• Title/Summary/Keyword: Intermolecular

Search Result 459, Processing Time 0.02 seconds

One-pot Four Component Reaction of Unsymmetrical 1-Methylbarbituric Acid with BrCN and Various Aldehydes in the Presence of Et3N and/or Pyridine

  • Jalilzadeh, Mohammad;Pesyan, Nader Noroozi
    • Journal of the Korean Chemical Society
    • /
    • v.55 no.6
    • /
    • pp.940-951
    • /
    • 2011
  • Reaction of 1-methylpyrimidine-(1H,3H,5H)-2,4,6-trione (1-MBA 1) as an unsymmetrical barbituric acid with cyanogen bromide and various aldehydes in the presence of triethylamine and/or pyridine afforded diastereomeric mixtures of new class of heterocyclic stable 5-aryl-1,1'-dimethyl- and 5-aryl-3,1'-dimethyl-1H,1'H-spiro[furo[2,3-d]pyrimidine-6,5'-pyrimidine]2,2',4,4',6'(3H,3'H,5H)-pentaones which are dimeric forms of 1-methyl barbiturate at the range of $0^{\circ}C$ to room temperature. In the reaction of some aldehydes with 1-MBA and BrCN were afforded a mixture of diastereomers. Another two aldehydes such as 4-cyano- and 2-hydroxybenzaldehydes gave exclusively two diastereomers in which binded to the salt of triethylammonium hydrobromide by intermolecular H-bond in ratio of 1:1. 4-Hydroxybenzaldehyde and 2-pyridinecarbaldehyde gave exclusively one diastereomer under the same condition. Aldehydes possessing strong electron-donor were produced exclusively two geometric isomers of Knoevenagel adduct (E- and Z-isomers). The structures of compounds were deduced by $^1H$ NMR, $^{13}C$ NMR and FT-IR spectroscopy. Mechanism of the formation is discussed.

Conformational Transition of Poly(γ-benzyl-L-glutamate)-Poly(ethylene glycol) Block Copolymers in Bulk

  • Choi, Young-Wook;Park, Young-Mi;Choo, Jae-Bum;Cho, Chong-Su;Sohn, Dae-Won
    • Bulletin of the Korean Chemical Society
    • /
    • v.28 no.5
    • /
    • pp.795-799
    • /
    • 2007
  • The bulk properties of poly(γ-benzyl-L-glutamate)-poly(ethylene glycol), PBLG-PEO, diblock copolymer were investigated. The helical transition from 7/2 to 13/5 for pure PBLG was at 120 oC while those of GE-1 and GE-2, which contain flexible PEO block 40 wt% and 60 wt% respectively, were shown at 135℃ on DSC experiments. FT-IR and XRD experiments were shown that the diblock copolymers maintained their α-helical structure in the temperature range between 25℃ and 175℃. Increasing relative size of coil part resulted in the increase of intermolecular packing distances. Due to well-maintained helical structure, lyotropic LC phases were observed for the PBLG-PEO block copolymer by the polarized optical microscope (POM). Especially, GE-3 copolymer, which has 12.5 wt% PEO contents, showed the smectic C phase. The competition of favorable aggregation energy between rod-rod and coil-coil, and unfavorable aggregation energy of rod-coil give rise to change the supramolecular structure in mixed solvent.

Topology effects on the LCST of end-capped poly(ethylene glycol)s

  • Kim, Jin Young;Moon, Hyo Jung;Ko, Du Young;Jeong, Byeongmoon
    • Biomaterials and Biomechanics in Bioengineering
    • /
    • v.2 no.1
    • /
    • pp.15-22
    • /
    • 2015
  • Poly(ethylene glycol) end-capped with pentafluorophenyl group(s) in ABA (FP-PEG-FP) and AB (mPEG-FP) types were prepared. Even though they were similar in composition, the lower critical solution temperature (LCST) of FP-PEG-FP was observed at $23^{\circ}C$, whereas that of mPEG-FP was observed at $65^{\circ}C$. To understand the large difference in solution behaviour of the two polymers, UV-VIS spectroscopy, microcalorimetry, 1H-NMR spectroscopy, and dynamic light scattering were used. FP-PEG-FP has two hydrophobic pentafluorophenyl groups at the ends of hydrophilic PEG (1000 Daltons), whereas mPEG-PF has a highly dynamic PEG (550 Daltons) block that are anchored to a hydrophobic pentafluorophenyl group. PF-PEG-PF not only has a smaller conformational degree of freedom than mPEG-PF but also can form extensive intermolecular aggregates, therefore, PF-PEG-PF exhibits a significantly lower LCST than mPEG-PF. This paper suggests that topological control is very important in designing a temperature-sensitive polymer.

Self-Healing Asphalt Prepared by using Ionic Epoxy Resin

  • Lee, Young-Jik;Seo, Jun-Young;Kim, Seo-Yeon;Lee, Seung-Hyun;Hong, Young-Keun
    • Elastomers and Composites
    • /
    • v.50 no.3
    • /
    • pp.167-174
    • /
    • 2015
  • Anionic epoxy compound was synthesized and added to asphalt aiming to prepare self-healing asphalt. Epoxy-modified asphalt showed excellent modification effect and healing effect as well. The results revealed that with 5% addition of polymer the tensile strength, impact strength and complex shear modulus of the polymer-modified asphalt increased by 65%. 64% and 35%, respectively. It seems that high interaction occurs between polymer and asphalt matrix. Self-healing efficiency of the polymer-modified asphalt based on tensile strength showed 100%, comparing to 79% of straight asphalt. In impact experiment the polymer-modified asphalt showed 99% of healing efficiency, comparing to 77% of straight asphalt. In rheological experiment the polymer-modified asphalt showed 103% of healing efficiency, comparing to 72% of straight asphalt. It appears that the ionic bonding existing in epoxy polymers contributed to high values of self-healing efficiency. The polymer which has high intermolecular force fills the crack of the asphalt, pulling the opponent side each other, and so the original properties were restored.

Spectrophotometric Determination of Antihistamines by Using Metal Indicators NN, EBT and Calcon as Color Developing Agents. (항 히스타민제의 흡광광도정량법)

  • 옥지원
    • YAKHAK HOEJI
    • /
    • v.18 no.2
    • /
    • pp.133-144
    • /
    • 1974
  • The metal indicator, acidic azo dyes NN, EBT and Calcon are utilized to analyse quantitatively chlorpheniramine, tripelenamine and diphenhydramine forming insoluble ion pair in aqueous solution at proper pH values between the acidic azo dyes and the sample molecules, these compexes are extracted by organic polar solvents, and organic layer is determined spectrophotometrically. Generally, the absorption maxima of the complexes are shifted to longer wavelengths compare to the absorption maxima of the dyes themselves. The binding ratio of the ion pair forming complex molecules in chloroform soln, are as follows ; NN-antihistamines (chlorpheniramine, tripelennamine, diphenhydramine) are NN-1 to antihisamine-1, EBT-antihistamines are EBT-2 to antithistamines a and Calcon-antihistamines are Calcon-3 to antithistamines-1. These coomplexes in chloroform soln. are very stable, and show higher absorbance than the other organic polar solvents. The binding state of complexes were presumed intermolecular hydrogen bond by their infrared spectra. In the mixture solution of three samples, the aqueous phase is buffered at pH 1.0, and benzene is used to extract ion pair of diphenhydramine EBT complex selectively. At pH 1.0 of aqueous layer, Calon-diphenhydramine complex is also extracted selectively by benzene. However, in this case very small amount of chlorpheniramine-calcon calcon simultaneously. The binding state of diphenhydramine-EBT and diphenhydramine-calcon in benzene are smae as the complexes in chloroform. But the absorption maxima of the complexes in benzene are shifted to shorter wavelenlgths than the complexes in chloroform.

  • PDF

Oxime Generation of Silk Fibers by Hydroxlammonium choride treatment

  • Bae, Do-Gyu
    • Journal of Sericultural and Entomological Science
    • /
    • v.41 no.2
    • /
    • pp.116-121
    • /
    • 1999
  • This study was aimed to explain the essence of Hydroxylammonium hydrochloride(H.A.) effect on degummed silk fiber increasing the colour sites due to oxime generating reaction. H.A. in aqueous solution caues to increase the amount of [H+] and reduce pH values as the concentration of H.A. increases. The rate of [H+] absorption of silk fiker in acidic solution differs on the basic of solution pH and shows a specific uptake in each pH, the lower the pH of solution, the higher the amount [H+] absorption. The pH of solution after treating of silk fiber in H.A. and HCl, showed more remaining [H+] in H.A. solution due to [H+] releasing under the procedure of oxime production. Also it was revealed that in higher concentration of H.A. the reaction for oxime fixation in silk fiber carried out stonger and as a result the bigger gap with acid uptake curve appeared. FT-IR analysis of silk fiber treated with H.A. revealed the creating of intermolecular H-bond at the 2,981-2.930 cm-1, which was not appeared for nontraeted silk fibers and shows H-bond between N-OH group in oue chain and C=) group in another chain of silk protein. Colourimetry of dyed silk fiber after H.A. tratment showed that the silk fiber treated with the high concentration of H.A. compare to low concentration, absorbed more dyeing molecules and so Showed less percontage of Whiteness.

  • PDF

Solvent and Concentration Effects on Carbonyl Stretching Frequencies: Dialkyl Ketones (카르보닐 신축진동 파수에 대한 용매 및 농도 효과: 디알킬 케톤)

  • Jung, Young-Mee;Kang, Jae-Soo;Nam, Sang-Il;Lee, Mu-Sang
    • Journal of the Korean Chemical Society
    • /
    • v.40 no.6
    • /
    • pp.415-419
    • /
    • 1996
  • Hydrogen bonding, dielectric effects and steric effects are all factors which determine the carbonyl stretching frequency, νC=O of ketones in solution. The νC=O frequency of ketones is affected by change in concentration of ketones in various solvents. The νC=O frequency shifts to lower frequency in nonpolar solvents and shifts to higher frequency in polar solvents with the increasing volume% of ketones. In acetonitrle, the νC=O frequency shifts to higher frequency as the volume% of ketones is increased except dimethyl ketone. The νC=O frequency shifts to lower frequency as the solvent system becomes increasingly polar or with the increasing extent of intermolecular hydrogen bonding, as in the case of increasing volume% chloroform in $CHCl_3$/$CCl_4$ solvent system.

  • PDF

Sonochemical Synthesis, Thermal Studies and X-ray Structure of Precursor [Zr(acac)3(H2O)2]Cl for Deposition of Thin Film of ZrO2 by Ultrasonic Aerosol Assisted Chemical Vapour Deposition

  • Hussain, Muzammil;Mazhar, Muhammad;Rauf, Muhammad Khawar;Ebihara, Masahiro;Hussain, Tajammal
    • Bulletin of the Korean Chemical Society
    • /
    • v.30 no.1
    • /
    • pp.92-96
    • /
    • 2009
  • A new precursor [$Zr(acac)_{3}(H_{2}O)_{2}$] was synthesized by Sonochemical technique and used to deposit thin $ZrO_{2}$ film on quartz and ceramic substrate via ultrasonic aerosol assisted chemical vapour deposition (UAACVD) at 300 ${^{\circ}C}$ in oxygen environment followed by annealing of the sample for 2-3 minutes at 500 ${^{\circ}C}$ in nitrogen ambient. The molecular structure of the precursor determined by single crystal X-ray analysis revealed that the molecules are linked through intermolecular hydrogen bonds forming pseudo six and eight membered rings. DSC and TGA/FTIR techniques were used to determine thermal behavior and decomposition temperature of the precursor and nature of evolved gas products. The optical measurement of annealed $ZrO_{2}$ film with tetragonal phase shows optical energy band gap of 5.01 eV. The particle size, morphology, surface structure and composition of deposited films were investigated by XRD, SEM and EDX.

Spectroscopic Properties of Flavonoids in Various Aqueous-Organic Solvent Mixtures

  • Park, Hyoung-Ryun;Daun, Yu;Park, Jong Keun;Bark, Ki-Min
    • Bulletin of the Korean Chemical Society
    • /
    • v.34 no.1
    • /
    • pp.211-220
    • /
    • 2013
  • The characteristic fluorescence properties of quercetin (QCT) and apigenin (API) were studied in various $CH_3OH-H_2O$ and $CH_3CN-H_2O$ mixed solvents. The structure of QCT is completely planar. API is not planar at the ground state but becomes nearly planar at the excited state. If the molecules are excited to the $S_1$ state in organic solvents, QCT exhibits no fluorescence due to excited state intramolecular proton transfer (ESIPT) between the -OH and the carbonyl oxygen, but API shows significant fluorescence because ESIPT occurs slowly. If the molecules are excited to the $S_2$ state, both QCT and API exhibit strong $S_2{\rightarrow}S_o$ emission without any dual fluorescence. As the $H_2O$ composition of both solvents increases, the fluorescence intensity decreases rapidly due to the intermolecular hydrogen bonding interaction. The theoretical calculation further supports these results. The change in fluorescence properties as a function of the solvatochromic parameters was also studied.

Energy Flow and Bond Dissociation of Vibrationally Excited Toluene in Collisions with N2 and O2

  • Ree, Jongbaik;Kim, Sung Hee;Lee, Sang Kwon
    • Bulletin of the Korean Chemical Society
    • /
    • v.34 no.5
    • /
    • pp.1494-1502
    • /
    • 2013
  • Energy flow and C-$H_{methyl}$ and C-$H_{ring}$ bond dissociations in vibrationally excited toluene in the collision with $N_2$ and $O_2$ have been studied by use of classical trajectory procedures. The energy lost by the vibrationally excited toluene upon collision is not large and it increases slowly with increasing total vibrational energy content between 5,000 and 45,000 $cm^{-1}$. Intermolecular energy transfer occurs via both of V-T and V-V transfers. Both of V-T and V-V transfers increase as the total vibrational energy of toluene increases. When the total energy content $E_T$ of toluene is sufficiently high, either C-H bond can dissociate. The C-$H_{methyl}$ dissociation probability is higher than the C-$H_{ring}$ dissociation probability, and that in the collision with $N_2$ is larger than with $O_2$.