절제된 정상위벽의 자기공명영상기법에 관한 연구:조직소견과의 비교

서보경,설혜영,이남준,차인호,정규병,김정혁,박철민,이지영,Seo, Bo-Gyeong,Seol, Hye-Yeong,Lee, Nam-Jun,Cha, In-Ho,Jeong, Gyu-Byeong,Kim, Jeong-Hyeok,Park, Cheol-Min,Lee, Ji-Yeong 대한영상의학회 2001 대한영상의학회지 Vol.45 No.5

목적:급속자기공명영상기법을 이용하여 절제된 정상위벽을 관찰하고,이를 조직소견과 비교 연구하여,위벽의 관찰을 위한 최적기법을 찾고자 하였다. 대상과 방법:25명 환자의 모두 41개 절제된 정상위조직을 수술후 수지(polyethylene)통에 넣고,생리식염수로 채워 자기공명영상을 시행하였다.T1강조FLASH,지방억제T1강조FLASH, T2강조TSE와 True-FISP 등 4가지 기법으로 위조직의 영상을 얻었다.자기공명영상에서는 위벽의 층수와 각층의 신호강도를 관찰하였고,이를 조직소견과 비교하였다.자기공명영상소견을 조직소견과 비교한 후 위벽 각층의 명확성과 각층간의 구분,및 전체 영상의 질에 대하여 비교하였다.4가지 기법 중 가장 좋은 방법은 3,가장 나쁜 방법은 0으로 하여 등급을 판정하였다. 결과:자기공명영상에서 위벽의 층수는 T1강조FLASH에서 2층이 41예 중 6예(14.6%),3층 31예(75.6%),및 4층 4예(9.8%)였고,지방억제T1강조FLASH에서 2층 6예(14.6%)와 3층 35예(85.4%),T2강조TSE에서 3층 24예(58.5%),4층 11예(26.8%),및 5층 6예(14.6%)였으며,True-FISP에서 1층 2예(4.9%),2층 8예(19.5%),3층 23예(56.0%),4층은 4예(9.8%), 및 5층 4예(9.8%)이었다.위벽의 신호강도는 T1강조FLASH와 지방억제T1강조FLASH에서 2층으로 보인 예는 위내강으로부터 고-중등도,3층인 경우는 고-저-고/중등도,4층인 예는 고-저-고-중등도신호강도였다.T2강조TSE에서는 3층으로 보인 예는 등도/고-저-중등도,4 층인 경우는 중등도-저-고-중등도/저,5층인 예는 저-고-저-고-저신호강도였다.자기공명 영상소견을 조직소견과 비교하였을 때 위벽이 3층으로 보인 경우 이것은 “점막층-점막하층-근층 ”에 해당하였다.관찰한 3가지 면 모두에서 T1강조FLASH,지방억제T1강조FLASH,T2강조TSE 기법이 True-FISP보다 통계적으로 유의하게 우수하였다(p=0.001).점막층의 명확성에 있어서 가장 우수한 기법은 T1강조FLASH와 지방억제T1강조FLASH이었고(p<0.05),점막하층의 명확성과 점막하층과 근층간의 구분은 T2강조TSE가 가장 우수하였다(p<0.05).전체적인 영상의 질은 T1강조FLASH와 T2강조TSE에서 가장 우수하였다(p<0.05). 결론:자기공명영상은 위벽의 각 층을 구별할 수 있는 우수한 검사로 조직소견과 높은 연관성을 보이며,전체 영상의 질,점막하층의 명확성 및 점막하층과 근층간의 구분이 T2강조TSE에서 가장 우수한다. Purpose: To evaluate normal human gastric wall layers in vitro using magnetic resonance*(MR) imaging, to correlate the results with the histologic findings, and to determine the optimal technique for evaluation of the gastric wall. Materials and Methods: Forty-one normal resected gastric specimens obtained from 25 patients were dissected and placed in a polyethylene tube filled with normal saline. MR imaging with four MR sequences, T1-weighted FLASH*(T1FLASH), fat-saturated T1-weighted FLASH, T2-weighted TSE*(T2TSE), and True-FISP, was performed. The number of gastric wall layers and signal intensity of each layer were determined, and after correlating MR images with the histologic findings, the conspicuity of each layer*(mucosa, submucosa, and muscle), the distinction between each layer, and overall image quality were assessed. results: The gastric wall was shown by TIFLASH to have two (n=6, 14-6%), three (n=31, 75.6%) and four layers (n=4, 9.8%); by fat-saturated TIFLASH to have two (n=6, 14.6%) and three (n=35, 85.4%) ; by T2TSE to have three (n=24, 58.5%), four (n=11, 26.8%), and five (n=6, 14.6%); and by True-FISP to have one (n=2, 4.9%), two (n=8, 19.5%), three (n=23, 56%), four (n=4, 9.8%), and five (n=4, 9.8%) . The signal intensity of each layer at T1FLASH and fat-saturated T1FLASH was high-intermediate from the lumen in two-layer cases, high-low-high/intermediate in three-layer cases, and high-low-high-intermediate in four-layer cases. The signal intensity of each layer at T2TSE was intermediate/high-low-intermediate in three-layer cases, intermediatelow-high-intermediate/low in four-layer cases, and low-high-low-high-low in five-layer cases. Three-layered gastric wall corresponded mostly to mucosa, submucosa, and muscle from the inner to outer layers, respectively. T1FLASH, fat-saturated T1FLASH, and T2TSE were superior to True-FISP in evaluating the gastric wall. T1FLASH and fat-saturated T1FLASH were the best sequences for demonstrating mucosa (p<0.05), and T2TSE was the best for submucosa and the distinction between this and muscle (p<0.05). Both T1FLASH and T2TSE provided the best overall image quality (p<0.05). Conclusion: In-vitro MR imaging is an excellent technique for the evaluation of layers of normal gastric wall. T2TSE is the sequence which best demonstrates the conspicuity of submucosa, the distinction between submucosa and muscle, and overall image quality.

유한요소법을 이용한 밸브 스프링 리테이너의 형상설계

신혁수, 김동범, 박진근, 이인환, 조해용 충북대학교 산업과학기술연구소 2013 산업과학기술연구 논문집 Vol.27 No.2

A valve spring retainer is a small disc and located at intake and exhaust valve stem of engine. The retainer supports a valve spring and transmits spring force to a valve. Force is applied to the retainer repeatedly by a rocker arm. Durability of the retainer is an important factor of performance. Weight of retainer affect dynamic performance of engine. Therefore, optimal strength and weight of the retainer design are needed. In this study, stress distribution and fracture load of retainer were analyzed by using FEM to design optimal strength and weight. Static load test was simulated by using commercial FEM code DEFORM-3D. Shapes of the retainer to reduce weight were designed and analyzed to verify validity of it. Simulated results and experimental ones were compared

Low doses of ionizing radiation suppress doxorubicin-induced senescence-like phenotypes by activation of ERK1/2 and suppression of p38 kinase in MCF7 human breast cancer cells

신재식,우상혁,이형찬,홍승우,유두현,홍석일,이왕재,이명석,진영우,안성관,진동훈,박인철 Sookmyung Women's University Research Institute of 2010 여성과 건강 Vol.6 No.1

Low doses of ionizing radiation suppress doxorubicin-induced senescence-like phenotypes by activation of ERK1/2 and suppression of p38 kinase in MCF7 human breast cancer cells

신재식,우상혁,이형찬,홍승우,유두현,홍석일,이왕재,이명석,진영우,안성관,진동훈,박인철 Sookmyung Women's University Research Institute of 2010 여성과 건강 Vol.6 No.1

Preparation and characterisation of divalent hard and soft metal (M = Ca, Co, Cu, Zn, Cd, Hg and Pb) complexes of 1,10-dithia-18-crown-6: structural versatility

Park, In-Hyeok,Park, Ki-Min,Lee, Shim Sung Royal Society of Chemistry 2010 Dalton Transactions Vol.39 No.40

<P>A range of divalent metal complexes (<B>1–10</B>) of 1,10-dithia-18-crown-6 (<B>L</B>) were synthesised in benzonitrile and structurally characterised. In particular cases (Cd, Hg and Pb), the anion effect on the resulting structures was investigated. The calcium(<SMALL>II</SMALL>) complex [Ca(<B>L</B>)(ClO<SUB>4</SUB>)<SUB>2</SUB>] (<B>1</B>) for <B>L</B>, adopting an ‘<I>egg</I>-<I>in</I>-<I>nest</I>’ conformation was isolated. The calcium centre is six-coordinate with a distorted trigonal prismatic geometry, being bound to four oxygens of <B>L</B> and two perchlorato ligands. When Co(ClO<SUB>4</SUB>)<SUB>2</SUB>·6H<SUB>2</SUB>O was employed, the purple complex [Co(<B>L</B>)(H<SUB>2</SUB>O)<SUB>3</SUB>]<SUB>2</SUB>(ClO<SUB>4</SUB>)<SUB>4</SUB> (<B>2a</B>) with a distorted octahedral geometry was obtained as a kinetic product, which then transformed to the solvato-complex [Co(C<SUB>6</SUB>H<SUB>5</SUB>CN)<SUB>4</SUB>(H<SUB>2</SUB>O)<SUB>2</SUB>](ClO<SUB>4</SUB>)<SUB>2</SUB> (<B>2b</B>, yellow) as a thermodynamic product. In contrast to <B>2a</B>, the reaction with Cu(ClO<SUB>4</SUB>)<SUB>2</SUB>·6H<SUB>2</SUB>O afforded an anion-coordinated complex [Cu(<B>L</B>)(ClO<SUB>4</SUB>)<SUB>2</SUB>]·2C<SUB>6</SUB>H<SUB>5</SUB>CN (<B>3</B>). In <B>3</B>, the copper centre is also six-coordinate, being bound to two oxygens and two sulfurs from <B>L</B>, in which the distorted octahedral geometry is completed by two perchlorato ligands. Reaction of <B>L</B> with Zn(ClO<SUB>4</SUB>)<SUB>2</SUB>·6H<SUB>2</SUB>O yielded the mononuclear species [Zn(<B>L</B>)(H<SUB>2</SUB>O)<SUB>3</SUB>]<SUB>2</SUB>(ClO<SUB>4</SUB>)<SUB>4</SUB> (<B>4</B>), in which the octahedral geometry of the zinc(<SMALL>II</SMALL>) is almost same as that of <B>2a</B>. <B>L</B> reacts with CdX<SUB>2</SUB> (X = ClO<SUB>4</SUB> and NO<SUB>3</SUB>) to yield [Cd(<B>L</B>)(ClO<SUB>4</SUB>)<SUB>2</SUB>] (<B>5</B>) and [Cd(<B>L</B>)(NO<SUB>3</SUB>)]<SUB>2</SUB>[Cd(NO<SUB>3</SUB>)<SUB>4</SUB>] (<B>6</B>), respectively. In perchlorato-complex <B>5</B>, all six donors in <B>L</B> participate in the coordination sphere, in which the eight-coordinated ‘<I>tight and bent</I>’ conformation is completed by two perchlorate ions, adopting a dicapped trigonal prismatic geometry. Interestingly, the nitrato-complex <B>6</B> features three separated units of formula [Cd(<B>L</B>)(NO<SUB>3</SUB>)]<SUB>2</SUB>[Cd(NO<SUB>3</SUB>)<SUB>4</SUB>]: two macrocyclic complex cation units and one cadmium quadru-nitrato complex anion unit. In the reaction with HgX<SUB>2</SUB> (X = ClO<SUB>4</SUB> and NO<SUB>3</SUB>), <B>L</B> afforded an unusual triple-decker type dinuclear complex [Hg<SUB>2</SUB>(<B>L</B>)<SUB>3</SUB>](ClO<SUB>4</SUB>)<SUB>4</SUB> (<B>7</B>) with 3 : 2 (<B>L</B> : M) stoichiometry and a 1 : 1 complex [Hg(<B>L</B>)(NO<SUB>3</SUB>)<SUB>2</SUB>]·2H<SUB>2</SUB>O (<B>8</B>) with an eight-coordinate mercury centre, adopting a distorted hexagonal bipyramidal geometry. <B>L</B> reacts with PbX<SUB>2</SUB> (X = ClO<SUB>4</SUB> and NO<SUB>3</SUB>) to yield [Pb(<B>L</B>)(ClO<SUB>4</SUB>)<SUB>2</SUB>] (<B>9</B>) and [Pb(<B>L</B>)(NO<SUB>3</SUB>)<SUB>2</SUB>] (<B>10</B>). In <B>9</B>, the lead(<SMALL>II</SMALL>) is six-coordinate, being bound to four oxygens, in which the distorted octahedral geometry is completed by two perchlorato ligands. In <B>10</B>, the lead(<SMALL>II</SMALL>) coordinates to four oxygens together with two bidentate nitrato-ligands to yield an overall metal coordination geometry of eight, adopting the ‘<I>egg</I>-<I>in</I>-<I>nest</I>’ conformation again.</P> <P>Graphic Abstract</P><P>Ten novel divalent metal complexes of 1,10-dithia-18-crown-6 (<B>L</B>) including the anion-coordinated monomercury(<SMALL>II</SMALL>) complex (nitrate form) and anion-free triple-decker dimercury(<SMALL>II</SMALL>) complex (perchlorate form) were synthesised and structurally ch

Glycemic Control Modifies Difference in Mortality Risk Between Hemodialysis and Peritoneal Dialysis in Incident Dialysis Patients With Diabetes : Results From a Nationwide Prospective Cohort in Korea

Lee, Mi Jung,Kwon, Young Eun,Park, Kyoung Sook,Kee, Youn Kyung,Yoon, Chang-Yun,Han, In Mee,Han, Seung Gyu,Oh, Hyung Jung,Park, Jung Tak,Han, Seung Hyeok,Yoo, Tae-Hyun,Kim, Yong-Lim,Kim, Yon Su,Yang, C Wolters Kluwer Health 2016 Medicine Vol.95 No.11

<▼1><P>Supplemental Digital Content is available in the text</P></▼1><▼2><P><B>Abstract</B></P><P>Although numerous studies have tried to elucidate the best dialysis modality in end-stage renal disease patients with diabetes, results were inconsistent and varied with the baseline characteristics of patients. Furthermore, none of the previous studies on diabetic dialysis patients accounted for the impact of glycemic control. We explored whether glycemic control had modifying effect on mortality between hemodialysis (HD) and peritoneal dialysis (PD) in incident dialysis patients with diabetes.</P><P>A total of 902 diabetic patients who started dialysis between August 2008 and December 2013 were included from a nationwide prospective cohort in Korea. Based on the interaction analysis between hemoglobin A<SUB>1c</SUB> (HbA<SUB>1c</SUB>) and dialysis modalities for patient survival (P for interaction = 0.004), subjects were stratified into good and poor glycemic control groups (HbA<SUB>1c</SUB>< or ≥8.0%). Differences in survival rates according to dialysis modalities were ascertained in each glycemic control group after propensity score matching.</P><P>During a median follow-up duration of 28 months, the relative risk of death was significantly lower in PD compared with HD in the whole cohort and unmatched patients (whole cohort, hazard ratio [HR] = 0.65, 95% confidence interval [CI] = 0.47–0.90, <I>P</I> = 0.01; patients with available HbA<SUB>1c</SUB> [n = 773], HR = 0.64, 95% CI = 0.46–0.91, <I>P</I> = 0.01). In the good glycemic control group, there was a significant survival advantage of PD (HbA<SUB>1c</SUB> <8.0%, HR = 0.59, 95% CI = 0.37–0.94, <I>P</I> = 0.03). However, there was no significant difference in survival rates between PD and HD in the poor glycemic control group (HbA<SUB>1c</SUB> ≥8.0%, HR = 1.21, 95% CI = 0.46–2.76, <I>P</I> = 0.80).</P><P>This study demonstrated that the degree of glycemic control modified the mortality risk between dialysis modalities, suggesting that glycemic control might partly contribute to better survival of PD in incident dialysis patients with diabetes.</P></▼2>

무증상 한국 성인의 대장 용종과 비만의 임상 고찰

지정훈 ( Jeong Hoon Ji ),박범준 ( Bum Joon Park ),박영수 ( Young Soo Park ),황진혁 ( Jin Hyeok Hwang ),정숙향 ( Sook Hyang Chung ),김나영 ( Na Young Kim ),이동호 ( Dong Ho Lee ),정현채 ( Hyun Chae Jung ),송인성 ( In Sung Song ) 대한소화기학회 2007 대한소화기학회지 Vol.49 No.1

목적: 대장암은 생활환경과 식생활의 변화와 더불어 최근 암 발생률, 사망률 모두 증가하고 있다. 이번 연구에서 대장암의 전구 병소로 잘 알려진 선종용종과 체질량지수를 이용한 비만과의 연관성에 대해 알아보고 대장 용종의 수, 크기, 조직 분류와 생화학검사 수치들을 비교하였다. 대상 및 방법: 2002년 3월부터 2005년 4월까지 분당서울대병원의 건강증진센터를 방문한 검진자에서 에스자결장경 검사를 시행했던 환자 6,706명과 이 중 대장내시경을 시행한 860명을 후향으로 분석했다. 체질량지수가 25 이상인 군을 비만군, 25 미만인 군을 대조군으로 정하였다. 이외의 변수로는 성별, 연령, 콜레스테롤, 중성지방, 당화혈색소, 고밀도지질단백, CRP 등이 있으며 이들과 함께 대장 용종의 육안 및 조직병리분류, 용종의 해부학 분포, 크기와 수 등을 체질량지수와 비교하였다. 결과: 대상 환자의 평균 연령은 51.1±10.5세였으며 연령분포는 18세에서부터 83세 사이였다. 남녀 비는 1.1:1이었다. 선종 빈도는 정상군 16.0%과 비만군 20.4%로 유의한 차이를 보였다. 대장내시경을 시행한 860명을 용종군과 대조군으로 나누어 비교하였을 때 대장 용종의 유무에 따른 체질량지수의 평균은 대조군에서 23.9±2.8, 용종군에서 24.3±2.8로 차이를 보이지 않았고 용종 크기에 따른 체질량지수 차이도 없었다. 체질량지수에 따른 대장 선종 빈도는 정상군에서 32.5%였으며 비만군에서는 38.5%로 차이를 보이지 않았으며, 관상선종군과 융모선종군의 체질량지수의 평균치는 각각 24.3±2.7, 24.4±3.1로 통계적인 유의성은 없었다. 그러나 대장내시경 검사에서 선종수가 4개 이상으로 증가하는 경우 체질량지수와 유의한 관계를 보였다. 이 외에 연령, 중성지방은 대장 용종의 유무에 따라 의미있는 차이를 보였다. 결론: 대장 선종 유무에 따른 체질량지수의 차이는 관찰되지 않았으나 대장 선종 수가 증가할수록 체질량지수의 차이가 있었으며 연령, 중성지방 등도 대장 선종 발생의 위험요소일 수 있음을 확인하였다. Background/Aims: Obesity is a rising problem in industrialized countries. Numerous epidemiologic studies have shown a positive association between obesity and colorectal polyps. There are few studies investigating the association between colorectal adenomatous polyps and body fat composition in Korea. We tried to examine the relationship between body fatness and colorectal adenomatous polyps in health check-up subjects in Korea. Methods: Six thousand seven hundred and six routine health check-up subjects, who visited our hospital between March 2002 and April 2005 and underwent distal colon examimation with sigmoidoscopy, were enrolled in this study. Among them, colonoscopy was done in 860 patients to evaluate the entire colon. We tried to reveal the relationship between body mass index (BMI) and size, location, number and histopathological type of polyps. BMI was used as an indicator of obesity. Results: The mean value of BMI in total polyp-free group (23.8±2.9) was not different from that of the polyp group (24.5±2.8, p=0.09). The frequency of rectosigmoid polyps in obese patients (20.4%) was higher than that in non-obese patients (16.0%, p<0.05). The frequency of adenomatous polyp was not different between obese and non-obese group. Number of polyps (≥4) correlated well with obesity. Moreover, age and triglyceride level in patients with colonic adenoma were significantly higher than in patients without colonic adenom. Conclusions: This study shows that obesity is not associated with colonic adenomatous polyp in Korean population. However, we observed that obesity may be associated with rectosigmoid colon polyps. Furthermore, age and triglyceride level might be the risk factors of colonic adenomatous polyps in Korean population. (Korean J Gastroenterol 2007;49:10-16)

Arsenic trioxide (As₂O₃) inhibits invasion of HT1080 human fibrosarcoma cells: Role of nuclear factor-κB and reactive oxygen species

Park, Myung-Jin,Lee, Jae-Young,Kwak, Hee-Jin,Park, Chang-Min,Lee, Hyung-Chahn,Woo, Sang Hyeok,Jin, Hyun-Ok,Han, Chul-Ju,An, Sungkwan,Lee, Seung-Hoon,Chung, Hee Yong,Park, In-Chul,Hong, Seok-Il,Rhee, C Wiley Subscription Services, Inc., A Wiley Company 2005 Journal of cellular biochemistry Vol.95 No.5

<P>In order to define the role of As<SUB>2</SUB>O<SUB>3</SUB> in regulating the tumor cell invasiveness, the effects of As<SUB>2</SUB>O<SUB>3</SUB> on secretion of matrix metalloproteinases (MMPs) and urokinase plasminogen activator (uPA), and in vitro invasion of HT1080 human fibrosarcoma cells were examined. As<SUB>2</SUB>O<SUB>3</SUB> inhibited cell adhesion to the collagen matrix in a concentration dependent manner, whereas the same treatment enhanced cell to cell interaction. In addition, As<SUB>2</SUB>O<SUB>3</SUB> inhibited migration and invasion of HT1080 cells stimulated with phorbol 12-myristate 13-aceate (PMA), and suppressed the expression of MMP-2, -9, membrane type-1 MMP, uPA, and uPA receptor (uPAR). In contrast, As<SUB>2</SUB>O<SUB>3</SUB> increased the expression of tissue inhibitor of metalloproteinase (TIMP)-1 and PA inhibitor (PAI)-1, and reduced the MMP-2, -9, and uPA promoter activity in the presence and absence of PMA. Furthermore, the promoter stimulating and DNA binding activity of nuclear factor-κB (NF-κB) was blocked by As<SUB>2</SUB>O<SUB>3</SUB>, whereas the activator protein-1 activity was unchanged. Pretreatment of the cells with N-acetyl-L-cysteine (NAC) significantly prevented suppression of MMPs and uPA secretion, DNA binding activity of NF-κB, and in vitro invasion of HT1080 cells by As<SUB>2</SUB>O<SUB>3</SUB>, suggesting a role of reactive oxygen species (ROS) in this process. These results suggest that As<SUB>2</SUB>O<SUB>3</SUB> inhibits tumor cell invasion by modulating the MMPs/TIMPs and uPA/uPAR/PAI systems of extracellular matrix (ECM) degradation. In addition, the generation of ROS and subsequent suppression of NF-κB activity by As<SUB>2</SUB>O<SUB>3</SUB> might partly be responsible for the phenomena. Overall, As<SUB>2</SUB>O<SUB>3</SUB> shows potent activity controlling tumor cell invasiveness in vitro. © 2005 Wiley-Liss, Inc.</P>

Higher Tumor Cellularity in Resected Pancreatic Ductal Adenocarcinoma Is a Negative Prognostic Indicator

In Kuk Cho,Haeryoung Kim,Jong-chan Lee,Jongchan Lee,김재환,Soomin Ahn,Hyunjin Park,Jin-Hyeok Hwang 거트앤리버 소화기연관학회협의회 2020 Gut and Liver Vol.14 No.4

Background/Aims: Desmoplasia is a prominent feature of pancreatic ductal adenocarcinoma (PDA). Stromal desmoplasia reflects the low cellularity that is characteristic of PDA, and it may play a role in PDA chemoresistance. In this retrospective study, we evaluated the relationship between tumor cellularity in resected PDA specimens and long-term patient outcomes. Methods: We retrospectively reviewed the data from 175 patients who underwent PDA resection between January 2010 and December 2015 at Seoul National University Bundang Hospital, and analyzed their clinicopathological features and the relationship between tumor cellularity (high vs low based on a cutoff of 30% cellularity) and patient outcomes. Results: The high-cellularity group had significantly shorter overall survival (OS) (18.7 months vs 26.6 months, p=0.006) and disease-free survival (11.0 months vs 16.9 months, p=0.031) than the low-cellularity group. Multivariate analysis revealed that high tumor cellularity was an independent risk factor for poor OS (hazard ratio, 2.008; 95% confidence interval, 1.361 to 2.962; p<0.001). Adjuvant therapy improved OS in the low-cellularity group (16.3 months vs 41.3 months, p=0.001) but not in the high-cellularity group (15.9 months vs 24.4 months, p=0.107). Conclusions: Tumor cellularity in PDA specimens may be a prognostic and predictive biomarker that could aid in identifying patients who would benefit from adjuvant therapy for PDA.

Homonuclear and Heteronuclear Complexes of Calix[4]-<i>bis</i>-monothiacrown-5 with Oligomer and Polymer Structures

Park, In-Hyeok,Kim, Ja-Yeon,Kim, Kihwan,Lee, Shim Sung American Chemical Society 2014 Crystal Growth & Design Vol.14 No.11

<P>Homo- and heteronuclear complexes (<B>1</B>–<B>7</B>) of calix[4]-<I>bis</I>-monothiacrown-5 (<B>L</B>) with mercury(II), cadmium(II), copper(I), and potassium(I) salts adopting dimer, tetramer, one-dimensional (1D), and two-dimensional (2D) polymer structures with different coordination modes and connectivity patterns were prepared and structurally characterized. Reactions of <B>L</B> with mercury(II) iodide and mercury(II) thiocyanate afforded a dimer complex [Hg<SUB>4</SUB>(<B>L</B>)<SUB>2</SUB>I<SUB>8</SUB>]·CH<SUB>2</SUB>Cl<SUB>2</SUB> (<B>1</B>) and a 1D coordination polymer {[Hg<SUB>2</SUB>(<B>L</B>)(SCN)<SUB>4</SUB>]·CH<SUB>2</SUB>Cl<SUB>2</SUB>}<SUB><I>n</I></SUB> (<B>2</B>), respectively, in which the exocyclic dimercury(II) complex units of <B>L</B> are doubly linked by the anions. Reactions of <B>L</B> with cadmium(II) iodide in the absence and the presence of mercury(II) iodide gave isostructural 1D coordination polymers [Cd<SUB>2</SUB>(<B>L</B>)I<SUB>4</SUB>]<SUB><I>n</I></SUB> (<B>3</B>) and {[Cd<SUB>2</SUB>(<B>L</B>)I<SUB>4</SUB>][CdHg(<B>L</B>)I<SUB>4</SUB>]}<SUB><I>n</I></SUB> (<B>4</B>), respectively. In the isostructure of <B>3</B> and <B>4</B>, the ligands are alternately linked by the exocyclic M-I<SUB>2</SUB>-M squares via monocadmium(II)-mediated and dicadmium(II)-mediated modes, respectively. Reaction of <B>L</B> with copper(II) thiocyanate in the presence of potassium(I) thiocyanate afforded a discrete complex {[(K<SUB>2</SUB><B>L</B>)<SUB>4</SUB>Cu<SUB>6</SUB>(SCN)<SUB>10</SUB>][K<SUB>2</SUB><B>L</B>]<SUB>2</SUB>[Cu(SCN)<SUB>3</SUB>]<SUB>3</SUB>·2CH<SUB>2</SUB>Cl<SUB>2</SUB>·CH<SUB>3</SUB>CN} (<B>5</B>) consisting of three separated parts: dipotassium(I) tetramer part linked with a oligomer copper(I) thiocyanate backbone, dipotassium(I) monomer part, and trithiocyanato copper(I) complex part. When a mixture of mercury(II) thiocyanate and potassium(I) thiocyanate was used, a grid-type 2D heteronuclear polymer complex [Hg<SUB>3</SUB>(K<SUB>2</SUB><B>L</B>)(SCN)<SUB>8</SUB>]<SUB><I>n</I></SUB> (<B>6</B>) in which the 1D mercury(II) thiocyanato backbones cross-linked by endocyclic dipotassium(I) complex units of <B>L</B> was isolated. One pot reaction of <B>L</B> with a mixture of iodide salts of potassium(I), mercury(II), and cadmium(II) gave a binary mixed product of a discrete complex [(K<SUB>2</SUB><B>L</B>)<SUB>2</SUB>(Cd<SUB>3</SUB>I<SUB>8</SUB>)][Cd<SUB>4</SUB>I<SUB>10</SUB>] (<B>7</B>) and a heteronuclear 2D network (<B>8</B>) which can be manually separated because of the colorless platy and orange–yellow block shapes of the crystals, respectively. In <B>7</B>, the endocyclic dipotassium(I) complex of <B>L</B> is linked by Cd<SUB>3</SUB>I<SUB>8</SUB> clusters.</P><P>The exocoordination based networking products of calix[4]-<I>bis</I>-monothiacrown-5 (<B>L</B>) including a 2D grid-type heteronuclear polymeric complex in which mercury(II) thiocyanato backbones are cross-linked by the dipotassium(I) complex units of <B>L</B> are reported.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/cgdefu/2014/cgdefu.2014.14.issue-11/cg501194n/production/images/medium/cg-2014-01194n_0012.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/cg501194n'>ACS Electronic Supporting Info</A></P>