Identification of native charge-transfer status of p-aminothiolphenol adsorbed on noble metallic substrates by surface-enhanced infrared absorption (SEIRA) spectroscopy

Li, Qianwen,Wang, Yanan,Li, Yali,Park, Yeonju,Chen, Yujing,Wang, Xu,Zhao, Bing,Ruan, Weidong,Jung, Young Mee Elsevier 2018 Spectrochimica acta. Part A, Molecular and biomole Vol.204 No.-

<P><B>Abstract</B></P> <P>p-Aminothiophenol (PATP) is a preferred molecule in research on surface-enhanced Raman scattering (SERS) because of its unique characteristics of high spectral activity, easily induced charge-transfer (CT), and sensitivity to molecular structural changes. However, some aspects are still unclear, such as the initial steady state of PATP on noble metallic substrates without strong additional excitation with incident and/or induced electromagnetic radiation. Information about the initial steady state, especially the intrinsic CT state, is of great importance to elucidate the dynamic processes of CT and/or molecular structural changes under additional excitation. To investigate the native state of an adsorbed molecule, a suitable probe method that does not disrupt the native state of the whole system, including both molecules and substrates, is required. SERS is not applied in this context because of its use of high-energy visible and near-infrared light. Herein, a low-energy probe method, surface-enhanced infrared-absorption (SEIRA) spectroscopy, is employed as a suitable method for studying the native adsorption state of PATP on silver nanoisland films. The molecular structure and adsorption state were investigated. The intrinsic CT state received particular attention by analyzing the CT-related vibration of B<SUB>2</SUB> modes. Using Fourier transform infrared (FTIR), transmission SEIRA and reflection SEIRA spectroscopy, we explained why the relative intensities of some bands were different under different conditions. A quasi-standing orientation of PATP adsorbed on the substrates was also confirmed. More importantly, we demonstrated that there is no perceptible CT between PATP and silver nanoisland films; in contrast, CT generally occurs in a disruptive manner in SERS. Density functional theory (DFT) calculations and the selection rules for infrared (IR) transmission and reflection-absorption spectroscopy were used to analyze the spectra throughout the paper. SEIRA proved to be an effective technique to explore the native adsorption state of molecules without the excessive external disturbance induced by excitation. The results are very important in providing insight into molecules in surface-interface chemistry, enhanced spectroscopy and photoelectronics.</P> <P><B>Highlights</B></P> <P> <UL> <LI> The native state of PATP was investigated when adsorbed on silver substrates. </LI> <LI> FTIR and SEIRA allow a probe method with less interference on surfaces. </LI> <LI> The intrinsic charge-transfer state was analyzed through the vibration modes of B<SUB>2</SUB>. </LI> </UL> </P> <P><B>Graphical Abstract</B></P> <P>[DISPLAY OMISSION]</P>

Fabrication of novel compound SERS substrates composed of silver nanoparticles and porous gold nanoclusters: A study on enrichment detection of urea

Li, Yali,Li, Qianwen,Sun, Chengbin,Jin, Sila,Park, Yeonju,Zhou, Tieli,Wang, Xu,Zhao, Bing,Ruan, Weidong,Jung, Young Mee Elsevier 2018 APPLIED SURFACE SCIENCE - Vol.427 No.2

<P><B>Abstract</B></P> <P>A new type of surface-enhanced Raman scattering (SERS) substrate was fabricated through the layer-by-layer self-assembly of silver nanoparticles (AgNPs, av. 45nm in diameter) and porous gold nanoclusters/nanoparticles (AuNPs, av. 143nm in diameter). The development of the porosity of the AuNPs was investigated, and successful SERS applications of the porous AuNPs were also examined. As compared with AgNP films, the enhancement factor of Ag-Au compound substrates is increased 6 times at the concentration of 10<SUP>−6</SUP> M. This additional enhancement contributes to the trace-amount-detection of target molecules enormously. The contribution is generated through the increase of the usable surface area arising from the nanoscale pores distributed three-dimensionally in the porous AuNPs, which enrich the adsorption sites and hot spots for the adsorption of probe molecules, making the developed nanofilms highly sensitive SERS substrates. The substrates were used for the detection of a physiological metabolite of urea molecules. The results reached to a very low concentration of 1mM and exhibited good quantitative character over the physiological concentration range (1∼20mM) under mimicking biophysical conditions. These results show that the prepared substrate has great potential in the ultrasensitive SERS-based detection and in SERS-based biosensors.</P> <P><B>Highlights</B></P> <P> <UL> <LI> A new type of SERS substrate, consisting of silver nanoparticles and porous gold nanoparticles was fabricated. </LI> <LI> An additional enhancement contribution generated from the porous characteristic of gold nanoparticles. </LI> <LI> The substrates were used for the detection of a physiological metabolite of urea molecules. </LI> <LI> The results exhibited good quantitative character over all the physiological concentration range (1∼20 mM). </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Dispersion of carbon nanotubes in aluminum improves radiation resistance

So, Kang Pyo,Chen, Di,Kushima, Akihiro,Li, Mingda,Kim, Sangtae,Yang, Yang,Wang, Ziqiang,Park, Jong Gil,Lee, Young Hee,Gonzalez, Rafael I.,Kiwi, Miguel,Bringa, Eduardo M.,Shao, Lin,Li, Ju unknown 2016 Nano energy Vol.22 No.-

<P><B>Abstract</B></P> <P>We can mass-produce metal/carbon nanotube (CNT) composites that show improved radiation tolerance. The 0.5wt% Al+CNT composite showed improved tensile strength without reduction of tensile ductility before radiation, and reduced void/pore generation and radiation embrittlement at high displacements per atom (DPA). Under helium ion irradiation up to 72DPA, the 1D carbon nanostructures survive, while sp<SUP>2</SUP> bonded graphene transforms to sp<SUP>3</SUP> tetrahedral amorphous carbon. Self-ion (Al) irradiation converts CNTs to a metastable form of Al<SUB>4</SUB>C<SUB>3</SUB>, but still as slender 1D nanorods with prolific internal interfaces that catalyze recombination of radiation defects, reducing radiation hardening and porosity generation. The 1D fillers may also form percolating paths of “nano-chimneys” that outgas the accumulated helium and other fission gases, providing an essential solution to the gas accumulation problem.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Dispersion of CNTs showed improved tensile strength without reduction of ductility. </LI> <LI> CNTs in Al reduced void/pore generation and radiation embrittlement at high DPA. </LI> <LI> Under He ion irradiation, 1D CNTs survive, while sp<SUP>2</SUP> bond transform to sp<SUP>3</SUP> carbon. </LI> <LI> Formation of metastable 1D Al<SUB>4</SUB>C<SUB>3</SUB> from CNTs still recombine radiation defects. </LI> <LI> This nanocomposite can help improve bulk properties for nuclear applications. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

A reagent-assisted method in SERS detection of methyl salicylate

Li, Yali,Li, Qianwen,Wang, Yanan,Oh, Joohee,Jin, Sila,Park, Yeonju,Zhou, Tieli,Zhao, Bing,Ruan, Weidong,Jung, Young Mee Elsevier 2018 Spectrochimica acta. Part A, Molecular and biomole Vol.195 No.-

<P><B>Abstract</B></P> <P>With the explosive application of methyl salicylate (MS) molecules in food and cosmetics, the further detection of MS molecules becomes particularly important. Here we investigated the detection of MS molecules based on surface-enhanced Raman scattering (SERS) in a novel molecule/assistant/metal system constructed with MS, 4,4′-(hexafluoroisopropylidene) bis (benzoic acid) and Ag nanoparticles (AgNPs). The minimum detection concentration is 10<SUP>−4</SUP> M. To explore the function of assisted reagent, we also referred another system without assistant molecules. The result demonstrates that SERS signals were not acquired, which proves that the assistant molecules are critical for the capture of MS molecules. Two possible mechanisms of MS/assistant/AgNPs system were speculated through two patterns of hydrogen bonds. The linker molecules acted as the role of the bridge between metallic substrates and target molecules through the molecular recognition. This strategy is very beneficial to the expanding of MS detection techniques and other hydrogen bond based coupling detections with SERS.</P> <P><B>Highlights</B></P> <P> <UL> <LI> A novel molecule/assistant/metal system was constructed to achieve the SERS detection of methyl salicylate. </LI> <LI> The intermolecular hydrogen bond was employed as the driving force to accomplish the assembly. </LI> <LI> The obstacle of non-adsorption of target molecules on substrates was solved through the hydrogen-bond-based assembly method. </LI> </UL> </P> <P><B>Graphical Abstract</B></P> <P>[DISPLAY OMISSION]</P>

Three new constituents from the aerial parts of Tetrastigma hemsleyanum

Wang, Cai Yi,Lee, Ji Sun,Su, Xiang Dong,Li, Hong Xu,Lee, Sang Kook,Wang, Heng-Shan,Kim, Young Ho,Yang, Seo Young ELSEVIER SCIENCE B.V., AMSTERDAM 2018 Phytochemistry letters Vol.2018 No.27

Extracellular loop 3 (EL3) and EL3-proximal transmembrane helix 7 of the mammalian type I and type II gonadotropin-releasing hormone (GnRH) receptors determine differential ligand selectivity to GnRH-I and GnRH-II.

Li, Jian Hua,Choe, Han,Wang, Ai Fen,Maiti, Kaushik,Wang, Chengbing,Salam, Abdus,Chun, Sang Young,Lee, Won-Kyo,Kim, Kyungjin,Kwon, Hyuk Bang,Seong, Jae Young American Society for Pharmacology and Experimental 2005 Molecular pharmacology Vol.67 No.4

<P>Mammalian type I and II gonadotropin-releasing hormone (GnRH) receptors (GnRHRs) show differential ligand preference for GnRH-I and GnRH-II, respectively. Using a variety of chimeric receptors based on green monkey GnRHR-2 (gmGnRHR-2), a representative type II GnRHR, and rat GnRHR, a representative type I GnRHR, this study elucidated specific domains responsible for this ligand selectivity. A chimeric gmGnRHR-2 with the extracellular loop 3 (EL3) and EL3-proximal transmembrane helix 7 (TMH7) of rat GnRHR showed a great increase in ligand sensitivity to GnRH-I but not to GnRH-II. Point-mutation studies indicate that four amino acids, Leu/Phe(7.38), Leu/Phe(7.43), Ala/Pro(7.46), and Pro/Cys(7.47) in TMH7 are critical for ligand selectivity as well as receptor conformation. Furthermore, a combinatory mutation (Pro(7.31)-Pro(7.32)-Ser(7.33) motif to Ser-Glu-Pro in EL3 and Leu(7.38), Leu(7.43), Ala(7.46), and Pro(7.47) to those of rat GnRHR) in gmGnRH-2 exhibited an approximately 500-fold increased sensitivity to GnRH-I, indicating that these residues are critical for discriminating GnRH-II from GnRH-I. [Trp(7)]GnRH-I and [Trp(8)]GnRH-I but not [His(5)]GnRH-I exhibit a higher potency in activating wild-type gmGnRHR-2 than native GnRH-I, indicating that amino acids at positions 7 and 8 of GnRHs are more important than position 5 for differential recognition by type I and type II GnRHRs. As a whole, these data suggest a molecular coevolution of ligands and their receptors and facilitate the understanding of the molecular interaction between GnRHs and their cognate receptors.</P>

Influence of backbone modification of difluoroquinoxaline-based copolymers on the interchain packing, blend morphology and photovoltaic properties of nonfullerene organic solar cells

Li, Yuxiang,Kim, Minseok,Wu, Ziang,Lee, Changyeon,Lee, Young Woong,Lee, Jin-Woo,Lee, Young Jun,Wang, Ergang,Kim, Bumjoon J.,Woo, Han Young The Royal Society of Chemistry 2019 Journal of Materials Chemistry C Vol.7 No.6

<P>In order to understand the influence of molecular ordering and orientation on the performance of nonfullerene (NF) solar cells, we synthesized a series of difluoroquinoxaline-based alternating copolymers: starting from poly(2,2′-bithiophene-<I>alt</I>-(2,3-bis(3,4-bis(octyloxy)phenyl)-6,7-difluoroquinoxaline)) (PDFQx-2T), we modified the polymeric backbone by incorporating fluorine atoms (PDFQx-2T2F) or thiophene (PDFQx-3T) or a benzene ring (PDFQx-2TB) in the bithiophene comonomeric unit. The structure modification significantly affected the photovoltaic performance with power conversion efficiencies (PCEs) of 3.95% for PDFQx-2TB:ITIC, 4.82% for PDFQx-2T:ITIC, 4.93% for PDFQx-2T2F:ITIC and 8.13% for PDFQx-3T:ITIC. The dramatic increase in the PCE of PDFQx-3T:ITIC was attributed to improvements in the short-circuit current density (<I>J</I>SC) and fill factor (FF). From the resonant soft X-ray scattering and grazing incidence X-ray scattering measurements, the PDFQx-3T polymers had well-developed, face-on oriented crystallites, allowing the formation of face-to-face alignment with the face-on ordered ITIC molecules at the interfaces. Also, the PDFQx-3T:ITIC blend films exhibited well intermixed blend morphology with smaller domain spacings. These combined features contributed to efficient charge generation with the highest exciton dissociation probability among the four different polymer:ITIC systems. In addition, dominant face-on orientation of both PDFQx-3T polymers and ITIC acceptors with a balanced crystalline coherence length ratio (CCLpolymer/CCLITIC) (0.87, based on the out-of-plane (010) diffraction peaks of PDFQx polymers and ITIC acceptors) led to a more balanced charge mobility than other blends, explaining the highest <I>J</I>SC and FF in the PDFQx-3T:ITIC NF devices.</P>

Regular Endurance Exercise Decreases Blood Pressure via Enhancement of Angiogenesis and VEGF Expression in Spontaneously Hypertensive Rats

Wei Li(이위),Hee-Geun Park(박희근),Young-Ran Lee(이영란),Hak-young Jang(장학영),Young Hwa Lee(이영화),Gan Li(감력),Sung-Ho Choo(추성호),Jong-Kui Jun(전종귀),Wang-Lok Lee(이왕록),Sang Ki Lee(이상기) 한국생명과학회 2012 생명과학회지 Vol.22 No.5

이 연구는 자연발생고혈압쥐(SHR)의 혈압, 골격근에서의 혈관생성 및 혈관내피세포성장인자 발현(VEGF)에 미치는 지구성운동의 효과를 조사하였다. 5주령 SHR와 WKY는 무작위로 정상혈압군(WKY, Wistar-Kyoto rat, n=9), 고혈압통제군(SHR-C, SHR Control, n=9) 및 고혈압운동군(SHR-E, SHR Exercise, n=9)으로 각각 분류하였고, 지구성운동은 트레드밀을 이용하였다(12-20 m/min, 0% grade, 60 min/day, 5 days/wk, 16 wk). 수축기혈압은 지구성운동에 의해 효과적으로 감소되었다(SHR-E vs. SHR-C, p<0.05). 골격근의 모세혈관밀도와 VEGF 단백발현은 고혈압통제군(SHR-C)이 정상혈압군(WKY)보다 모두 감소되었으나, 지구성운동(SHR-E)이 고혈압통제군(SHR-C)에 비해 모두 증가되었다. 이러한 결과들은 지구력운동 트레이닝이 SHR 골격근의 VEGF 단백발현의 증가를 통해 모세혈관밀도를 향상시키고, 이러한 모세혈관밀도의 향상이 SHR의 혈압상승을 억제할 수 있다는 것을 의미한다. This study investigated the effect of endurance exercises on blood pressure, angiogenesis, and the vascular endothelial growth factor (VEGF) expression in the skeletal muscle of spontaneously hypertensiverats (SHR). Five week old SHRs and Wistar-Kyoto rats (WKY) were randomly divided into 3 groups: Wistar-Kyoto rats (WKY, n=9), SHR control (SHR-C, n=9), and SHR endurance exercise training (SHR-E, n=9). Endurance exercise training was performed on a treadmill (12-20 m/min, 0% grade, 60 min/day, 5 days/week, 16 weeks). Systolic blood pressure was monitored with the tail-cuff method. The expression of VEGF protein and capillary density were identified using western blotting and H&E staining in the soleus muscle, respectively. Systolic blood pressure was reduced by endurance exercise in SHR (p<0.05). The capillary density of skeletal muscles in SHR-C was lower than in WKY (p<0.05), but it was recovered by endurance exercise training (SHR-E) compared to SHR-C (p<0.05), and VEGF protein was also increased by endurance exercise training compared to SHR-C (p<0.05). These data suggest that the enhancement of capillary density via an increase of VEGF expression in skeletal muscles by endurance exercise training could be an important factor to inhibit blood pressure elevation in SHR.

Genome-wide association studies approach and post-GWAS study in rice

Gang Li,Min-Young Yoon,Won-Hee Ra,Jae-Wan Park,Qiang He,Aye Aye Khaing,Xiao-Qiang Wang,Win Htet Oo,Feng-Peng Li,Byoung Kook Yun,Chang-Yong Lee,Yong-Jin Park 한국육종학회 2013 한국육종학회 심포지엄 Vol.2013 No.07

AGenome-wide association studies (GWAS) have proven a useful technique for identifying genetic loci responsible for natural variation in rice. With the fast developed next-generation sequencing technology, it is possible for people to carry out GWAS by phenotyping different traits. However, how to make full use of huge data, abandon unnecessary data, and solve the problem of data application effectively seems still an obstacle for many researchers. Taking the case of whole-genome resequencing of Korean authentic rice core set, here we present a general technological path of GWAS including: 1) a schematic view of sequencing-based GWAS in rice; 2) a user-friendly and interactive web application for GWAS in rice by the aid of experience from Arabidopsis; 3) Haplotype and association analysis of candidate genes in a certain mechanism pathway, giving 10 starch synthesis genes as example; and 4) functional validation by Trans- and Mata-Omics analysis.

동충하초균주로 발효한 감초의 주요성분 함량 변화 및 NO 생성 억제 효과

왕자옥(Ziyu Wang),이매(Mei Li),이커(Ke Li),손병구(Beung Gu Son),강점순(Jum Soon Kang),이용재(Yong Jae Lee),박영훈(Young Hoon Park),김선태(Sun Tae Kim),정재철(Jae-Chul Jung),이영근(Young Guen Lee),최영환(Young Whan Choi) 한국생명과학회 2017 생명과학회지 Vol.27 No.1

약용식물의 발효는 새로운 식품의 소재 개발이 가능하나, 발효 균주는 대부분 이스트, 유산균, 박테리아 등이 이용되고 있다. 본 연구에서는 감초와 번데기 단독 또는 감초에 발효원인 번데기를 20%와 50%로 첨가한 혼합물의 배지에 눈꽃 동충하초(Paecilomyces tenuipes)와 밀리타리스 동충하초(Cordyceps militaris)를 이용하여 고체배양방법을 확립하였다. 동충하초 발효물을 식품소재로 개발하기 위하여 식용 가능한 용매인 에탄올 95%, 70%, 50%, 25% 및 물로서 추출한 다음 동충하초로부터 생성된 cordycepin과 감초의 지표성분인 liquiritin, liquiritigenin과 glycirrhizin의 함량 및 NO생성 억제효과를 조사하였다. Cordycepin함량은 감초에 번데기를 50%로 혼합한 배지에 밀리타리스 동충하초 균주을 접종하여 발효한 발효물을 70% EtOH추출하였을 경우에 가장 많았으며, 번데기를 첨가하지 않은 밀리타리스 동충하초 발효물 추출물보다 함량이 33배 정도 증가하였다. 또한 추출용매의 극성이 70% EtOH보다 높거나 낮아지면 감소하는 경향이었으며, 특히 발효원으로서 번데기의 첨가는 cordycepin의 함량을 현저하게 증가시켰다. Liquiritin의 함량은 발효하지 않은 감초보다 눈꽃 동충하초와 밀리타리스 동충하초로 발효한 모든 추출물에서 감소하였다. Liquiritigenin의 함량은 눈꽃 동충하초로 발효한 추출물이 밀리타리스 동충하초 발효 추출물보다 현저히 증가하였으나, 밀리타리스 동충하초 균쥬의 발효 추출물은 발효하지 않은 감초추출물과 거의 차이가 없었으며, 두 균주 모두 번데기의 첨가량이 증가할수록 liquiritigenin의 함량이 감소하는 경향이었다. 감초에 번데기의 첨가량 또는 추출 용매의 극성이 증가하면 liquiritin과 glycyrrhizin의 함량은 현저히 감소하였다. 이상의 결과로부터, cordycepin 함량은 C. militaris 균주로 liquiritigenin은 P. tenuipes로 발효시에 현저하게 증가하였으나, liquiritin과 glycyrrhizin은 감소하였다. 감초를 동충하초로 발효시에 번데기의 첨가는 주요 성분의 변화를 현저하게 유도하였다. 동충하초 발효 추출물은 NO생성 억제효과가 증가하였으며, 고극성 용매추출물에서 그 효과가 현저하였다. 감초의 발효시에 생성된 cordycepin과 liquiritin, liquiritigenin 및 glycyrrhizin의 함량은 발효원으로서 첨가되는 번데기, 추출용매의 극성, 발효 균주의 종류 등에 따라서 현저한 차이가 있었다. 이러한 결과는 동충하초 균주를 이용한 기능성 식품 소재를 개발하기 위한 기초 자료로서 활용이 가능할 것으로 기대된다. Traditional Korean fermented herbal plants are potential sources of new food that promote health, but they are still produced by yeast, fungi or bacteria fermentation. In the present work, mushroom (Paecilomyces tenuipes and Cordyceps militaris) fungal dongchunghacho were used to fermented Glycyrrhiza uralensis Fischer (licorice) or mixed with pupa. The pupa were tested as solid substrates for the production of corcycepin, liquiritin, and liquiritigenin. The fermented substrates were analyzed the content of cordycepin, liquiritin, liquiritigenin, and glycirrhizin productivity and inhibitory activity of NO. The cordycepin content of 70% EtOH extract from the fermented mixture of licorice and 50% pupa with C. militaris increased maximum at 33 times. Pupa was very excellent for the production of cordycepin. The liquiritin content was decreased in all the assays inoculated with P. tenuipes and C. militaris dongchunghachos. The liquiritigenin content was higher when fermented with P. tenuipes than C. militaris. The addition of pupa significantly reduced the liquiritin content and glycyrrhizin production. As a result, the liquiritigenin content increased in fermented P. tenuipes and C. militaris, and liquiritin and glycyrrhizin decreased. The inhibition of NO production in the different ethanolic extracts fermented with licorice and pupa was also significantly increased and higher than that of a nonfermented extract in higher polar solvent extracts. The contents of cordycepin and biological active compounds were altered in accordance with the concentration of pupa and fungi. This study provides basic data for use in developing dongchunghacho fungi as a functional food resource.