabolism in the mycelium of P. brumalis. Polyporus spp. are known to generate flavor components such as methyl 2,4-dihydroxy-3,6-dimethyl benzoate; 2-hydroxy-4-methoxy-6-methyl benzoic acid; 3-hydroxy-5-methyl phenol; and 3-methoxy-2,5-dimethyl phenol in submerged cultures (Hoffmann and Esser 1978). Drimanes of sesquiterpenes were reported as metabolites from P. arcularius and shown to exhibit antimicrobial activity against Gram-positive bacteria such as Staphylococcus aureus (Fleck et al. 1996). The main metabolites of P. brumalis, ${\beta}$-Eudesmol and ${\beta}$-eudesmane, were categorized as eudesmane-type sesquiterpene structures. The eudesmane skeleton could be biosynthesized from FPP-derived IPP, and approximately 1,000 structures have been identified in plants as essential oils. The biosynthesis of eudesmol from P. brumalis may thus be an important tool for the production of useful natural compounds as presumed from its identified potent bioactivity in plants. Essential oils comprising eudesmane-type sesquiterpenoids have been previously and extensively researched (Wu et al. 2006). ${\beta}$-Eudesmol is a well-known and important eudesmane alcohol with an anticholinergic effect in the vascular endothelium (Tsuneki et al. 2005). Additionally, recent studies demonstrated that ${\beta}$-eudesmol acts as a channel blocker for nicotinic acetylcholine receptors at the neuromuscular junction, and it can inhibit angiogenesis in vitro and in vivo by blocking the mitogen-activated protein kinase (MAPK) signaling pathway (Seo et al. 2011). Variation of nutrients was conducted to determine an optimum condition for the biosynthesis of sesquiterpenes by P. brumalis. Genes encoding terpene synthases, which are crucial to the terpene synthesis pathway, generally respond to environmental factors such as pH, temperature, and available nutrients (Hoffmeister and Keller 2007, Yu and Keller 2005). Calvo et al. described the effect of major nutrients, carbon and nitrogen, on the synthesis of secondary metabolites (Calvo et al. 2002). P. brumalis did not prefer to synthesize sesquiterpenes under all growth conditions. Results of differences in metabolites observed in P. brumalis grown in PDB and modified medium highlighted the potential effect inorganic sources such as $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ on sesquiterpene synthesis. ${\beta}$-eudesmol was apparent during cultivation except for when P. brumalis was grown on $MgSO_4$-free medium. These results demonstrated that $MgSO_4$ can specifically control the biosynthesis of ${\beta}$-eudesmol. Magnesium has been reported as a cofactor that binds to sesquiterpene synthase (Agger et al. 2008). Specifically, the $Mg^{2+}$ ions bind to two conserved metal-binding motifs. These metal ions complex to the substrate pyrophosphate, thereby promoting the ionization of the leaving groups of FPP and resulting in the generation of a highly reactive allylic cation. Effect of magnesium source on the sesquiterpene biosynthesis was also identified via analysis of the concentration of total carbohydrates. Our current study offered further insight that fungal sesquiterpene biosynthesis can be controlled by nutrients. To profile the metabolites of P. brumalis, the cultures were extracted based on the growth curve. Despite metabolites produced during mycelia growth, there was difficulty in detecting significant changes in metabolite production, especially those at low concentrations. These compounds may be of interest in understanding their synthetic mechanisms in P. brumalis. The synthesis of terpene compounds began during the growth phase at day 9. Sesquiterpene synthesis occurred after growth was complete. At day 9, drimenol, farnesol, and mevalonic lactone (or mevalonic acid lactone) were identified. Mevalonic acid lactone is the precursor of the mevalonic pathway, and particularly, it is a precursor for a number of biologically important lipids, including cholesterol hormones (Buckley et al. 2002). Farnesol is the precursor of sesquiterpenoids. Drimenol compounds, bi-cyclic-sesquiterpene alcohols, can be synthesized from trans-trans farnesol via cyclization and rearrangement (Polovinka et al. 1994). They have also been identified in the basidiomycota Lentinus lepideus as secondary metabolites. After 12 days in the growth phase, ${\beta}$-elemene caryophyllene, ${\delta}$-cadiene, and eudesmane were detected with ${\beta}$-eudesmol. The data showed the synthesis of sesquiterpene hydrocarbons with bi-cyclic structures. These compounds can be synthesized from FPP by cyclization. Cyclic terpenoids are synthesized through the formation of a carbon skeleton from linear precursors by terpene cyclase, which is followed by chemical modification by oxidation, reduction, methylation, etc. Sesquiterpene cyclase is a key branch-point enzyme that catalyzes the complex intermolecular cyclization of the linear prenyl diphosphate into cyclic hydrocarbons (Toyomasu et al. 2007). After 20 days in stationary phase, the oxygenated structures eudesmol, elemol, and caryophyllene oxide were detected. Thus, after growth, sesquiterpenes were identified. Per these results, we showed that terpene metabolism in wood-rotting fungi occurs in the stationary phase. We also showed that such metabolism can be controlled by magnesium supplementation in the growth medium. In conclusion, we identified P. brumalis as a wood-rotting fungus that can produce sesquiterpenes. To mechanistically understand eudesmane-type sesquiterpene biosynthesis in P. brumalis, further research into the genes regulating the dynamics of such biosynthesis is warranted.

  • PDF