Chiral Diene Ligands for Asymmetric Catalysis

115 (The 115th General Meeting of the Korean Chemical Society)

: 2015 4 15~17(~) 3

: KINTEX

: PLEN-1

:

: , : 16:30, :

Chiral Diene Ligands for Asymmetric Catalysis

Tamio Hayashi

Institute of Materials Research and Engineering, A*STAR, Department of Chemistry, National University

of Singapore

As conceptually new chiral ligands, we reported the synthesis of enantiomerically pure chiral dienes,

whose basic diene skeleton is bicyclo[2.2.1]hepta-2,5-diene (nbd*) or bicyclo[2.2.2]octa-2,5-diene (bod*).

They have two alkyl or aryl substituents on the double bonds, one on each of the two double bonds. The

chiral diene ligands were found to be better than the conventional chiral ligands represented by chiral

bisphosphines in terms of both catalytic activity and enantioselectivity in some of the catalytic

asymmetric reactions. Their high performance was observed in rhodium-catalyzed asymmetric addition of

organoboron reagents to ,-unsaturated ketones, N-sulfonylimines, and many other related reactions [1].

In this symposium, I will present some of recent advances on the asymmetric carbon-carbon bond

forming reactions catalyzed by chiral diene/rhodium complexes [2].

[1] A review: Shintani, R.; Hayashi, T. Aldrichimica Acta 2009, 42, 31.

[2] (a) T. Nishimura, A. Noishiki, G. C. Tsui, T. Hayashi, J. Am. Chem. Soc. 2012, 134, 5056. (b) T.

Nishimura, Y. Takiguchi, T. Hayashi, J. Am. Chem. Soc. 2012, 134, 9086. (c) T. Nishimura, A. Noishiki,

T. Hayashi, Angew. Chem. Int. Ed. 2013, 52, 1777. (d) Lim, K. M.-H.; Hayashi, T. J. Am. Chem. Soc.

2015, 137, in press, and references cited therein.


: 2015 4 15~17(~) 3

: KINTEX

: AWARD-1

:

: , : 09:00, :

AFM in water: Biomarker quantification and single molecule analysis

1 1,*

(POSTECH) 1(POSTECH)

(Atomic Force Microscope)

.

AFM ,

DNA sequence (J. Am. Chem. Soc.,

13754, 2014) chaperone AKR2A ribosome RPL23A receptor OEP7 peptide

,

DNA, mRNA, microRNA, biomarker copy

modification .


: 2015 4 15~17(~) 3

: KINTEX

: POLY1-1

: Current Trends in Carbon and Carbon-composite Polymers

: , : 09:00, :

Semiconducting Polymers and Small Molecules for Transistors and

Solar Cells

Iain McCulloch

Centre for Plastic Electronics and Department of Chemistry, Imperial College, London, UK

The power conversion efficiency (PCE) of single junction organic solar cells has increased significantly

during the last decade to 9-10%, now approaching the threshold considered necessary to commercialize

the technology. During this period, the structural diversity of semiconducting donor polymers for solar

cells has increased dramatically, enabling accelerated development of bulk heterojunction (BHJ) organic

solar cells based on polymer donor materials and molecular fullerene derivatives. One aspect of this

presentation is to illustrate one molecular design strategy used to optimise a new class of donor polymer.

However, the development of electron accepting materials that lead to BHJs with high PCE has been

significantly slower. The most commonly used n-type acceptors to date remain [6,6]-phenyl-C61-butyric

acid methyl ester (PC61BM) and its slightly larger counterpart PC71BM. These fullerene acceptors have

significant limitations including weak absorption and poor tunability of absorption over the range of

intense regions of the solar spectrum; morphological instability in thin film blends over time; high

synthetic costs and limited scope for synthetic control over electronic and structural properties. For these

reasons, we have developed new, synthetically simple electron acceptor materials, based on rhodanine

end groups, which have high lying LUMO energy levels and much larger absorption coefficients that

fullerenes. In BHJ devices with P3HT donor polymer, the rhodanine molecules were demonstrated to

outperform the fullerenes. Our synthetic strategy was to make dumbbell shaped dimeric fullerenes

where the fullerenes are linked via an alkyl bridge between the ester functional group on PCBM. This was

shown to inhibit large scale crystallisation.


: 2015 4 15~17(~) 3

: KINTEX

: POLY1-2


: , : 09:30, :

Versatile and scalable approaches to chemical processing of

nanocarbons

Milo Shaffer

Department of Chemistry, Imperial College, London, UK

Chemical functionalisation is critical to a wide range of nanotube applications, but needs to be versatile

and applicable at scale. Existing approaches tend to rely on liquid phase reactions, often requiring

damaging sonication or lengthy work up through filtration or centrifugation. The formation of

individualized functionalised single wall nanotubes (SWNTs) is a particular challenge. One approach is to

shift the modification reaction into the gas phase. We have developed a generic, scalable furnace

treatment, based on the thermochemical activation of the CNTs, followed by reaction with functional

organic monomers1. This approach allows the introduction of a wide variety of functional groups onto the

CNT surface whilst maintaining the excellent properties of the untreated materials. The underlying

mechanism of the reaction has been established and the distribution of the functionalised sites studied

using tagging experiments. The reaction is extremely versatile and can be carried out with a variety of

monomers. The reaction and the subsequent product purification can be carried out entirely in the gas-

phase, greatly simplifying work-up and improving scalability; the approach is fundamentally compatible

with the scale and equipment of many industrial nanotube synthesis processes, and is applicable to multi-

walled nanotubes, SWNTs, and other carbon-based materials6. The surface properties of these products

have been studied by direct wetting experiments on the nanoscale, dispersion studies, and inverse gas

chromatography (IGC)2. Water dispersible materials with cationic, anionic, and non-ionic surface

functionalities provide simple processing routes to a range of applications, and are particularly well suited

to studying biological interactions5,6.A different approach to nanotube processing, relies on reductive

charging. Using a liquid ammonia process3, pure nanotubides can be redissolved, purified, or optionally

functionalised without sonication. A key step is to control the ratio of charge to carbons, as it determines

both the yield and the nature of the dissolved material. The G/D ratios observed during the dissolution

sequence, as a function of metal:carbon ratio, demonstrate a new purification method for removing

carbonaceous impurities from pristine SWNTs. The production of individualised SWNT solutions has

been confirmed by neutron scattering. A similar approach can be applied to graphene nanoplatelets4. The

resulting nanocarbon ions can be readily chemically grafted for a variety of applications, depending on

the reagent, charge density, and ionic concentration in the reaction medium9. The nature of the reactivity

of charged graphenides is unusual, due to the continuum density of states of these otherwise molecularly

discrete species10. Interestingly, the chemical charging agent can be avoided by a pure electrochemical

process that yields both nanotube anions5 and cations8, suitable for purification, functionalization, or

electrodeposition, as desired.

1. R. Menzel et al, Chem. Sci., 2010, 1, 603-8.

2. R. Menzel et al, Langmuir, 2009, 25(14), 8340; R. Menzel et al, Carbon, 2012, 134(20) 8302

3. S Fogden al, ACS Nano, 2012, 6, 54-62

4. E Milner et al, J Am Chem Soc, 2012,8302

5. S Chen et al, Biomaterials, 2014, 35, 4729

6. Hu et al, Faraday Disc., 2014, 173, 273

7. Hodge et al, ACS Nano, 2013, 1769-1778

8. Hodge et al, Nature Comm, 2013, 1989

9. Morishita et al, J Mat Chem, 2014, 2, 15022

10. Hodge et al, Faraday Disc., 2014, 172, 311


: 2015 4 15~17(~) 3

: KINTEX

: POLY1-3


: , : 10:00, :

Mechanical and Electrical Properties of Carbon Nanotube Fibers

* 1

(KIST) 1 /

(CNT)

. (PAN)

.

CNT CNT

. CNT

.

.


: 2015 4 15~17(~) 3

: KINTEX

: POLY1-4


: , : 10:25, :

Hybrid Nanomaterials Based on Defective Nanocarbons: Promising

Energy and Biomedical Applications

(UNIST)

Carbon nanomaterials including fullerenes, carbon nanotubes, and graphenes represent the most important

class of materials today; their unique physical and chemical attributes advance their roles across most

advanced scientific and technology platforms. Defective nanocarbons such as graphene oxide and carbon

nanoparticles can offer various opportunities due to their facile synthetic nature, rich surface functional

groups as well as interesting photophysical properties. In particular, as a benign alternative to

semiconducting quantum dots, carbogenic nanoparticles (also known as carbon dots, CDs) have recently

received considerable attention by virtue of their interesting physical, optical, and chemical properties,

such as their photoluminescence, photostability, and electron transfer behavior. In the first part of the

presentation, the hybrid of carbon-dot-supported silver nanoparticles are exploited to exhibit the versatile

surface plasmon resonance of in polymer optoelectronic devices such as PLED and PSC with a record-

high efficiency. Moreover, a novel design is described of highly biocompatible, fluorescent, folic acid-

functionalized CDs as carriers for the photosensitizer to achieve simultaneous biological imaging and

targeted photodynamic therapy. In addition, our early effort in taking advantages of highly biocompatible

and photoluminescent CDs in other theranostic applications will be presented.


: 2015 4 15~17(~) 3

: KINTEX

: POLY1-5


: , : 10:55, :

Preparation of carbon materials using high energy radiation

Carbon materials are widely used for a variety of applications such as energy, environment, electronics,

and bioelectronics. They have been prepared by various chemical and physical methods. Among them,

high energy radiation-based method is an attractive way to prepare and modify carbon materials due to

several advantages, such as an eco-friendly process without any harsh chemical agents, a temperature-

independent process, fast and easy controllability, and a low processing cost. In this talk, the preparation

and modification of carbon materials by high energy radiation, such as electron beams, ion beams, and -

rays, will be presented.


: 2015 4 15~17(~) 3

: KINTEX

: POLY1-6


: , : 11:15, :

()

"

"

.

. "PAN ,

Pitch , " ,

PAN 90% .

Point ,

.

/

.


: 2015 4 15~17(~) 3

: KINTEX

: POLY1-7


: , : 11:40, :

Diverse Carbon-based Nanohybrid Materials for Energy Devices,

Photocatalysis, and Sensing

Nanostructured carbons have already been recognized as critical element in recent nanotechnological

applications with the development of graphene, along with conventional carbon nanotubes or graphites.

Coupling carbon moieties with semiconductors play a central role in enhancing the performance of

energy conversion and stroge devices, photocatalysis for solar fuel generation and environmental

remediation, and electrocatalytic activities. Integrating carbons with noble metal nanostructures have also

shown premise for advanced catalytic and sensing properties. A massive amount of efforts have been

devoted to the understanding of the interface properties and developing tailored hybrid nanoarchitectures.

In this presentation, fabrication of diverse types of hybrid carbon nanostructures utilizing self-assembly,

direct carbonization, hybridization of graphene, etc. will be introduced first and their detailed structural

assessment is discussed. Application of the resultant nanostructures in electrodes of energy conversion

and storage devices, visible light active photocatalysts for solar fuel and degradation of organic pollutants,

and surface-plasmon-based enhanced optical biosensing will be the main subject of discussion.Block-

copolymer-templated diverse hybrid graphitic carbons have shown promising properties as electrodes in

solar cell, fuel cell and metal-air battery. Similar types of carbon nanostructures exhibited viable activity

in visible light photocatalysis for water splitting and degradation of toxic chemicals. Finally, charged-,

doped-, or neat-graphene oxides and their reduced analogues were assembled in surface plasmon sensing

devices and enhanced sensing was demonstrated based on well-defined multilayer thin film geometries.


: 2015 4 15~17(~) 3

: KINTEX

: POLY1-8


: , : 12:05, :

PAN pitch

,

. polyacrylonitrile pitch

. , (

) .

.

, .

, crystallinity .

functional group morphological

. --

.

.


: 2015 4 15~17(~) 3

: KINTEX

: POLY2-1

: Current Trends in Responsive Polymers

: , : 13:30, :

Enhanced Plasmonic Sensing and Catalysis of Hybrid Metal

Nanostructures Mediated by Responsive Polymers

Stimuli-responsive polymers have been exploited in diverse nanotechnological applications. We introduce

our recent efforts to utilize pH- or temperature-sensitive polymers to enhance the function of

photocatalysis, electrocatalysis, and optical sensing. Smart bimetallic core@shell nanoparticles were

fabricated based on gold nanoparticles (AuNPs) decorated with pH-sensitive polymer shell. The

bimetallic nanostructures of AuNP@P4VP nanocomposites containing another type of metal NP at the

P4VP periphery exhibit a controlled sensing property in terms of the change in the refractive index of

surrounding media and a typical electrocatalytic activity for methanol oxidation reaction. A plasmonic

coupling sensing device was also designed, comprising gold nanoparticles (AuNPs) separated from Au

substrate through a stimuli-sensitive polymer linker layer. Plasmonic nanostructures coupled with thermo-

responsive poly(N-isopropylacrylamide) (PNIPAM) polymers were used to investigate the unique

plasmonic-coupling-based SPR sensing properties associated with swelling-shrinking transitions in the

polymer linker brush. Noble metal nanostructure coupled with responsive polymer were used to probe

unique plasmonic mediated photocatalytic properties associated with swelling-shrinking transitions in

polymer chains triggered by specific external stimuli.


: 2015 4 15~17(~) 3

: KINTEX

: POLY2-2


: , : 14:00, :

Volume phase transition of light responsive hydrogels and their

application

Hydrogels are three-dimensional network structures of hydrophilic polymers by physical and chemical

cross-linking and can be expanded their volumes by absorption water. Some of them change its

equilibrium swelling state in responds to external stimuli, such as pH, light, temperature, and electric field.

We have found that composite hydrogels consisting of photo-thermal conversion materials embedded

within a thermally responsive polymer matrix provide an efficient means to trigger changes in volumetric

swelling by visible light irradiation. We maximized degree of volume change triggered by light by

adjusting the lower critical solution temperature (LCST) of the hydrogels, providing highly responsive

hydrogels that show rapid and significant light-induced volume change. Base on light-responsibility of

hydrogels, we have successfully fabricated light-controlled actuators, microfluidic valve, and smart

window for energy saving. For more potential applications, light-responsive hydrogels were prepared

with controlled size and shape by using microfluidic device and alginate templating method.


: 2015 4 15~17(~) 3

: KINTEX

: POLY2-3


: , : 14:50, :

Noncovalent Polymer-Gatekeeper in Mesoporous Silica Nanoparticles

as a Targeted Drug Delivery Platform

(UNIST)

Nanoscopic delivery vehicles capable of encapsulating drug molecules and releasing them in response to

external stimuli are of great interest due to implications in therapeutic applications. Micellar assemblies

are promising scaffolds to overcome many of the problems faced with traditional chemotherapies because

of their capacity for non-covalent, hydrophobic guest molecule binding. However, the stability of

encapsulation with such self-assembled systems is limited during blood circulation because of a requisite

concentration for assembly formation and low encapsulation stability. Thus, deliberate molecular design

for stable encapsulation, targeting and triggered release is required. For this purpose, we have developed a

facile synthetic method for highly stable, polymer-caged hollow nanoparticles using a simple intra/inter-

chain crosslinking reaction. We show a simple method for the preparation of biocompatible nanovehicles

that provides the ability to encapsulate hydrophobic or hydrophilic drug molecules. We can control the

size of the nano-carriers and release kinetics depending on crosslinking in responsive to stimuli. Nano-

carriers showed great stability to encapsulate drug molecules and drugs were only released inside cell. In

addition, we can use surface modified nano-carriers for target delivery system. Hence, the stimuli

responsive nano-carrier formation using self-crosslinking polymers and the corresponding method of

surface modification are a promising platform for creating polymer nanogels for a range of biomedical

applications, from drug delivery to biosensing.


: 2015 4 15~17(~) 3

: KINTEX

: POLY2-4


: , : 15:20, :

/ Lower Critical Solution

Temperature (LCST)

, , , ,

. ,

,

. ,

poly(ethylene oxide) (PEO) . ,

PEO

. /

, turbidity LCST ,

. , ,

, , -, -

.


: 2015 4 15~17(~) 3

: KINTEX

: POLY2-5


: , : 15:50, :

Cross-linkable and Degradable Layer-by-Layer Assembly under

Cytocompatible Conditions for Cell-Encapsulation

* 1 2

1(KAIST) 2(UNIST)

Layer-by-layer (LbL) assembly has recently emerged as a highly versatile and promising method for

biochemical and biomedical applications. Accordingly, it is urgently necessary to develop a

cytocompatible LbL assembly technique that is stable and offers on-demand degradation and

functionalization. In this study, we developed a simple and biocompatible LbL technique that cross-links

the layers through covalent bonds under physiological conditions without requirement of any post-

treatments or additives. By utilizing the dynamic nature of the disulfide bond, stable LbL films can be

spontaneously formed during the process, further functionalized using thiol-maleimide chemistry, and

degraded in response to glutathione. In addition, we demonstrated that the method is applicable to plate

surfaces, spherical nanoparticles, and even living cells.


: 2015 4 15~17(~) 3

: KINTEX

: INOR1-1

: New Visions in Organometallics and Nanochemistry

: , : 09:00, :

Palladium(II) Coordination Cages

Diverse poly-pyridyl N-donor ligands that can coordinate two or more remote metal centers were used to

construct desirable molecular structures. Unique cage complexes [(Me4en)3Pd3(L1)2](X)6 (L1 = 1,3,5-

tris(isonicotinoyloxyethyl)cyanurate; X-= BF4- and ClO4

-) were constructed. A single water molecule in a

skeletal cage was reversibly associated and dissociated via a combination of the adequate space, polar

environment, and conformational flexibility of the cage. In Suzuki-Miyaura C-C cross-coupling reactions,

the cage complex showed significant catalytic activity along with the effects of the isolated single water

molecule. On the other hand, we reported the synthesis and operation of a nano-dimension 24 24 15

3 ball-joint-type host-guest system consisting of unprecedented conglomerate of two distinct helical

metallacyclophanes, chiral isomer (P)-[Pd3X6(L2)2]@(M)-[Pd3X6(L2)(L3)] and its enantiomer (M)-

[Pd3X6(L2)2]@(P)-[Pd3X6(L2)(L3)], via the reaction of racemic helical metallacyclophanes, (P,M)-

[Pd3X6(L2)2] with tridentate L3, or direct reaction of 10 small components (six palladium(II), three L2, and

one L3, L2 = N,N,N-tris(2-pyridinylethyl)-1,3,5-benzenetricarboxamide; L3 = N,N,N-tris(3-

pyridinylpropyl)-1,3,5-benzenetricarboxylate; X- = Cl- and Br-). The host-guest aggregation can be

ascribed to one interaction and three -NHO=C- hydrogen-bonds along with the combined helicity.

The host-guest system shows a reversible equilibrium between the aggregate and its dissociated species in

solution. Such equilibrium control of the host-guest system is reminiscent of left and right ball-and-

socket joint behavior.


: 2015 4 15~17(~) 3

: KINTEX

: INOR1-2


: , : 09:25, :

Nanostructured Bulk Thermoelectric Materials for Energy Harvesting

Applications

Upon confronting present energetic and environmental challenges, the global need for utilizing exhausted

waste heat has been accelerated. In effect, thermoelectric materials are gathering a great interest as a

potential alternative energy source because of their capability of direct energy conversion between heat

and electricity. The increase of thermoelectric efficiencies is one of the main challenges of our scientific

community. The performance of a thermoelectric material is assessed with the figure of merit ZT defined

as (S2????/k)T; where S is the Seebeck coefficient (or thermopower), ???? electrical conductivity,

thermal conductivity, and T is the temperature. Recent theoretical and experimental studies show that the

use of thermoelectric materials comprising nanostructured components increases ZT relative to that of the

bulk counterparts of these materials. Minimizing thermal conductivity while maintaining the electrical

conductivity is the key point in formation of nanoscaled or nanocomposite thermoelectric. Controlling the

size and content of the nanoscale constituents within the bulk materials is especially important to achieve

high ZT. Thus, new routes for the preparation of these components as nanoscale powders are essential for

incorporating them as nanoscale constituents of the bulk materials. In this presentation, an overview of

recent advances in the development of high performance nanoscaled thermoelectric materials.


: 2015 4 15~17(~) 3

: KINTEX

: INOR1-3


: , : 09:50, :

Electrical Activation of Mg-doped GaN Epitaxial Layer by

Electrochemical Method

GaN Optoelectric

n-type GaN p-type GaN . n-GaN

, p-GaN n-GaN ~10% . p-GaN

, GaN

, p-GaN .

p-GaN . p-GaN

Mg-H complex , dangling bond hole

.

,

Mg-H

. ,

, ,

SIMS .

1 order , hole

.

. LED Near-UV LED , LED ~30%

. Leakage

mechanism , LED

.

, .


: 2015 4 15~17(~) 3

: KINTEX

: INOR1-4


: , : 10:15, :

Facet-controlled alloy nanoparticles: Design, Synthesis, and

Application

Alloying and dealloying behaviors in the nanoscale particles are greatly different from those of bulk

materials, because the surface energy of nanoparticles is significant in determining the overall particle

energy. We have been particularly interested in the alloy formation in the facet nanoparticles; facet-

controlled nanoparticles can now generate geometrically precise energy gradients within the entire

nanoparticle and therefore geometrically-predetermined phase segregation is now feasible. Herein I

present our recent efforts in the nanoscale alloy formation and nanoparticle-specific reactivities with the

ultimate goal of development of atom efficient and highly active nanocatalysts for energy applications.


: 2015 4 15~17(~) 3

: KINTEX

: INOR1-5


: , : 10:50, :

Improved Photoelectrochemical Water Splitting Efficiency by the

Formation of Metal Oxide Composite

Artificial photosynthetic systems are promising approaches to convert sunlight into chemical fuels.The

most popular strategy is photoelectrochemical (PEC) water splitting to produce hydrogen sustainably.

Metal oxide composites, typically comprising a primary photon absorbing semiconductor with a

secondary semiconductor that may play a number of assisting roles, are constructed using various

materials to elucidate the processes of electron-hole separation and charge transport through the

composite. These composite structures are divided into four different configurations depending on the

possible electron-hole separation mechanism. These systems elucidate the effect of conduction and

valence band positions of the individual components of composite materials.


: 2015 4 15~17(~) 3

: KINTEX

: INOR1-7


: , : 11:20, :

-

()(KAIST)


: 2015 4 15~17(~) 3

: KINTEX

: INOR2-1

: Recent Advances in Organometallic Chemistry

: , : 13:30, :

N-Heterocyclic Carbenes Mimicking Transition Metal Complexes

(POSTECH)

N-heterocyclic carbenes (NHCs) are well-known to stabilize main group radicals and radical ions.

Pioneered by the Bertrand and other groups, phosphoryl, silyl, boryl and other organic radicals stabilized

by NHCs have been isolated and characterized. A successful preparation of the radical compounds was

explained by NHCs pi-acceptor character, which imparts remarkable stability because the significant

portion of the spin density of the radicals resides on the carbene carbon. We found that NHCs could

stabilize nitric oxide (NO) radical in a solution phase to form stable NHC NO radicals. Although nitrous

oxide was dominantly formed during the thermolysis of NHC nitric oxide compounds, nitric oxide was

also found to be thermally transferred to other N-heterocyclic carbenes. This suggests potential biological

applications for NO delivery. Furthermore, this study adds another example of stable singlet carbenes

acting as mimics for transition metal centers. Further studies on carbenes reactivity with other small

molecules will deepen our understanding of this interesting resemblance. Full characterization of the

compounds including X-ray crystallography, EPR, UV-vis, and cyclic voltammetry will be presented in

addition to the mechanistic studies and NO transfer experiments.


: 2015 4 15~17(~) 3

: KINTEX

: INOR2-2


: , : 14:00, :

Cycloaddition of Carbon Dioxide to Epoxides Using Catalysts

Cyclic carbonates could be easily synthesized via the cycloaddition of CO2 to epoxides, and they could be

widely used as polar aprotic solvents, electrolytes for lithium ion batteries, and precursors for

polycarbonates, enantiopure aminoalcohols, thermosetting coatings, and pharmaceutical intermediate. For

the synthesis of cyclic carbonates, many examples of homogeneous catalytic systems were reported in the

literature. The new advances of catalysts such as metal-based and metal-free compounds for

cycloaddition reaction will be presented. Acknowledgment: This work was financially supported by the

Korean Ministry of Education (MOE) and the National Research Foundation of Korea (NRF) through the

Creative Human Resource Training Project for Regional Innovation (grant number 2014H1C1A1066874).


: 2015 4 15~17(~) 3

: KINTEX

: INOR2-3


: , : 15:00, :

Briphos: A New Class of -Acceptor Ligand Induced by Geometrical

Constraints

(KAIST)

There has been continuing interest in transition metal catalysis: it is hoped that these reactions will help in

the development of unprecedented chemical reactions as well as to providing green chemical processes in

the pharmaceutical and find-chemical industries. Indeed, the catalytic performance of the studied

transition metals highly depends on the character of the ligands that bind to the central metal atoms. Thus

the investigation of ligand effects has been one of the major research topics in the field of transition metal

catalysis.We here report a new class of bicyclic bridgehead phosphoramidite (briphos) ligand based on

the bicyclo[3,3,1]nonane structure. We show that the geometrical constraints in briphos with respect to its

linear analogs enhance -acceptor ability. Furthermore, facile tuning of briphos leads to highly efficient

ligands showing dramatic ligand acceleration effect (LAE), new catalytic reactivity in Rh(I)-catalyzed

conjugate additions of aryl boronic acids.The design of briphos ligand is based on our observation that

internal hydrogen bonds significantly promote the imine formation of benzophenone and the imine

products have been used for stereoselective generation of axial compounds and chiral-at-metal

complexes.Reference1. Lee, A.; Ahn, S.; Kang, K.; Seo, M.-S.; Kim, Y.; Kim, W. Y.; Kim, H. Org. Lett.

2014, 16, 54902. Seo, M.-S., Lee, A., Kim, H. Org. Lett. 2014, 16, 2950 3. Seo, M.-S., Kim, K., Kim, H.

Chem. Comm. 2013, 49, 11623


: 2015 4 15~17(~) 3

: KINTEX

: INOR2-4


: , : 15:30, :

Organometallic compounds of transition metals and/or main group

metals for precise polymerization of olefin and/or styrene

*

Organolithium compounds were efficiently utilized in the construction of various transition metal

complexes for olefin polymerizations in our laboratory. Complexes 1-3 exhibited high activity, high 1-

octene incorporation, and high molecular weight in ethylene/1-octene copolymerizations. Complexes 4

and 5 showed excellent catalytic performances in 1-decene oligomerizations for lubricant basestock and

in ethylene/norbornene copolymerizations, respectively. Recently, we expanded utilization of the main

group organometallic compounds, alkyllithium and dialkylzinc, to the area of "catalyzed chain growth" to

construct polyolefin-block-polystyrene.


: 2015 4 15~17(~) 3

: KINTEX

: PHYS1-1

: Biophysical Chemistry: Biological Phenomena Viewed by Physical Chemistry

: , : 09:00, :

Computer Simulation Techniques in Biophysical Problems

With ever-increasing computational power and developments in user-friendly simulation software,

computer simulations have now become indispensible tools in studying biophysical problems including

enzyme catalysis, membrane structure and dynamics, and even cell functions. However, since biological

systems are still too complex to be studied by first-principle computational techniques, various levels of

approximations and techniques are employed depending on the systems of interest. In this talk, I will

briefly overview currently available particle-based computer simulation techniques by introducing several

biophysical problems I have been investigating in recent years.


: 2015 4 15~17(~) 3

: KINTEX

: PHYS1-2


: , : 09:30, :

Implications of DNA sequence composition in the chromosome

structure and epigenetics

(UNIST)

The chromosome spends most of its lifetime in the interphase in which it is only loosely condensed and

hence viewed as a dynamic polymer. Its structure and dynamics globally affect the gene expression but it

is only recent that its average structure was presented through the Hi-C technique by showing the intra-

and inter-chromosomal contact map of the whole DNA. We recently discovered that the Hi-C contact

map highly and universally correlates with the local AT content. From all-atom molecular dynamics

simulations, we hypothesized that the polycation-driven condensation of the DNA explains such global

behavior. We proved the hypothesis by designing a simple in vitro system for the single molecule

measurement of dsDNA-to-dsDNA interaction.


: 2015 4 15~17(~) 3

: KINTEX

: PHYS1-3


: , : 10:00, :

Upconverting nanoparticles: a versatile platform for wide-field two-

photon microscopy

(GIST)

Lanthanide ion-doped upconversion nanoparticles (UCNPs), which emit in the visible range upon

absorption of NIR photons, have attracted great attention in the area of biological imaging owing to their

advantageous properties. First, two-photon upconversion of NIR excitation to the emission of a visible

photon is so efficient that a tiny CW laser with the output of tens of milliwatts is sufficient as the

excitation source even for single-particle detection. Therefore, inexpensive wide-field two-photon

imaging can easily be achieved with UCNPs, which is not possible with organic fluorophores and

femtosecond laser systems used in conventional two-photon microscopy. Second, by employing NIR

excitation, one can suppress cellular autofluorescence, hardly induce photo-damage to cells, and achieve

relatively deep penetration into tissues. In addition, UCNPs are extremely photo-stable without any

photoblinking and photobleaching, and finally, their cytotoxicity turns out to be very low. All these

aspects strongly suggests that the UCNP-based imaging should provide an excellent platform for non-

scanning wide-field two-photon microscopy, which is capable of high-speed, high-contrast,

biocompatible, uninterrupted, and long-term imaging. Such advanced concepts in microscopy were fully

demonstrated in our study on the real-time tracking of single UCNPs in live cells. Furthermore, we

employed this technique to investigate the mechanism of gene delivery, addressing the issues such as

DNA release, cell division.


: 2015 4 15~17(~) 3

: KINTEX

: PHYS1-4


: , : 10:40, :

Energetics and Dynamics of Transport of Ions and Biomolecules

through Cyclic Peptide Nanotubes

Cyclic peptide nanotubes (CPNs) are synthetic proteins which transport ions and biomolecules through

lipid bilayer membranes. We used molecular dynamics (MD) simulations to calculate potential of mean

force (PMF), position-dependent diffusion coefficients, and force autocorrelation functions (FACs) for

ions and glucose through CPNs embedded in a DMPC lipid bilayer membrane.


: 2015 4 15~17(~) 3

: KINTEX

: PHYS1-5


: , : 11:10, :

Probing protein interactions and dynamics in a single living cell

(POSTECH) /

Dynamic interactions between membrane proteins and ligands determine correct cellular responses to

diverse environmental changes. Because various protein complexes on a plasma membrane participate in

cellular functions, technique identifying complex interactions of membrane proteins with spatio-temporal

resolution in a single living cell is highly demanding. Here I present an imaging technique of membrane

protein interactions that utilizes the accurate measurement of diffusion coefficient of membrane proteins

by tracking individual proteins in a single living cell. We validated this approach that can measure the

interactions between ligands and membrane proteins using an epidermal growth factor receptor and show

its applicability in measuring dissociation constant of ligands and mutant specific interactions in a single

living cell. We extended our technique to G protein-coupled receptors, which confirms the dissociation of

Gi-protein at the downstream of ligand interactions. Our results demonstrate that our approach would be a

powerful technique for investigating the various interactions of membrane proteins and the processes of

signal transduction in a single living cell.


: 2015 4 15~17(~) 3

: KINTEX

: PHYS1-6


: , : 11:40, :

NMR dynamics study of Z-DNA binding proteins and miRNAs

Left-handed Z-DNA is a higher energy conformation than B-DNA and is induced by high salt, negative

supercoiling, and complex formation with Z-DNA binding protein (ZBPs). ZBPs have been identified in

RNA editing enzyme (ADAR1), DNA-dependent activator of interferon regulatory factor (DAI), viral

E3L protein and protein kinase containing Z-DNA binding domains (PKZ). In this study, we determined

the solution structure of the free from of caZPKZ by multidimensional heteronuclear NMR spectroscopy.

We also performed NMR experiments on complexes of caZPKZ with DNA duplexes, dT(CG)3 and

d(CG)3 under various NaCl concentrations. We investigated changes in the conformation and dynamics

of caZPKZ induced by increment of NaCl concentration. Comparison of these results to that of ZADAR1

provides the molecular basis for B?Z transition mechanism of ZBPs, which is modulated by

conformational dynamics of a key tyrosine residue in the 3 helix.In plants, the DCL1 enzyme processed

primary miR156a into miR156a/miR156a* duplex via a loop-to-base processing mecanism. Some pairing

mutants on the B5 bulge (P-B5 mutants) caused earlier flowering than wild-type pri-miR156a. Here, we

have investigated the structural and/or dynamics changes of the miR/miR* duplex region induced by P-

B5 mutations. This study provides insight into the molecular mechanism on the second cleavage reaction

at lower stem structure by DCL1.


: 2015 4 15~17(~) 3

: KINTEX

: PHYS2-1

: Recent Trends in Physical Chemistry

: , : 13:25, :

Something happening in a non-adiabatic region: A proton-coupled

electron-transfer case

A brief description on the backgrounds leading to the interests about non-adiabatic regions of chemical

changes will be followed by discussions on detailed dynamics of a proton-coupled electron-transfer

(PCET) process as a representative case of the non-adiabatic regions. To capture the 'microscopic yet

dynamical view' of the non-adiabatic stage, the time-dependent quantum wave-packet propagation

method in conjunction with high-level electron correlation theories, MRCI and IP-EOM-CC methods,

was applied to the dynamics of the charge-transfer (CT) excited state of FHCl corresponding to F+HCl-.

The dynamics of this CT state, generated by the photo-detachment of an electron from the precursor anion

FHCl-, corresponds to a bidirectional PCET with two dissociation channels: the electron transfer (ET,

generating FH and Cl) and proton transfer (PT, generating F and HCl) paths. Calculated branching ratio

of ET/PT disclosed a surprising fact that PT prevail over ET. More importantly, a detailed analysis of the

non-adiabatic region suggests that the proton movement starts about 3 femto-seconds earlier than the net

adjustment of electrons distribution, and the electron adjustment is triggered by the initial movement of

the proton. A few more model systems of X-H-Y will be discussed too, and some comments on recent

researches related to this topic will be made as a closing remark.


: 2015 4 15~17(~) 3

: KINTEX

: PHYS2-2


: , : 13:45, :

Transient Chemical Species : A Study of Reaction Dynamics and

Applications

Two topics related to transient organic species will be presented.

a) Atom-radical reaction dynamics: Oxidation reaction dynamics of a series of hydrocarbon radicals has

been examined as prototypal radical-radical oxidation reactions. High-resolution laser spectroscopy in a

crossed-beam configuration was applied to examine the nascent rovibrational state distributions and

Doppler profiles of the reactive scattering products. The analyses of the product energy and population

distributions demonstrated the existence of unusual dynamic characteristics and competition between the

addition and abstraction reaction mechanisms at the molecular level. These features in sharp contrast with

those of the oxidation reactions of closed-shell hydrocarbon molecules will be discussed with the aid of

the ab initio and quantum statistical calculations.

b) Organic electronic devices Semiconducting -conjugated organic clusters were utilized to prepare the

various organic devices such as OFETs (Organic Field-effect Transistors), OLEFETs (Organic Light-

Emitting Field Effect Transistors), inverters, etc. The weakly bound and highly directional neutral cluster

beams were quite efficient in producing the high-quality thin films leading to significant improvements in

surface morphology, crystallinity and packing density at room temperature. The OFETs and OLEFETs

demonstrated good field-effect characteristics, stress-free operational stability, and electroluminescence

under ambient conditions. In the cases of organic CMOS inverters ideal performance was realized by

integration of unipolar OFETs.


: 2015 4 15~17(~) 3

: KINTEX

: PHYS2-3


: , : 14:05, :

Femtosecond X-ray liquidography captures the formation of chemical

bond in the solution phase

(KAIST)

The pump-probe X-ray diffraction and scattering techniques have now been fully established as a

powerful method to investigate molecular structural dynamics [1-5]. We have employed the techniques to

study structural dynamics and spatiotemporal kinetics of many molecular systems including diatomic

molecules, haloalkanes, organometallic complexes and protein molecules over timescales from ps to

milliseconds. X-ray crystallography, the major structural tool to determine 3D structures of proteins, can

be extended to time-resolved X-ray crystallography with a laser-excitation and X-ray-probe scheme, but

has been limited to a few model systems due to the stringent prerequisites such as highly-ordered and

radiation-resistant single crystals. These problems can be overcome by applying time-resolved X-ray

diffraction directly to protein solutions rather than protein single crystals. To emphasize that structural

information can be obtained from the liquid phase, this time-resolved X-ray solution scattering technique

is named time-resolved X-ray liquidography (TRXL) in analogy to time-resolved X-ray crystallography

where the structural information of reaction intermediates is obtained from the crystalline phase. We will

present our recent results including the achievement of femtosecond TRXL by using an X-ray free

electron laser.[1] Direct observation of bond formation in solution with femtosecond X-ray scattering,

K. H. Kim, J. G. Kim, S. Nozawa, T. Sato, K. Y. Oang, T. W. Kim, H. Ki, J. Jo, S. Park, C. Song, T. Sato,

K. Ogawa, T. Togashi, K. Tono, M. Yabashi, T. Ishikawa, J. Kim, R. Ryoo, J. Kim, H. Ihee*, S. Adachi,

Nature, 2015, in press.[90] Volume-conserving trans-cis isomerization pathways in photoactive yellow

protein visualized by picosecond X-ray crystallography, Y. O. Jung, J. H. Lee, J. Kim, M. Schmidt, K.

Moffat, V. Srajer, H. Ihee*, Nat. Chem., 2013, 5, 212-220.[3] Visualizing Solution-Phase Reaction

Dynamics with Time-Resolved X-ray Liquidography, H. Ihee*, Acc. Chem. Res., 2009, 42, 356-366

(Review Article).[4] Tracking the structural dynamics of proteins in solution using time-resolved wide-

angle X-ray scattering, M. Cammarata*, M. Levantino, F. Schotte, P. A. Anfinrud, F. Ewald, J. Choi, A.

Cupane, M. Wulff, H. Ihee*, Nature Methods, 2008, 5, 881-887.[22] Ultrafast X-ray diffraction of

transient molecular structures in solution, H. Ihee*, M. Lorenc, T. K. Kim, Q. Y. Kong, M. Cammarata,

J. H. Lee, S. Bratos, M. Wulff, Science, 2005, 309, 1223-1227.


: 2015 4 15~17(~) 3

: KINTEX

: PHYS2-4


: , : 14:30, :

Unprecedented colorimetric responses of polydiacetylene based

nanofibers

* 1 2

1 2

Polydiacetylene (PDA) polymers, which were typically prepared by UV irradiation, display unique the

blue to red color transition upon environmental stimulation. We report for the first time that

polydiacetylenes (PDAs) can be alternatively prepared via plasma induced polymerization process. The

degree of polymerization and color transitions could be manipulated by controlling the power of plasma

radio frequency, exposure time and by using acrylic mask. In the current study, 10, 12-pentacosadiynoic

acid (PCDA) monomers embedded electro-spun fibers, PCDA-HEG embedded fiber bearing

hexaethylene glycols (HEG) as head groups and their combinations were explored to study the steric

factors of head groups in color transition. We could also demonstrate that patterned colorimetric and

fluorometric images could be obtained through a simple acrylic mask with plasma. These results

demonstrate not only the first example of PDA polymerization via plasma but also a great potential of

plasma process to be used as patterning applications.


: 2015 4 15~17(~) 3

: KINTEX

: PHYS2-5


: , : 15:05, :

Study on graphene nanoribbon and residual polymer on graphene

using Raman spectroscopy

.

.

defect density .

hexagonal graphene

.

tensile strain . :1. Yoon, W., Lee, Y., Jang, H.,

Jang, M., Kim, J. S., Lee, H. S., Im, S., Boo, D., Park, J., and Ju, S. -Y., Graphene Nanoribbons Formed

by a Sonochemical Graphene Unzipping using Flavin Mononucleotide as a Template, Carbon, 81, 629-

638 (2014, article).2. Koo, E. -H., and Ju, S. -Y., Role of Residual Polymer on Chemical Vapor Grown

Graphene by Raman Spectroscopy, Carbon, 86, 318-324 (2015, article).


: 2015 4 15~17(~) 3

: KINTEX

: PHYS2-6


: , : 15:30, :

Electron Transport Characteristics of Molecular & Nano Structures on

the Organic Electronic Devices

Organic electronic devices based on conjugated small molecules and nano structures have been

extensively investigated as promising building blocks for nanoscale optical and electronic devices, such

as organic light emitting diode (OLED), organic photovoltaic (OPV) solar cell, thin film field effect

transistors (OFET), sensor and molecular electronic devices. However, only the electron transfer can

reveal the desired device functions, which strongly depends on the electronic structures of molecular and

nano components. Therefore, it is very important to understand how electron flows in a molecular and

nano structures and how to manipulate the electron transport behaviors for the development of new

functional organic electronic materials. The electron transport behavior can be classified by the phase of

organic materials. If the organic electronic devices are composed of bulk solid states, such as crystal and

amorphous, the electron transport is governed by inter-molecular hopping mechanism based on the

Marcus theory. Whereas, on the single molecule and nanostructure, the electron transport can be

explained by the intra-molecular ballistic transfer mechanism based on Non-equilibrium Greens function

(NEGF) theory. Therefore, controlling the bulk and molecular properties, such as morphology, growth

direction, and physical and chemical properties, can allow us to design new functional organic electronic

devices.In this presentation, I would like to introduce designed molecular and nano structures, and their

characteristic electron transport behaviors for on the organic electronic devices.


: 2015 4 15~17(~) 3

: KINTEX

: PHYS2-7


: , : 15:55, :

Equilibrium Dynamics in Electrolytes of Li-Ion Battery Studied by

Ultrafast Pump-probe and Two-Dimensional IR Spectroscopy

Electrolytes are ubiquitous and indispensable in all electrochemical devices including electrolytic cells,

capacitors, fuel cells, or batteries. Moreover, their function is the same in devices for serving as the

medium for the ion transport between electrodes. The electrolyte determines how fast the energy could be

released by controlling the rate of mass flow within the battery. After making solid electrolyte interphase

on the carbonaceous anode, there is no decomposition in electrolyte and Li ion transport occurs through

electrolyte. Thus, it has been suggested that the solvation structures and dynamics of Li ions in liquid

electrolyte play an essential role to Li-based battery performance. To mimic commercial electrolyte

composition composed of carbonates, Li ion were dissolved in diethylcarbonate (DEC) and its solvation

behavior was observed with IR spectroscopy as well as time-resolved IR spectroscopies including IR

pump-probe and 2D-IR experiments. IR spectroscopic results combined with DFT study reveals the

possible solvation structure and major interaction site for Li ion. Subsequent 2D-IR experiments show

that there is fast equilibrium solvation dynamics around Li-ion, which might give some clues about the

molecular mechanism of Li ion transport through electrolyte.


: 2015 4 15~17(~) 3

: KINTEX

: ANAL1-1

: Recent Trends in Separation Analysis I: Fundamentals

: , : 09:00, :

Analysis of polyethylene terephthalate (PET) by LC-MS and MALDI-

TOF

()

Polyethylene terephthalate (PET) is the most common thermoplastic polymer of the polyester resin family.

The PET polymer is used in fiber and stretch blown plastic bottles as well as high end films, especially

for the electro-optical application. Depending on the polymerization process and thermal treatment, the

PET shows different physical and chemical properties. This semi crystalline polymer contains wide range

of oligomers affecting the polymer properties in a different way. Thus it is strongly needed to extract and

identify the oligomer from the PET polymer and to investigate the detailed synthesized mechanism. In

this work we use the several extraction techniques and LC-MS as well as MALDI-TOF to analyze the

oligomers in detail. The cyclic and linear oligomers with molecular weight up to 7,000 are completely

identified. Thus using the separation and MASS spectrometry provides the sufficient valuable information

to improve the PET quality in a delicate manner.


: 2015 4 15~17(~) 3

: KINTEX

: ANAL1-2


: , : 09:25, :

Recent trends in Sports Doping Control

(KIST)

In 1999, the International Olympic Committee (IOC) led the way to creating the World Anti-Doping

Agency (WADA) through a collective initiative of sport and governments. WADA seeks to foster a

doping-free culture in sport. It combines the resources of sport and government to enhance, supplement

and coordinate existing efforts to educate athletes about the harmful effects of doping, reinforce the ideal

of fair play and detect those who cheat themselves and their sport.The use of performance-enhancing

drugs in sport is cheating. They are associated with serious medical complications and, above all, their

use is illegal. Procedures to detect prohibited substances in sports have been in operation for many years

and the analytical techniques used currently detect minute traces of substances, which may have been

taken several weeks ago. In this presentation, the state of the art analytical instruments, technology and

various applications will be introduced for anti-doping purpose.This work was supported by Korea

Institute of Science and Technology.


: 2015 4 15~17(~) 3

: KINTEX

: ANAL1-3


: , : 09:50, :

A Multi-Task, Multi-Dimensional Immunoaffinity Capillary

Electrophoresis for the Selective Purification and Characterization of

Protein Biomarkers in Biosamples

Norberto A. Guzman

Immuno-Engineering and Bioanalysis, Princeton Biochemicals, Inc., U.S.A.

The long-term survival of patients with chronic diseases, in particular cancer, is influenced significantly

by the detection of early-stage disease. Determination of accurate protein biomarkers in biological fluids

and cellular structures is of great value in early diagnosis of a disease, surveillance and asymptomatic

screening, and the most promising approach to improve prognosis. Biomarker-based companion

diagnostics are also becoming of great value in predicting response to treatment. Companion biomarkers

are designed to identify responsive patient sub-populations or those likely to experience adverse drug

effects. Using companion biomarkers yields safer and more efficacious drug products, reduces clinical

trials and development costs, improves post-marketing safety profiles and salvages therapies that

otherwise would not be granted approval. The advent of personalized medicine will require change in the

traditional paradigms for developing and commercializing new pharmaceutical products. Today, less than

1% of current drugs have a companion diagnostic, and 60% of the drugs in clinical trials have a

companion diagnostic in mind. Some drugs which have been withdrawn from market or Phase 3

development due to serious adverse events may have had a different fate if combined with a companion

diagnostic to identify responders or to closely monitor toxicity.

The proteome represents all the possible gene products of a cell. Any protein may exist in multiple forms

that vary within a particular cell or in different cells, because of modifications derived from co-

translational, post-translational, regulatory and degradative processes that affect protein structure,

localization, function and turnover. Therefore, a combination of proteomic techniques should be capable

to characterize all proteins in a biological system, including complex features, like isoforms, chemical or

enzymatic modifications, interactions and functional structures.

Immunoaffinity capillary electrophoresis (IACE), which benefits by using the power of highly selective

affinity capture agents with the high-resolving power of capillary electrophoresis (CE), has demonstrated

to be a useful tool for the isolation, separation, and quantification of proteins and peptides. When coupled

to one or more sensitive detectors, such as a laser-induced fluorescence detector (LIF) and/or a mass

spectrometer (MS), IACE is becoming an important tool for the characterization of proteins and peptides

present at a wide range of concentrations in simple and complex matrices. Furthermore, when IACE-LIF

and/or IACE-MS are coupled with artificial intelligence based pattern recognition systems, it could result

in a powerful tool to study early changes in the underlying pathophysiology of many diseases and toxic

conditions.

In this seminar I will discuss the use of a multi-dimensional, multi-task immuno-separation instrument

adapted to be coupled to one or more detectors, including a mass spectrometer, for the capture, separation,

quantification, and characterization of protein and peptides biomarkers in biological fluids, cell extracts

and exhaled breath. Furthermore, I will address the use of IACE for the analysis of isoforms, modified

proteins and peptides, degradants, and protein-drug conjugates. The IACE instrument can be

manufactured as a portable miniaturized point-of-care instrument to be used in doctors office,

ambulances, and remote locations.


: 2015 4 15~17(~) 3

: KINTEX

: ANAL1-4


: , : 10:35, :

Sequential injection - capillary electrophoresis: Fundamental design

and applications

Michael Charles Breadmore Daniel Gstoettenmayer Adam J Gaudry Ala Alhusban Joan

Marc Cabot Leile Ranjbar Hong Heng See Petr Smjekal*

School of Chemistry, University of Tasmania, Australia

Traditional capillary electrophoresis instrumentals operate in the batch mode: the capillary is transferred

from one vial to another for flushing, injection and separation. This is advantageous because of the

flexibility and level of automated throughput that can be achieved, particularly for method development

and optimisation. However, it is also limited in the ability to couple with other processes streams. Flow-

based systems offer an alternative instrument design that makes it easier to achieve regular and routine

monitoring of a particular sample as a function of time. Here, the construction and capabilities of a

number of flow-based capillary electrophoresis systems based on sequential injection will be discussed.

Unique to this design is the ability to efficiently inject all ions from a specific sample volume under

stacking conditions to provide superior detection limits. Applications of these systems for water

monitoring, cell cultures and for homemade explosives will be discussed.


: 2015 4 15~17(~) 3

: KINTEX

: ANAL1-5


: , : 11:10, :

Development of a Multiuple Channel Capillary Electrophoresis System

(KRISS)

Capillary electrophoresis (CE) features unique advantages of high separation efficiency and small sample

volume-requirement. In addition, instrumentation for electrophoretic separation is simple, which

facilitates implementation of multiple channel separation for high throughput analysis. We have devised a

sample introduction method that allows simultaneous introduction of multiple samples without the help of

individualized sample wells. In a hydrophobic environment created with a non-polar solvent, aqueous

samples attached at the tips of sample loaders autonomously form hydrophilic sample bridges with the

entrances of CE channels. The hydrophilic bridges not only prevent samples from dispersing toward

others but also maintain themselves against possible agitations. Therefore, samples are to be intendedly

introduced into the separation channels without interfering others, which renders highly simple apparatus

design acceptable. Our plan is to develop an automated multiple channel CE analysis system for high

throughput analysis of routine samples based on the unique sample introduction method. The goal of

development is to realize a highly competitive commercial instrument.


: 2015 4 15~17(~) 3

: KINTEX

: ANAL1-6


: , : 11:35, :

The chemical structures of newely identified analogures of drugs in

adulterated foods

The various forms of dietary supplements have been developed, because consumer demand for dietary

supplements that support their new or continuing healthy lifestyle has increased steadily in recent years.

The various forms of analogues of erectile dysfunction and anti-obesity drugs in the dietary supplements

which produced to avoid skillfully the regulation of the Ministry of Food and Drug Safety have been

increased. Recently, the most widely prescribed drug, sibutramine, was withdrawn from the market.

However, phosphodiesterase-5 (PDE-5) inhibitors have been developed to treat erectile dysfunction (ED)

and various ED drugs such as sildenafil, tadalafil, vardenafil, and mirodenafil have come onto the market.

Some manufacturers dope synthetic drugs into these products to increase treatment efficacy. To date, the

57 analogues of drugs such as PDE-5 inhibitors and sibutramine in adulterated health food products have

been identified and our laboratory has been continuously identifying these kind of drugs. The 8 illegal

analogues of drugs identified in adulterated foods in 2013 to 2014 were registered in the Criteria and

Standards for Food by MFDS and the analogues are continuously being discovered. The 6 out of 8

newely identified analogues of drugs have been first reported in Korea. The structures of 8 analogues of

erectile dysfunction(ED) were consistent with a proproxyphenyl-linked sildenafil, an acetylated product

of aminotadalafil or methylated tadalafil, and the new analogues were also found as impurities in illegal

analogues of drugs. Many analogues of ED may exist because of their chemical structures and the

analogues are becoming increasingly diversified and sophisticated in terms of their products and

processes. Therefore, it is essential to continuously monitor existing and newly identified analogues of

ED, along with elucidating its structural characteristics.


: 2015 4 15~17(~) 3

: KINTEX

: ANAL2-6

: Recent Trends in Separation Analysis II: Applications

: , : 15:45, :

Online MW sorting-based enzyme reactor for jumping over the

limitation of conventional shotgun proteomics

(KRISS)

In general proteomics, advanced mass spectrometry coupled with diverse liquid chromatography

techniques (LC-MS) has been considered as a fundamental way to both identify and quantify protein(s) of

interest in biological sample, as well as to study protein post-translational modifications (PTMs). To this

end, proteolytic preparation for protein sample, which is an essential step for bottom-up proteomic

analysis, is carried out by in-gel or in-solution digestion with various proteases. However, it is well

known that this step is generally labor-intensive and time-consuming (over 12 hours). In this presentation,

we introduce a microbore hollow fiber enzyme reactor (mHFER)-LC-MS platform developed recently for

online digestion with complementing the issues in general proteolytic preparation. Furthermore, we also

present a simple, ease-to-use, and online antibody-specific shotgun proteomics for understanding the

biological functions of protein PTMs study


: 2015 4 15~17(~) 3

: KINTEX

: ANAL2-1


: , : 13:30, :

Chemical profiling of various alkaloids in herbal medicines using pH

control liquid-liquid extraction and LC-ESI-tandem mass

spectrometry

Alkaloids with significant biological effects are frequently found to be the main constituents of various

herbal medicines. Several types of alkaloids extracted from Fangchi (F.) and Corydalisis (C.) species

were characterized using liquid chromatography-electrospray ionization tandem mass spectrometry (LC-

ESI-MS/MS). These interesting compounds were extracted from F. and C. species by sonication with 70%

CH3OH, and the extract was partitioned at pH values of 2 and 12. LC chromatographic separation of

alkaloids were investigated on reversed-phase C18 column with pH variation and composition of mobile

phase. Separation of these alkaloids in herbal extracts was found to be significantly affected on mobile

phase composition using gradient elution. Chemical profiling of alkaloids in F. and C. species was

successfully obtained for the classification of geographic origins and quality evaluation of herbal

medicines. Eight-types of alkaloids (aporpine, protoberberine, tetrahydroprotoberberine,

benzylisoquinoline, protopine, phthalide, morpine, and bisbenzylisoquinoline) observed in herbal

medicines were analyzed by electrospray ionization tandem mass spectrometry in positive ion mode.

Several types of fragmentations such as inductive and -cleavage, retro-Diels-Alder cleavage,

imminolization process or simple bond cleavage were observed according to their structural

characteristics. These fragmentation patterns could enable to instantly classify the specific alkaloid type

in MS/MS spectra of various alkaloids. Based on the MS/MS fragmentations, some of new alkaloids were

observed in herbal medicines.


: 2015 4 15~17(~) 3

: KINTEX

: ANAL2-2


: , : 13:55, :

Direct Characterization of Glycosylated Proteins by Ultrahigh-

Performance Nano LC-MS/MS

* Lance Wells1

1The Complex Carbohydrate Research Center, The University of Georgia

Protein post-translational modification (PTM) increases the functional diversity of the proteome by the

covalent addition of proteins. Therefore, identifying and understanding PTMs is critical in the study of

protein bioscience. Protein glycosylation is acknowledged as one of the major post-translational

modifications, with significant effects on protein folding, conformation, stability and activity. The need to

characterize glycoproteins continues to increase as more irrefutable examples of the essential role that

covalent carbohydrates in the proteins play in biological processes and functions. The extant challenge of

glycobiology and glycotechnology is to approach the extremely low level of sensitivity, used for PTM

analysis over the protein identification.In this study, several biologically important proteomic samples

was analyzed by shotgun proteomics method, the resulting modified peptides are separated and detected

by ultrahigh-performance nano liquid chromatography-tandem mass spectrometry (nano LC-MS/MS).

We, for the first time, identified specific O-GlcNAc modification sites of Oct1 and O-linked

glycosylation site of Tango1 with the state-of-the-art nano LC-Orbitrap Fusion Tribrid mass spectrometer.

Additionally, we focused on the analysis of native glycopeptide of endopolygalacturonases (EPGs) from

Botryotinia fuckeliana and polygalacturonase inhibiting proteins (PGIPs) from Phaseolus vulgaris to

define their structural interaction. The reports offer comprehensive information for the glycosylation

characterization of the EPGs and PGIPs including site identification of glycan attachment,

microheterogeneity determination of glycosylation, and N- and O-linked glycan profiles.This work

presents an overview of the methods, which have been successfully applied to the detection of level-

limited glycopeptides in the glycoproteins.Key Words: Oct1, Tango1, PGIPs, EPGs, Glycosylation, Site

mapping, and Nano LC-MS/MS


: 2015 4 15~17(~) 3

: KINTEX

: ANAL2-3


: , : 14:20, :

A novel derivatization method of free cyanide including cyanogen

chloride for the sensitive and rapid analysis of cyanide in chlorinated

drinking water by liquid chromatography-tandem mass spectrometry

A novel derivatization method of free cyanide (HCN + CN-) including cyanogen chloride in chlorinated

drinking water was developed with D-cysteine and hypochlorite. The optimum conditions (0.5 mM D-

cysteine, 0.5 mM hypochlorite, pH 4.5, and a reaction time of 10 min at room temperature) were

established by the variation of parameters. Cyanide (C13N15) was chosen as an internal standard. The

formed -thiocyanoalanine was directly injected into a liquid chromatography-tandem mass spectrometer

without any additional extraction or purification procedures. Under the established conditions, the limits

of detection and the limits of quantification were 0.07 ?g/L and 0.2 ?g/L, respectively, and the inter-day

relative standard deviation was less than 4% at concentrations of 4.0, 20.0, and 100.0 ?g/L. The method

was successfully applied to determine CN- in chlorinated water samples. The detected concentration

range and detection frequency of CN- were 0.20-8.42 ?g/L (14/24) in source drinking water and 0.21-

1.03 ?g/L (18/24) in chlorinated drinking water.


: 2015 4 15~17(~) 3

: KINTEX

: ANAL2-4


: , : 14:55, :

Determination of vaccenic and elaidic acid in commonly consumed

foods using a silver ion cartridge solid phase extraction method

coupled with GC GC-TOFMS

This study aimed to develop an analytical method for accurately estimating the ratio of vaccenic to elaidic

acid (V/E value). To estimate an accurate V/E value, a silver ion cartridge (SIC) solid phase extraction

(SPE) method was performed for removing cis-fatty acids. The removal efficiency of cis-fatty acids was

greater than 97.8%. However, the analytical values of total trans-fatty acids (TFAs) were not significantly

different between with SIC SPE method and without SIC SPE method. Comparison tests of the V/E

values produced by two different methods (without SIC SPE method and with SIC SPE method) using

comprehensive two-dimensional gas chromatography combined with time-of-flight mass spectrometry

(GC GC-TOFMS) were also carried out. Those two methods exhibited significant differences in the

estimated V/E values because removing cis-fatty acids affected the V/E value but did not affect the total

TFAs. The SIC SPE method coupled with GC GC-TOFMS suggested in this research is available to

estimate accurate V/E values in commonly consumed foods, such as margarines, milk products and beef

tallow.


: 2015 4 15~17(~) 3

: KINTEX

: ANAL2-5


: , : 15:20, :

Digital Microfluidics as a Versatile Bioanalysis Tool

(KRISS)

Digital microfluidics (DMF) is a fluid handling technique in which discrete droplets are manipulated on

the surface of an array of electrodes. In this talk, I will present two recent projects using solid samples on

a DMF device. First, I will describe the work integrating solid-phase microextraction (SPME) in DMF. In

the new system, a SPME fiber is used to extract analytes from a complex sample, and is then inserted into

a DMF device. Solvent droplets are then used to extract analytes from the fiber with continuous actuation,

followed by analysis with liquid chromatography and mass spectrometry. Compared to conventional

methods, the new technique allows for fast, efficient desorption of analytes from the SPME fiber using a

small volume of solvent. The miniaturized system allows for preconcentration of analytes and was

applied the analysis of steroid hormones in human urine. Second, I will describe our work implementing

magnetic particle-based immunoassays in DMF. To increase the assay throughput, a new platform

capable of performing complete immunoassays with minimal manual intervention was developed. This

instrument comprises three core components: a Pogo pin interface for digital microfluidic control, an

integrated photomultiplier tube for chemiluminescent detection, and an adjustable magnet for particle

separation. Using this automation system allowed for parallel sample processing and full factorial design

of experiments (DOE) optimization. Relative to macroscale methods, this DMF approach reduced reagent

volumes and analysis time, and moreover, this represents the first DOE optimization for immunoassays

implemented in a microfluidic system. I propose that these techniques have great potential for numerous

applications in bioanalysis and beyond.


: 2015 4 15~17(~) 3

: KINTEX

: BIO1-1

: Infectious Disease Research in Biochemistry and Structural Biology

: , : 09:15, :

Foot-and-mouth disease virus: a major global agricultural problem in

need of antiviral therapy

Foot-and-mouth disease (FMD) is a highly contagious disease of the cloven-hoofed animals caused by the

foot-and-mouth disease virus (FMDV; family Picornaviridae; genus Aphthovirus). FMD is the most

economically important veterinary pathogen due to its highly infectious nature, ability to cause persistent

infection and long-term effects on the condition and productivity of the many animal species it affects.

Due to the enormous socioeconomic consequences related to an FMD incursion, the main concern of

FMD-free major livestock producing countries is to prevent the introduction of the virus and/or to rapidly

eradicate it in case of an outbreak. Although vaccines have been crucial in controlling and eradicating

FMD from some parts of the world, the disease still affects millions of animals around the globe and

remains as the most important veterinary disease limiting trade of animals and animal products. The use

of current FMD vaccines to induce early protection is limited; thus, alternative/supplementary methods to

rapidly reduce the spread of FMDV in outbreak situations are urgently needed. One possible alternative

would be the use of antiviral drugs in a vaccinated zone to control viral dissemination and fill the

immunity-gap between time of vaccination and development of protective immunity. Unfortunately,

there are not yet commercially available antiviral therapies for prevention or treatment of FMDV

infection. In this presentation, the current efforts to discover FMD-antiviral drugs will be reviewed to help

and provide insights to investigators for identification of potential therapeutics to fight against this

devastating animal disease.


: 2015 4 15~17(~) 3

: KINTEX

: BIO1-2


: , : 09:40, :

Regulating the regulators: Basic concept and clinical application for

PD-1/PD-L1 interaction

For more than 100 years, immunotherapy for infectious disease and cancer has played an ever-increasing

role as a therapeutic regimen even though there are not many approved drugs and regimens. Activating

the immune system for therapeutic benefit in infectious disease and cancer has long been a goal in

immunology and oncology. After repetitive failures, the tide has finally changed due to the success of

recent proof-of-concept clinical trials using antibodies to blockade immune inhibitory molecules such as

CTLA-4 and PD-1. These successes suggest that tolerance raised by immune suppressive

microenvironment is a major obstacle for immunotherapy and therefore, blocking the tolerance is the first

step to rejuvenate antigen-specific T cell immune responses. In this seminar, the basic concept of T cell

exhaustion and the role of inhibitory molecules expressed by the exhausted T cells and regulatory T cells.

In addition, a representative inhibitory molecule, PD-1, and its current clinical use to treat infectious

disease and cancer will be introduced. Finally, future strategy to enhance the efficacy of the regulator

blockade therapy will be discussed.


: 2015 4 15~17(~) 3

: KINTEX

: BIO1-3


: , : 10:05, :

Characterization and Lead optimization of a novel hepatitis C virus

inhibitor acting on early and late steps of the viral life cycle

Marc P. Windisch

Institut Pasteur Korea Hepatitis Research

Approx. 200 million patients Hepatitis are chronically infected with hepatitis C virus (HCV) and are at

risk of developing life threatening liver diseases. Until to date, there are obvious unmet medical needs

which encouraged us to identify, characterize and develop novel HCV interventions.

We devised strategies using the infectious HCV cell culture system and carried out a phenotypic, target-

free screening campaign. By excluding compounds active in the replicon system and including those

active on HCV E1/E2 mediated entry, we identified inhibitors interfering with early and late steps of the

HCV life cycle. A promising hit was selected and further characterized in order to determine the

mechanism of action, antiviral potency and to evaluate properties crucial for drug development.

By conducting time-of-addition experiments with this favorable hit compound, inhibition of attachment

and internalization of HCV particles was observed. In addition, cell-to-cell spread and the secretion of

infectious virions was inhibited, whereas HCV RNA secretion and density of viral particle was unaffected.

Furthermore, this potent (EC50 0.0005uM, CC50 >5uM) inhibitor is synergistic in combination with

selected direct acting antivirals and IFN-alpha, and viral drug resistance profiling revealed the HCV

glycoprotein E1 as putative molecular target. Concerning DMPK, amongst other properties, metabolic

stability, solubility, CYP inhibition and other PK properties are being evaluated and improved.

In summary, we identified and characterized a very potent novel inhibitor acting on early and late steps of

the HCV life cycle. A Lead optimization campaign has been initiated to further improve drug-like

properties and to evaluate in vivo efficacy in order to move towards preclinical studies.


: 2015 4 15~17(~) 3

: KINTEX

: BIO1-4


: , : 10:45, :

Recognition of Lipopolysaccharides by TLR4 and its Accessory

Proteins

(KAIST)

Lipopolysaccharide (LPS) is a bacterial glycolipid that is the major component of the outer membrane of

gram-negative bacteria. It serves as an early warning signal of infection by initiating a potent immune

response. Lipid A, the lipid part of the LPS, is responsible for the majority of the immunological activity

of LPS and binds to the cell surface receptor, TLR4-MD-2 heterodimer. LPS binds to the hydrophobic

pocket in MD-2 and induces the dimerization of TLR4. Efficient activation the TLR4 signal in vivo

requires accessory proteins, LBP and CD14. LBP is a serum glycoprotein that can extract LPS from

bacterial membranes or vesicles released from it. CD14 accepts a monomeric form of LPS from LBP and

delivers it to the TLR4-MD-2 complex. The structures of these LPS recognition proteins in a complex

with LPS and related molecules provide us insight into how our immune system recognizes bacterial

infections and initiates efficient defense mechanisms. I will summarize recent structural studies of these

LPS receptors and accessory proteins.


: 2015 4 15~17(~) 3

: KINTEX

: BIO1-5


: , : 11:10, :

Structure-guided discovery of a novel inhibitor against class C beta-

lactamases with extended substrate spectrum

The emergence and dissemination of drug-resistant pathogens are great threat to public health in the

world. The expression of beta-lactamases, which inactivate antibiotics, is a prevalent resistance

mechanism of bacteria to beta-lactam antibiotics. Therefore, the development of inhibitors against beta-

lactamases is a challenge to treat drug-resistant pathogens. Recently, a non-beta-lactam inhibitor against

class C beta-lactamases has been discovered in my lab. The chemical structure of this novel inhibitor is

different from those of existing inhibitors. In addition, this inhibitor exhibited an in vivo efficacy without

side-effects in mouse models. In this talk, I present the molecular features of this inhibitor.


: 2015 4 15~17(~) 3

: KINTEX

: BIO1-6


: , : 11:35, :

Structural biology of cell-shape determining proteins from

Helicobacter pylori

Helicobacter pylori is the major human pathogen associated with various gastrointestinal diseases such as

gastritis, ulcer, and gastric cancer. Its colonization of the human gastric mucosa requires high motility,

which depends on the helical cell shape. At least seven cell shape-determining genes (csd1, csd2,

csd3/hdpA, ccmA, csd4, csd5, and csd6) have been identified in H. pylori. These proteins play key roles

in determining the cell shape through modifications of the cell-wall peptidoglycan by alteration of

crosslinking or by trimming of peptidoglycan muropeptides. To provide a framework for a better

understanding of their molecular functions and for the discovery of novel inhibitors that would prove

helpful in fighting infections by H. pylori, we are carrying out determination of their crystal structures by

X-ray crystallography. Csd4 is a Zn-dependent D,L-carboxypeptida

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