• Bulletin of the Korean Chemical Society
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• v.18 no.10
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• pp.1061-1066
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• 1997

The complexes M(CO)4-1,2-(PPh2)2-1,2-C2B10H10 (M=Cr 2a, Mo 2b, W 2c) have been prepared in good yields from readily available bis-diphenylphosphino-o-carboranyl ligand, closo-1,2-(PPh2)2-1,2-C2B10H10 (1), by direct reaction with Group Ⅵ metal carbonyls. The infrared spectra of the complexes indicate that there is an octahedral disposition of chelate bis-diphenylphosphino-o-carboranyl ligand around the metal atom. The crystal structure of 2a was determined by X-ray diffraction. Complex 2a crystallizes in the monoclinic space group P21/n with cell parameters a = 12.2360(7), b = 17.156(1), c = 16.2040(6) Å, V = 3354.1(3) Å3, and Z =4. Of the reflections measured a total of 2514 unique reflections with F2 > 3σ(F2) was used during subsequent structure refinement. Refinement converged to R1 = 0.066 and R2 = 0.071. Structural studies showed that the chromium atom had a slightly distorted pseudo-octahedral configuration about the metal center with two phosphine groups of o-carborane occupying the equatorial plane cis-orientation to each other. These metal carbonyl complexes are rapidly converted to the corresponding metal carbene complexes, [(CO)3M=C(OCH3)(CH3)]-1,2-(PPh2)2-1,2-C2B10H10 (M= Cr 3a, Mo 3b, W 3c), via alkylation with methyllithium followed by O-methylation with CF3SO3CH3.

• Korean Journal of Soil Science and Fertilizer
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• v.36 no.6
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• pp.376-383
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• 2003

To utilize composts more efficiently, combining composts with fertilizer to meet crop requirements is an appealing alternative. A pot experiment was conducted to study the effect of application rate of composted pig manure blended with fertilizer on the availability and loss of fertilizer-N. Chinese cabbage (Brassica campestris L. cv. Samjin) plants were cultivated for 30 and 60 days. 15N-Labeled urea ($5.24\;^{15}N\;atom\;%$) was added to soil at $450mg\;N\;kg^{-1}$, and unlabeled compost ($0.37\;^{15}N\;atom\;%$) was added at 0, 200, 400, and $600mg\;N\;kg^{-1}$. The amount of plant-N derived from urea was not affected by compost application at rate of $200mg\;N\;kg^{-1}$. However, compost application at 400 and $600mg\;N\;kg^{-1}$ significantly (P<0.05) increased plant assimilation of N from urea irrespective of sampling time, probably because of physicochemical changes in the soil properties allowing urea-N to be assimilated more efficiently. The amount of immobilized urea-N increased with increasing rate of compost application at both growth periods, as the results of increased microbial activities using organic C in the compost. Total recovery of urea-N (as percentage of added N) by Chinese cabbage and soil also increased with increasing rate of compost from 71.5 to 95.6% and from 67.0 to 88.2% at the 30- and 60-days of growth, respectively. These results suggest that increasing rate of compost blending increases plant uptake of fertilizer-N and enhances immobilization of fertilizer-N, which leads to decrease in loss of fertilizer-N. However, information about the fate of immobilized N during future crop cultivation is necessary to verify long-term effect of compost blending.

• Applied Biological Chemistry
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• v.43 no.2
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• pp.95-99
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• 2000

A series of hetero ring (X) substitued chalcone derivatives with farnesyl protein transferase (FPTase) inhibition activities $(pI_{50})$ values determined in vitro is analyzed by modified Free-Wilson (F-W) and Hansch method for quantitative structure activity relationship (QSARs). On the basis of F-W analysis on the FPTase inhibitory activity of a training set of the compounds, none of the (X)-substituents were not contribute the activity. But the net charge of ${\alpha}$ carbon atom is contribute the activity than that of ${\beta}$ carbon atom. And the relative orders of the (Y)-substituents on the activity are ortho>meta>para-substituents. According to Hansch approach, the activities would depend largely on the optimal, $(R_{opt.}=-0.35)$ resonance effect with ortho substituted $(I_o>0)$ electron donating group (R<0) and STERIMOL parameter, $B_1$ constant. The inhibition activity between hetro ring substituents have been a proportioned with each others and none substituent(H), 45 showed the highest FPTase inhibition $(pI_{50}=4.30)$ activity.

• Journal of the Korean Chemical Society
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• v.37 no.1
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• pp.105-111
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• 1993

The stability constants for lanthanides complexes with optically active L-proline (1 : 1) were determined in aqueous solution in the ionic medium of 0.1 M $NaClO_4$ at 25$^{\circ}C$ using a pH titration method. The results show called "gadolinium break" between lighter and heavier lanthanides. The linear relation between the stability constant (log$\beta$1) and the pKa values of ligands indicates that L-proline acts as a bidentate ligand in the complexation. The thermodynamic parameters (${\Delta}H$ and ${\Delta}S$) were also determined using an enthalpy titration method at the same condition. The positive endothermic enthalpy change and positive entropy change clearly indicate that the driving force for the complexation is an entropy effect. The comparison of the thermodynamic parameters of L-proline complexes with anthranilate complexes supports the conclusion that the heterocyclic nitrogen atom and carboxylate of L-proline are involved in the chleate formation. The enthalpy values for L-proline are more positive than the ones for anthranilate complex. The difference in enthalpy change for the complex formation between L-proline complex and anthranilate complex is explained in terms of the basicity of the nitrogen donor atom in the ligand. The relatively large entropy change may be described by the extra dehydration related to the rigidity of L-proline ring.

• Journal of the Korean Chemical Society
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• v.31 no.4
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• pp.352-358
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• 1987

Rate constants for the hydrolysis of para-substituted phenyl N-(p-chlorobenzoyl)chloroformimidate (I) derivatives in 1 : 4 dioxane-water at $25^{\circ}C$ have been determined. Rate data, substituent effect $(\rho\>{\rho}^+)$, product analysis and MO calculation indicate that the uncatalyzed reaction proceeds through an $S_N1$ mechanism involving the formation of azocarbonium ion (II) below pH 3.0, and the base-catalyzed reaction proceeds through an $S_N2$ mechanism via transition state (III) above pH 4.0. The relative stability of four peri planar conformational isomers were (E-ap) > (Z-ap) > (E-sp) > (Z-ap), respectively, and the most stable stereo structures shows that the Y-substituted phenyl group $(C_6H_4-Y)$ occupy vertical $(90^{\circ})$ position on the plane of the benzimidochloroformyl group in (E-ap) conformer. The nucleophilic substitution of water molecule occurs by sigma attack to the activatived azomethine carbon atom of (I) derivatives.

• Carbon letters
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• v.16 no.3
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• pp.192-197
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• 2015

In the present work, we propose a molecule (C₁₄H₁₄) that can be used as a building block of hexagonal diamond-type crystals and nanocrystals, including wurtzite structures. This molecule and its combined blocks are similar to diamondoid molecules that are used as building blocks of cubic diamond crystals and nanocrystals. The hexagonal part of this molecule is included in the C₁₂ central part of this molecule. This part can be repeated to increase the ratio of hexagonal to cubic diamond and other structures. The calculated energy gap of these molecules (called hereafter wurtzoids) shows the expected trend of gaps that are less than that of cubic diamondoid structures. The calculated binding energy per atom shows that wurtzoids are tighter structures than diamondoids. Distribution of angles and bonds manifest the main differences between hexagonal and cubic diamond-type structures. Charge transfer, infrared, nuclear magnetic resonance and ultraviolet-visible spectra are investigated to identify the main spectroscopic differences between hexagonal and cubic structures at the molecular and nanoscale. Natural bond orbital population analysis shows that the bonding of the present wurtzoids and diamondoids differs from ideal sp³ bonding. The bonding for carbon valence orbitals is in the range (2s^0.982p^3.213p^0.02)-(2s^0.942p^3.313p^0.02) for wurtzoid and (2s^0.932p^3.293p^0.01)-(2s^0.992p^3.443p^0.01) for diamantane.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.32 no.5
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• pp.199-204
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• 2022

A new three-dimensional Gd-MOF, [Gd(p-XBP4)₄(H₂O)]·W(CN)₈; (1; p-XBP4 = N,N'-p-phenylenedimethylenbis (pyridin-4-one)) has been synthesized by slow-evaporation and its crystal structure was characterized by single-crystal X-ray diffraction (SCXRD) analysis. For each Gd^III ion, there are seven coordination sites, which are occupied by six oxygen atoms of six p-XBP4 ligands and one oxygen atom from the water molecule. The [W(CN)₈]^3- anion exists for charge balance with cationic framework. The Gd^II ions are interconnected by the p-XBP4 ligand to form the three-dimensional structure. Considering the magnetic property of lanthanide ions, magnetic studies of Gd-MOF were investigated by direct-current (DC) magnetic susceptibilities measurements.

• Journal of the Korean institute of surface engineering
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• v.34 no.5
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• pp.414-420
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• 2001

A 30-kV plasma immersion ion implantation setup (P $I^3$) has been equipped with a self-developed 6'-magnetron to perform hard coatings with enhanced adhesion by P $I^3$D(P $I^3$ assisted deposition) process. Using ICP source with immersed Ti antenna and reactive magnetron sputtering of Ti target in $N_2$/Ar ambient gas mixture, the TiN films were prepared on Si substrates at different pulse bias and ion-to-atom arrival ratio ( $J_{i}$ $J_{Me}$ ). Prior to TiN film formation the nitrogen implantation was performed followed by deposition of Ti buffer layer under A $r^{+}$ irradiation. Films grown at $J_{i}$ $J_{Me}$ =0.003 and $V_{pulse}$=-20kV showed columnar grain morphology and (200) preferred orientation while those prepared at $J_{i}$ $J_{Me}$ =0.08 and $V_{pulse}$=-5 kV had dense and eqiaxed structure with (111) and (220) main peaks. X-ray diffraction patterns revealed some amount of $Ti_{x}$ $N_{y}$ in the films. The maximum microhardness of $H_{v}$ =35 GN/ $M^2$ was at the pulse bias of -5 kV. The P $I^3$D technique was applied to enhance wear properties of commercial tools of HSS (SKH51) and WC-Co alloy (P30). The specimens were 25-kV PII nitrogen implanted to the dose 4.10$^{17}$ c $m^{-2}$ and then coated with 4-$\mu\textrm{m}$ TiN film on $Ti_{x}$ $N_{y}$ buffer layer. Wear resistance was compared by measuring weight loss under sliding test (6-mm $Al_2$ $O_3$ counter ball, 500-gf applied load). After 30000 cycles at 500 rpm the untreated P30 specimen lost 3.10$^{-4}$ g, and HSS specimens lost 9.10$^{-4}$ g after 40000 cycles while quite zero losses were demonstrated by TiN coated specimens.s.

• Journal of Photoscience
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• v.9 no.2
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• pp.362-363
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• 2002

Since chlorophyll a and bacteriochlorophyll a are asymmetric molecules, an external ligand can coordinate to the central Mg atom either from the chiorin macrocycle side where the C13$^2$-methoxycarbonyl moiety protrudes (denoting as the 'back' side) or frome the other side (the 'face' side). We investigated which side of the macrocycle is favored for the ligand coordination, by survey of the highly resolved crystal structures of various photosynthetic proteins and theoretical model calculations. It is found that chlorophyll a as well as bacteriochlorophyll a and b in the photosynthetic proteins mostly bind their ligands on the 'back' sides. This finding was confirmed by the theoretical calculations for methyl chlorophyllide a and methyl bacteriochlorophyllide a as models: the 'back' type ligand-(bacterio )chlorophyll complex was more stable than the 'face' type one. The calculations predicted influence of the Cl3$^2$-stereochemistry on the choice of the side of the ligand coordination, which is discussed in relation to the presence of the Cl3$^2$-epimer of chlorophyll a in photosystem I reaction center [I].

• Journal of Korea Foundry Society
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• v.21 no.5
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• pp.286-289
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• 2001

The glass formation behavior was investigated in the melt spun Zr-Ti-Cu-Ni-X (X=B, P and Si) ribbons. The magnitude of supercooled liquid region of Zr-Ti-Cu-Ni alloy increased with an addition of alloying element. The glass transition temperature and the crystallization temperature increased and the magnitude of supercooled liquid region decreased with increasing the content of alloying elements. The largest supercooled liquid region was observed in the Si containing alloy. This is believed to be due to the dense atom packing with the optimum atomic size ratio of constituent elements.