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Kinetics and Mechanism of the Anilinolysis of 1,2-Phenylene Phosphorochloridate in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.9
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    • pp.3355-3360
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    • 2011
  • The nucleophilic substitution reactions of 1,2-phenylene phosphorochloridate (1) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $-15.0^{\circ}C$. The studied substrate of 1,2-phenylene phosphorochloridate is cyclic five-membered ring of phosphorus ester, and the anilinolysis rate of 1 is much faster than its acyclic analogue (4: ethyl phenyl chlorophosphate) because of extremely small magnitude of the entropy of activation of 1 compared to 4. The Hammett and Bronsted plots exhibit biphasic concave upwards for substituent X variations in the nucleophiles with a break point at X = 3-Me. The values of deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) change from secondary inverse ($k_H/k_D$ < 1) with the strongly basic anilines to primary normal ($k_H/k_D$ > 1) with the weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the transition state (TS) variation from a predominant backside attack to a predominant frontside attack, in which the reaction mechanism is a concerted $S_N2$ pathway. The primary normal DKIEs are substantiated by a hydrogen bonded, four-center-type TS.

Kinetics and Mechanism of the Pyridinolysis of S-Aryl Phenyl Phosphonochloridothioates in Acetonitrile

  • Adhikary, Keshab Kumar;Lumbiny, Bilkis Jahan;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.10
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    • pp.3743-3747
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    • 2011
  • Kinetic studies on the reactions of Y-S-aryl phenyl phosphonochloridothioates with X-pyridines have been carried out in MeCN at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles are biphasic concave upwards with a break point at X = H. The Hammett plots for substituent Y variations in the substrates are biphasic concave upwards with a break point at Y = H, and the sign of ${\rho}_Y$ is changed from unusual negative (${\rho}_Y$ < 0) with the weaker electrophiles to positive (${\rho}_Y$ > 0) with the stronger electrophiles. The stepwise mechanism is proposed on the basis of the ${\rho}_X$, ${\beta}_X$, and ${\rho}_{XY}$ values as follows: a ratelimiting leaving group departure from the intermediate involving a frontside attack and product-like TS for the stronger nucleophiles and weaker electrophiles; a rate-limiting leaving group departure from the intermediate involving a backside attack and product-like TS for the weaker nucleophiles and electrophiles; a rate-limiting bond formation involving a frontside attack for the stronger nucleophiles and electrophiles; a rate-limiting bond formation involving a backside attack for the weaker nucleophiles and stronger electrophiles. The substituent effects of X and Y on the pyridinolysis mechanisms of $R_1R_2P$(=S)Cl-type substrates are discussed.

Comparative analysis of the acoustic characteristics of different types of cymbal transducers (심벌 트랜스듀서의 종류별 음향 특성 비교 분석)

  • Choi, Youji;Shim, Hayeong;Roh, Yongrae
    • The Journal of the Acoustical Society of Korea
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    • v.38 no.3
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    • pp.256-265
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    • 2019
  • Several types of cymbal transducers used for underwater detection have been studied. Representative types are Moonie, convex cymbal, and concave cymbal transducers. In this study, we analyzed the characteristics of these three types of transducers for underwater broadband projectors and compared them together. First, the influence of structural variables on the acoustic characteristics of the transducers was analyzed. Based on this, we derived the structure of each transducer type to have a specific center frequency and the maximum bandwidth. As a result of comparing the performance of the optimized transducers, the convex cymbal transducer turned out to be best in terms of both broad bandwidth and high power.

A Study on Micropattern Fabrication and Tribology Characteristics by Photolithography Process (포토리소그래피 공정에 의한 마이크로 패턴 제작과 tribology 특성 연구)

  • T.H. Jang;J.H. Park;Y.W. Kwon;B.R. Cho;T.G. Kim
    • Journal of the Korean Society for Heat Treatment
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    • v.36 no.3
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    • pp.137-144
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    • 2023
  • Micro electro mechanical systems (MEMS) and precision machines require excellent friction and wear characteristics to improve energy efficiency generated during sliding motion. In this study, DLC thin film with high hardness and low friction was deposited on STS304 substrate material by CVD method, and dot-shaped convex and concave micropatterns were fabricated by photolithography process. The diameter of the pattern was 20 ㎛, the pitch was 40 ㎛, and a pattern having a mesh type arrangement was fabricated and an abrasion test was performed. The results of the wear test on the micro pattern confirmed that the friction coefficient characteristics were improved compared to STS 304 and DLC thin films. In addition, in this result, the micro-pattern showed 11.4% more improved friction coefficient than the DLC thin film. The friction coefficient characteristics for convex and concave patterns of the same size showed almost similar results.

COSMIC RAY ACCELERATION AT BLAST WAVES FROM TYPE Ia SUPERNOVAE

  • Kang, Hye-Sung
    • Journal of The Korean Astronomical Society
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    • v.39 no.4
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    • pp.95-105
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    • 2006
  • We have calculated the cosmic ray(CR) acceleration at young remnants from Type Ia supernovae expanding into a uniform interstellar medium(ISM). Adopting quasi-parallel magnetic fields, gasdynamic equations and the diffusion convection equation for the particle distribution function are solved in a comoving spherical grid which expands with the shock. Bohm-type diffusion due to self-excited $Alfv\acute{e}n$ waves, drift and dissipation of these waves in the precursor and thermal leakage injection were included. With magnetic fields amplified by the CR streaming instability, the particle energy can reach up to $10^{16}Z$ eV at young supernova remnants(SNRs) of several thousand years old. The fraction of the explosion energy transferred to the CR component asymptotes to 40-50 % by that time. For a typical SNR in a warm ISM, the accelerated CR energy spectrum should exhibit a concave curvature with the power-law slope flattening from 2 to 1.6 at $E{\gtrsim}0.1$ TeV.

Mutational Analysis Elucidates the Role of Conserved 237 Arginine in 23S rRNA Methylation, Which is in the Concave Cleft Region of ErmSF (ErmSF에서 두 도메인 사이에 존재하는 잘 보존된 237번 아르지닌 잔기의 위치 지정 치환 변이의 효소 활성 검색을 통한 역할 규명)

  • Jin, Hyung Jong
    • Korean Journal of Microbiology
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    • v.49 no.2
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    • pp.105-111
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    • 2013
  • The Erm family of adenine-$N^6$ methyltransferases (MTases) is responsible for the development of resistance to macrolide-lincosamide-streptogramin B antibiotics through the methylation of 23S ribosomal RNA. Recently, it has been proposed that well conserved amino acids in ErnC' located in concave cleft between N-terminal 'catalytic' domain and C-terminal 'RNA-binding' domain interacts with substrate RNA. We carried out the site-directed mutagenesis and studied the function of the ErmSF R237 mutant in vitro and in vivo. R237 amino acid residue is located in the concave cleft between two domains. Furthermore this residue is very highly conserved in almost all the Erm family. Purified mutant protein exhibited only 51% enzyme activity compared to wild-type. Escherichia coli with R237A mutant protein compared to the wild-type protein expressing E. coli did not show any difference in its MIC (minimal inhibitory concentration) suggesting that even with lowered enzyme activity, mutant protein was able to efficiently methylate 23S rRNA to confer the resistance on E. coli expressing this protein. But this observation strongly suggests that R237 of ErmSF probably interacts with substrate RNA affecting enzyme activity significantly.

Adsorption isotherm and kinetics analysis of hexavalent chromium and mercury on mustard oil cake

  • Reddy, T. Vishnuvardhan;Chauhan, Sachin;Chakraborty, Saswati
    • Environmental Engineering Research
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    • v.22 no.1
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    • pp.95-107
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    • 2017
  • Adsorption equilibrium and kinetic behavior of two toxic heavy metals hexavalent chromium [Cr(VI)] and mercury [Hg(II)] on mustard oil cake (MOC) was studied. Isotherm of total chromium was of concave type (S1 type) suggesting cooperative adsorption. Total chromium adsorption followed BET isotherm model. Isotherm of Hg(II) was of L3 type with monolayer followed by multilayer formation due to blockage of pores of MOC at lower concentration of Hg(II). Combined BET-Langmuir and BET-Freundlich models were appropriate to predict Hg(II) adsorption data on MOC. Boyd's model confirmed that external mass transfer was rate limiting step for both total chromium and Hg(II) adsorptions with average diffusivity of $1.09{\times}10^{-16}$ and $0.97m^2/sec$, respectively. Desorption was more than 60% with Hg(II), but poor with chromium. The optimum pH for adsorptions of total chromium and Hg(II) were 2-3 and 5, respectively. At strong acidic pH, Cr(VI) was adsorbed by ion exchange mechanism and after adsorption reduced to Cr(III) and remained on MOC surface. Hg(II) removal was achieved by complexation of $HgCl_2$ with deprotonated amine ($-NH_2$) and carboxyl (COO-) groups of MOC.

Seed and seed coat morphology in monotypic and endemic genera of Korean angiosperms

  • Se-Moon AHN;Hye-Rin KIM;Kweon HEO
    • Korean Journal of Plant Taxonomy
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    • v.53 no.2
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    • pp.102-109
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    • 2023
  • The basic information of ovule and seed characteristics was investigated for five monotypic and endemic genera in the Korean peninsula as categorized by the Flora of Korea category. The carpels and seeds were sectioned with a rotary microtome. Mature seeds were coated with platinum using an ion sputter and observed using a scanning electron microscope. As a result, Abeliophyllum was found to be anatropous and a unitegmic ovule, with a slightly colliculate seed surface and exotestal seed coat type. The ovule of Coreanomecon was anatropous and bitegmic, having a distinct echinate seed surface, and exo-endotestal seed coat type with a prismatic crystal in the mesotesta. The ovule of Hanabusaya was anatropous and a unitegmic, with a long reticulate seed surface sculpture, and distinct exotestal seed coat type. In addition, a wing developed at the opposite side of the raphe bundle. Megaleranthis was an anatropous and bitegmic ovule, having a small pentagonal disk shape, a concave seed surface and exotestal seed coat type. Finally, Pentactina was also anatropous and a unitegmic ovule, reticulate seed sculpture, and endotestal seed coat type. These data will be proving to be a source of good information for securing bio-sovereignty in the near future.

Study on Fabrication of a Large Concave Mirror Surface Using a Swing-Arm Type Profilometer (스윙암 방식의 형상 측정기를 이용한 대형 반사경의 정밀가공에 관한 연구)

  • Lee, Ki-Am;Kim, Ock-Hyun;Lee, Eung-Suk
    • Journal of the Korean Society of Manufacturing Process Engineers
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    • v.7 no.3
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    • pp.41-46
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    • 2008
  • Generally optical components are fabricated by grinding, lapping and polishing processes. Those processes take long time to obtain optical high surface quality. In the case of large optical components, the on-machine measurement is strongly recommended because the workpiece is fragile and difficult to set up for fabricating and measuring. This paper is concerned about a swing-arm mechanism which can be used for on-machine measurement of a surface profile with a sensing probe end-effect, and also for grinding or lapping the surface with a corresponding tool. The measuring accuracy and uncertainty using a swing arm type profilometer have been studied. The experimental results show that this method is useful specially in lapping process with the accuracy of $5{\mu}m$. Those inspection data are provided for correcting the residual figuring error in next processes.

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Kinetics and Mechanism of the Anilinolysis of Aryl Ethyl Isothiocyanophosphates in Acetonitrile

  • Barai, Hasi Rani;Adhikary, Keshab Kumar;Lee, Hai Whang
    • Bulletin of the Korean Chemical Society
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    • v.34 no.6
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    • pp.1829-1834
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    • 2013
  • The nucleophilic substitution reactions of Y-aryl ethyl isothiocyanophosphates with substituted X-anilines and deuterated X-anilines were investigated kinetically in acetonitrile at $75.0^{\circ}C$. The free energy relationships with X in the nucleophiles exhibited biphasic concave downwards with a break point at X = H. A stepwise mechanism with rate-limiting bond formation for strongly basic anilines and with rate-limiting bond breaking for weakly basic anilines is proposed based on the negative and positive ${\rho}_{XY}$ values, respectively. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) changed gradually from primary normal with strongly basic anilines, via primary normal and secondary inverse with aniline, to secondary inverse with weakly basic anilines. The primary normal and secondary inverse DKIEs were rationalized by frontside attack involving hydrogen bonded, four-center-type TSf and backside attack involving in-line-type TSb, respectively.