• Title/Summary/Keyword: Asymmetric reaction

Search Result 140, Processing Time 0.02 seconds

Estimation of Vertical Interaction Force to the End of a Surgical Instrument by Measuring Reaction Force to the Trocar Support (트로카 고정부에 작용하는 반력을 측정하여 수술도구 말단의 수직방향 상호작용 힘을 추정하는 방법)

  • Kim, Suyong;Kim, Cheongjun;Lee, Doo Yong
    • Journal of Institute of Control, Robotics and Systems
    • /
    • v.22 no.8
    • /
    • pp.615-618
    • /
    • 2016
  • This paper proposes a method to estimate vertical interaction force to the end of the surgical instrument by measuring reaction force at the part supporting the trocar. Relation between the force to the trocar and the interaction force is derived using the beam theory. The vertical interaction force is modeled as a function of the reaction force to the trocar and the distance between the drape plate and the trocar. Experimental results show that error is induced by the asymmetric shape of the trocar tip because contact position between the instrument and the trocar tip is changed depending on the direction of the interaction force. The theoretical relation, therefore, is compensated and reduced. Average $L_2$ relative error of the estimated force in the x-direction and the y-direction is 5.81 % and 5.99 %, respectively.

Synthesis of Asymmetric Pyrazoline Derivatives from Phenylthiophenechalcones; DFT Mechanistic Study

  • Aboelnaga, Asmaa;Mansour, Eman;Ahmed, Hoda. A.;Hagar, Mohamed
    • Journal of the Korean Chemical Society
    • /
    • v.65 no.2
    • /
    • pp.113-120
    • /
    • 2021
  • New phenylthiophenechalcones,1-(biphenyl-4-yl)-3-(5-phenylthiophen-2-yl)prop-2-en-1-one (3a) and 3-(5-phenylthiophen-2-yl)-1-(4-(piperidin-1-yl) phenyl) prop-2-en-1-one (3b) were synthesized, next, their treatment with thiosemicarbazide in ethanol afforded their pyrazoline derivatives (4a) and (4b), respectively. The molecular structures of the synthesized compounds were confirmed via elemental analysis, FT-IR, 1H, 13C NMR and mass spectroscopy. The geometrical elucidation of four suggested conformers has been studied for these compounds. DFT calculations have been performed to study the stability and the structural parameters of the predicted conformers and revealed that orientation of the biphenyl and the phenylthiophene moieties affect the stability of the estimated conformers of the synthesized chalcones and pyrazoline. Moreover, two reaction mechanisms have been proposed to illustrate the reaction products and the DFT calculations have been used to confirm the reaction mechanism of the pyrazoline compounds.

A New Strategy to Improve the Efficiency and Sustainability of Candida parapsilosis Catalyzing Deracemization of (R,S)-1-Phenyl-1,2-Ethanediol Under Non-Growing Conditions: Increase of NADPH Availability

  • Nie, Yao;Xu, Yan;Hu, Qing Sen;Xiao, Rong
    • Journal of Microbiology and Biotechnology
    • /
    • v.19 no.1
    • /
    • pp.65-71
    • /
    • 2009
  • Microbial oxidoreductive systems have been widely used in asymmetric syntheses of optically active alcohols. However, when reused in multi-batch reaction, the catalytic efficiency and sustainability of non-growing cells usually decreased because of continuous consumption of required cofactors during the reaction process. A novel method for NADPH regeneration in cells was proposed by using pentose metabolism in microorganisms. Addition of D-xylose, L-arabinose, or D-ribose to the reaction significantly improved the conversion efficiency of deracemization of racemic 1-phenyl-1,2-ethanediol to (S)-isomer by Candida parapsilosis cells already used once, which afforded the product with high optical purity over 97%e.e. in high yield over 85% under an increased substrate concentration of 15 g/l. Compared with reactions without xylose, xylose added to multi-batch reactions had no influence on the activity of the enzyme catalyzing the key step in deracemization, but performed a promoting effect on the recovery of the metabolic activity of the non-growing cells with its consumption in each batch. The detection of activities of xylose reductase and xylitol dehydrogenase from cell-free extract of C. parapsilosis made xylose metabolism feasible in cells, and the depression of the pentose phosphate pathway inhibitor to this reaction further indicated that xylose facilitated the NADPH-required deracemization through the pentose phosphate pathway in C. parapsilosis. moreover, by investigating the cofactor pool, the xylose addition in reaction batches giving more NADPH, compared with those without xylose, suggested that the higher catalytic efficiency and sustainability of C. parapsilosis non-growing cells had resulted from xylose metabolism recycling NADPH for the deracemization.

Production of D-Lactic Acid from DL-Lactonitrile by Pseudomonas sp. (Pseudomonas sp.에 의한 DL-Iactonitrile로부터 D-lactic acid의 생산)

  • 김현수;황인균;정남현;방원기
    • Microbiology and Biotechnology Letters
    • /
    • v.30 no.4
    • /
    • pp.373-379
    • /
    • 2002
  • By using DL-acetonitrile as enzyme inducer, 90 bacteria were isolated from a field soil. Among the isolated strains, the strain WJ-003 showed the highest activity for production of D-lactic acid from DL-lactonitrile, and was partially identified as Pseudomonas sp. The production condition of D-lactic acid from DL-lactonitrile using resting cells as an enzyme source was optimized as follows: the reaction mixture contained 10 mM of DL-lactonitrile, 20 g of wet cells in 11 of 20 mM potassium phosphate buffer (pH 7.0) and the reaction was carried out at $30^{\circ}C$. After 18 h of reaction, 0.843 g/l of D-lactic acid was produced which corresponded to a conversion ratio of 93.7% and an optical purity of 99.8%. Additionally, when 10 mM of DL-lactonitrile was added once more to the reaction mixture at 14 h, 1.64 g/1 of D-lactic acid was produced after 28 h. In this experiment, the conversion ratio was 91.1% and optical purity 99.8%.

Clinical study of blood flow and vascular reaction in Taeumin CVA patients using Transcranial Doppler (Transcranial Doppler를 이용(利用)한 태음인 중풍환자의 혈류속도(血流速度)와 혈관(血管) 반응성(反應性)에 대한 임상적(臨床的) 고찰(考察))

  • Lim, Jong-Pil;Bae, Na-Young;Han, Kyung-Soo;Ahn, Taek-Won
    • Journal of Haehwa Medicine
    • /
    • v.15 no.2
    • /
    • pp.263-272
    • /
    • 2006
  • Purpose Brain vessles have autoregulation function, so even when perfusion pressure drops, cerebral blood flow remain stable by vasodilation. Latest research on this reserve of cerebral vessels is being done using TCD, which measures the reserve of the vessels. We did a research comparing cerebral vessel and peripheral vessel reserve between Taeumin, who are more likely to suffer CVA, and the normal. We observed blood flow of Internal carotid artery siphon and radial indicis artery of the two group with TCD. Method We picked 20 people out of patients diagnosed as cerebral infarction at Cheon-An Oriental hospital of Daejeon University. They were diagnosed as Taeumin with QSCCII questionnaire and constitutional differentiation. Using TCD, we measured highest blood flow rate, mean blood flow and asymmetric counting blood flow of Internal carotid artery siphon and radial indicis artery at rest. And then we measured again after stimulating cerebral vessels, by triggering hypercapnia by self apnea and peripheral vessels by palm heating. Result At rest, mean blood flow rate of Internal carotid artery siphon showed significant decrease compared to control group. Blood flow rate of Internal carotid artery siphon after hypercapnia showed significant decline in highest blood flow rate and mean blood flow compared to control group. Cerebral vessel reaction after the hypercapnia induction showed great change in experiment group than the control group. Peripheral vessel reaction after palm heating showed significant decline in experiment group compared to control group. Conclusion In conclusion, measuring the alteration of blood flow used in diagnosing cerebral infarction, is more sensitive when vessel stimulation is done. Non-invasive TCD is effective especially in case of Taeumin who are more likely to suffer vascular disorder than others.

  • PDF

Successive Synthesis of Well-Defined Star-Branched Polymers by an Iterative Approach Based on Living Anionic Polymerization

  • Higashihara Tomoya;Inoue Kyoichi;Nagura Masato;Hirao Akira
    • Macromolecular Research
    • /
    • v.14 no.3
    • /
    • pp.287-299
    • /
    • 2006
  • To successively synthesize star-branched polymers, we developed a new iterative methodology which involves only two sets of the reactions in each iterative process: (a) an addition reaction of DPE or DPE-functionalized polymer to a living anionic polymer, and (b) an in-situ reaction of 1-(4-(4-bromobutyl)phenyl)-1-phenylethylene with the generated 1,1-diphenylalkyl anion to introduce one DPE functionality. With this methodology, 3-, 4-, and 5-arm, regular star-branched polystyrenes, as well as 3-arm ABC, 4-arm ABCD, and a new 5-arm ABCDE, asymmetric star-branched polymers, were successively synthesized. The A, B, C, D, and E arm segments were poly(4-trimethylsilylstyrene), poly(4-methoxystyrene), poly(4-methylstyrene), polystyrene, and poly(4-tert-butyldimethylsilyloxystyrene), respectively. All of the resulting star-branched polymers were well-defined in architecture and precisely controlled in chain length, as confirmed by SEC, $^1H$ NMR, VPO, and SLS analyses. Furthermore, we extended the iterative methodology by the use of a new functionalized DPE derivative, 1-(3-chloromethylphenyl)-1-((3-(1-phonyletheny1)phenyl) ethylene, capable of introducing two DPE functionalities via one DPE anion reaction site in the reaction (b). The number of arm segments of the star-branched polymer synthesized by the methodology could be dramatically increased to 2, 6, and up to 14 by repeating the iterative process.

The Chirality Conversion Reagent for Amino Acids Based on Salicyl Aldehyde

  • Yoon, Hoe-Jin;Jung, Hein;Ahn, Yun-Soo;Nandhakumar, Raju;Kim, Jun-Soo;Kim, Kwan-Mook
    • Bulletin of the Korean Chemical Society
    • /
    • v.33 no.5
    • /
    • pp.1715-1718
    • /
    • 2012
  • 2-Hydroxy-6-(1-(3-phenylurylphenyl)ethoxy)-benzaldehyde ($\mathbf{2}$) has been synthesized in racemic form from 1,3-Dihydroxybenzene via formylation and reaction with 3-phenyluryl-methylbenzylbromide. The optically pure form of $\mathbf{2}$ was separated by normal silica column chromatography from the imine diastreomer which was obtained by the reaction of racemic mixture of $\mathbf{2}$ with optically pure leucinol. The absolute configuration of the separated enantiomer of $\mathbf{2}$ was decided from the energy calculation of the corresponding imine diastereomers. The activity of $\mathbf{2}$ as a chirality conversion reagent (CCR) for amino acids was determined by $^1H$ NMR analysis. The efficiency of $\mathbf{2}$ is not better than the previous CCRs based on binaththol. Compound $\mathbf{2}$, however, has lower molecular weight compared to other CCRs. This work demonstrates that asymmetric carbon can control the selectivity of amino acids.

Ussing's flux ratio theorem for nonlinear diffusive transport with chemical interactions

  • Bracken, A.J.;McNabb, A.;Suzuki, M.
    • 제어로봇시스템학회:학술대회논문집
    • /
    • 1994.10a
    • /
    • pp.747-752
    • /
    • 1994
  • Ussing's flux ratio theorem (1978) reflects a reciprocal relationship behavior between the unidirectional fluxes in asymmetric steady diffusion-convection in a membrane slab. This surprising result has led to many subsequent studies in a wide range of applications, in particular involving linear models of time dependent problems in biology and physiology. Ussing's theorem and its extensions are inherently linear in character. It is of considerable interest to ask to what extent these results apply, if at all, in situations involving, for example, nonlinear reaction. A physiologically interesting situation has been considered by Weisiger et at. (1989, 1991, 1992) and by McNabb et al. (1990, 1991) who studied the role of albumin in the transport of ligands across aqueous diffusion barriers in a liver membrane slab. The results are that there exist reciprocal relationships between unidirectional fluxes in the steady state, although albumin is chemically interacting in a nonlinear way of the diffusion processes. However, the results do not hold in general at early times. Since this type of study first started, it has been speculated about when and how the Ussing's flux ratio theorem fails in a general diffusion-convection-reaction system. In this paper we discuss the validity of Ussing-type theorems in time-dependent situations, and consider the limiting time behavior of a general nonlinear diffusion system with interaction.

  • PDF

Coordination Chemistry of Chlorophylls: Which Side of the Chlorin Macrocycle is Favored for the Ligand Coordination\ulcorner

  • Oba, Toru;Tamiaki, Hitoshi
    • Journal of Photoscience
    • /
    • v.9 no.2
    • /
    • pp.362-363
    • /
    • 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].

  • PDF

Biocatalytic production of chiral epoxide: Epoxide hydrolase-catalyzed enantioselective resolution

  • Lee, Eun-Yeol
    • Proceedings of the Korean Society of Life Science Conference
    • /
    • 2001.11a
    • /
    • pp.21-28
    • /
    • 2001
  • A newly isolated Aspergillus niger possessing the novel epoxide hydrolase(EHase) activity was investigated for the enantioselective hydrolysis of racemic aromatic epoxides. The gene encoding EHase was cloned by RT-PCR, and molecular characteristics of the EHase gene were compared with other microbial EHases. The cloned gene encodes 398 amino acids with a deduced molecular mass of 44.5 kDa and pI of 4.83, and sequence homology with other microbial EHase was low. Functional recombinant EHase could be obtained by heterologous expressions in E. coli. Enantioselectivity of recombinant EHase was tested for valuable aromatic epoxide intermediates. Reaction conditions of EHase-catalyzed asymmetric resolution were optimized for the production of chiral styrene oxide.

  • PDF