• Title/Summary/Keyword: Primary Resonance

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The α-Effect in Hydrazinolysis of 4-Chloro-2-Nitrophenyl X-Substituted-Benzoates: Effect of Substituent X on Reaction Mechanism and the α-Effect

  • Kim, Min-Young;Kim, Tae-Eun;Lee, Jieun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.8
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    • pp.2271-2276
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    • 2014
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reaction of 4-chloro-2-nitrophenyl X-substituted-benzoates (6a-6h) with a series of primary amines including hydrazine in 80 mol % $H_2O$/20 mol % DMSO at $25.0^{\circ}C$. The Br${\o}$nsted-type plot for the reaction of 4-chloro-2-nitrophenyl benzoate (6d) is linear with ${\beta}_{nuc}$ = 0.74 when hydrazine is excluded from the correlation. Such a linear Br${\o}$nsted-type plot is typical for reactions reported previously to proceed through a stepwise mechanism in which expulsion of the leaving group occurs in the rate-determining step (RDS). The Hammett plots for the reactions of 6a-6h with hydrazine and glycylglycine are nonlinear. In contrast, the Yukawa-Tsuno plots exhibit excellent linear correlations with ${\rho}_X$ = 1.29-1.45 and r = 0.53-0.56, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by resonance stabilization of the substrates possessing an electron-donating group (EDG). Hydrazine is ca. 47-93 times more reactive than similarly basic glycylglycine toward 6a-6h (e.g., the ${\alpha}$-effect). The ${\alpha}$-effect increases as the substituent X in the benzoyl moiety becomes a stronger electron-withdrawing group (EWG), indicating that destabilization of the ground state (GS) of hydrazine through the repulsion between the nonbonding electron pairs on the two N atoms is not solely responsible for the substituent-dependent ${\alpha}$-effect. Stabilization of transition state (TS) through five-membered cyclic TSs, which would increase the electrophilicity of the reaction center or the nucleofugality of the leaving group, contributes to the ${\alpha}$-effect observed in this study.

Schwannoma of the Orbit

  • Kim, Kwang Seog;Jung, Jin Woo;Yoon, Kyung Chul;Kwon, Yu Jin;Hwang, Jae Ha;Lee, Sam Yong
    • Archives of Craniofacial Surgery
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    • v.16 no.2
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    • pp.67-72
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    • 2015
  • Background: A schwannoma is a benign, slow-growing peripheral nerve sheath tumor that originates from Schwann cells. Orbital schwannomas are rare, accounting for only 1% of all orbital neoplasms. In this study, we retrospectively review orbital schwannomas and characterize clinical, radiologic, and histologic features of this rare entity. Methods: A retrospective review was performed to identify patients with histologically confirmed orbital schwannoma, among a list of 437 patients who had visited our hospital with soft tissue masses within the orbit as the primary presentation between 2010 and 2014. Patient charts and medical records were reviewed for demographic information, relevant medical and family history, physical examination findings relating to ocular and extraocular sensorimotor function, operative details, postoperative complications, pathologic report, and recurrence. Results: Five patients (5/437, 1.1%) were identified as having histologically confirmed orbital schwannoma and underwent complete excision. Both computed tomography (CT) and magnetic resonance imaging (MRI) studies were not consistent in predicting histologic diagnosis. There were no complications, and none of the patients experienced significant scar formation. In two cases, patients exhibited a mild postoperative numbness of the forehead, but the patients demonstrated full recovery of sensation within 3 months after the operation. None of the five patients have experienced recurrence. Conclusion: Orbital schwannomas are relatively rare tumors. Preoperative diagnosis is difficult because of its variable presentation and location. Appropriate early assessment of orbital tumors by CT or MRI and prompt management is warranted to prevent the development of severe complications. Therefore, orbital schwannomas should be considered in the differential diagnosis of slow-growing orbital masses.

Contrast-Enhanced MR Angiography of Supra-Aortic Arteries: Review of Current Techniques, Diagnostic Accuracy and Common Pitfalls in Steno-Occlusive Diseases

  • Lee, Jeong-Hyun;Kim, Jin-Hyoung;Kim, Hyun-Jeong;Park, Choong-Gon;Lee, Deok-Hee;Lee, Ho-Kyu;Kim, ang-Joon;Suh, Dae-Chul
    • Proceedings of the KSMRM Conference
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    • 2003.10a
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    • pp.97-97
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    • 2003
  • Contrast-enhanced MR angiography (CE-MRA) gradually occupies its position as a primary evaluation tool forsteno-occlusive disease of supra-aortic cervical arteries. It has several advantages over time-of-flight (TOF) technique such as shorter imaging time, less saturation effect, and less flow- and motion-related artifacts. Diverse methods of k-space sampling, imaging sequences, and strategies for image acquisitiontiming have been introduced since its early clinical application. Especially, methods of k-space sampling and image acquisition timing are very important to achieve maximal arterial enhancement and suppress venous signal while maintaining large scan coverage and high spatial resolution. In addition, regardless of several advantages over TOF technique, it still has a tendency to overestimate the degree of stenosis in patients with carotid or vertebralartery disease. In this exhibit, we will overview the current techniques of CE-MRA with special attention to methods of k-space sampling and image acquisition timing. We will also discuss diagnostic accuracy of CE-MRA in patients with supra-aortic cervical artery stenosis and artifacts frequently misinterpreted as steno-occlusive lesion on CE-MRA.

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Management of Recurrent Vestibular Schwannomas

  • Kim, Wook-Ha;Park, Chul-Kee;Kim, Dong-Gyu;Jung, Hee-Won
    • Journal of Korean Neurosurgical Society
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    • v.39 no.2
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    • pp.87-91
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    • 2006
  • Objective : Management of recurrent vestibular schwannomas[VS] after microsurgery or radiosurgery is a complicated subject. However, few studies have documented the outcome of recurrent VS. The authorsreviewclinicalexperience of recurrent VS management and analyzed the efficacy of treatment modalities. Methods : Between 1990 and 2002, 293 patients harboring unilateral VS underwent, microsurgery, radiosurgery, microsurgery followed by radiosurgery. Of these, 26 procedures [in 20 patients] were performed to assessed from an increased tumor size by magnetic resonance imaging[MRI]. The mean age of patients with recurred VS was 46.9 years and the mean follow-up period was 68 months. Radiological characteristics were investigated and growth rates of recurred tumors were calculated by measuring changes in tumor diameter on MRI after treatment. Results : MRI characteristics revealed a lobulated contour in 75% and a cyst in 60% of the patients. Only 1 patient showed neither lobulation nor a cyst. The average diameter of the recurrent tumors were 36.9mm. The overall tumor control rate for initial management was 87.4%, 94.7%, and 98.5% for microsurgery, radiosurgery, and microsurgery plus radiosurgery, respectively. However, control rates for recurrent tumors were lower at 85%, 63%, and 80%, respectively. Conclusion : A cystic nature and a lobulated tumor contour are frequent clinical characteristics of recurrent VS. Microsurgery or microsurgery followed by radiosurgery shows little difference in tumor control rate for primary and recurrent VS. However, radiosurgery alone appears to be less beneficial for recurrent VS.

Gamma Knife Radiosurgery after Stereotactic Aspiration for Large Cystic Brain Metastases

  • Park, Won-Hyoung;Jang, In-Seok;Kim, Chang-Jin;Kwon, Do-Hoon
    • Journal of Korean Neurosurgical Society
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    • v.46 no.4
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    • pp.360-364
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    • 2009
  • Objective : Several treatment options have proven effective for metastatic brain tumors, including surgery and stereotactic radiosurgery. Tumors with cystic components, however, are difficult to treat using a single method. We retrospectively assessed the outcome and efficacy of gamma knife radiosurgery (GKRS) for cystic brain metastases after stereotactic aspiration of cystic components to decrease the tumor volume. Methods : The study population consisted of 24 patients (13 males, 11 females; mean age, 58.3 years) with cystic metastatic brain tumors treated from January 2002 to August 2008. Non-small cell lung cancer was the most common primary origin. After Leksell stereotactic frame was positioned on each patient, magnetic resonance images (MRI)-guided stereotactic cyst aspiration and GKRS were performed (mean prescription dose : 20.2 Gy). After treatment, patients were evaluated by MRI every 3 or 4 months. Results : After treatment, 13 patients (54.2%) demonstrated tumor control, 5 patients (20.8%) showed local tumor progression, and 6 patients (25.0%) showed remote progression. Mean follow-up duration was 13.1 months. During this period, 10 patients (41.7%) died, but only 1 patient (4.2%) died from brain metastases. The overall median survival after these procedures was 17.8 months. Conclusion : These results support the usefulness of GKRS after stereotactic cyst aspiration in patients with large cystic brain metastases. This method is especially effective for the patients whose general condition is very poor for general anesthesia and those with metastatic brain tumors located in eloquent areas.

A Korean boy with atypical X-linked adrenoleukodystrophy confirmed by an unpublished mutation of ABCD1

  • Jwa, Hye Jeong;Lee, Keon Su;Kim, Gu Hwan;Yoo, Han Wook;Lim, Han Hyuk
    • Clinical and Experimental Pediatrics
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    • v.57 no.9
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    • pp.416-419
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    • 2014
  • X-linked adrenoleukodystrophy (X-ALD) is a rare peroxisomal disorder, that is rapidly progressive, neurodegenerative, and recessive, and characteristically primary affects the central nervous system white matter and the adrenal cortex. X-ALD is diagnosed basaed on clinical, radiological, and serological parameters, including elevated plasma levels of very long chain fatty acids (VLCFA), such as C24:0 and C26:0, and high C24:0/C22:0 and C26:0/C22:0 ratios. These tests are complemented with genetic analyses. A 7.5-year-old boy was admitted to Department of Pediatrics, Chungnam National University Hospital with progressive weakness of the bilateral lower extremities. Brain magnetic resonance imaging confirmed clinically suspected ALD. A low dose adrenocorticotropic hormone stimulation test revealed parital adrenal insufficiency. His fasting plasma levels of VLCFA showed that his C24:0/C22:0 and C26:0/C22:0 ratios were significantly elevated to 1.609 (normal, 0-1.390) and 0.075 (normal, 0-0.023), respectively. Genomic DNA was extracted from peripheral whole blood samples collected from the patient and his family. All exons of ABCD1 gene were amplified by polymerase chain reaction (PCR) using specific primers. Amplified PCR products were sequenced using the same primer pairs according to the manufacturer's instructions. We identified a missense mutation (p.Arg163Leu) in the ABCD1 gene of the proband caused by the nucleotide change 488G>T in exon 1. His asymptomatic mother carried the same mutation. We have reported an unpublished mutation in the ABCD1 gene in a patient with X-ALD, who showed increased ratio of C24:0/C22:0 and C26:0/C22:0, despite a normal VLCFA concentrations.

Clinical Experience with Treatment of Angioleiomyoma

  • Woo, Kyoung Sik;Kim, Sang Hun;Kim, Han Seong;Cho, Pil Dong
    • Archives of Plastic Surgery
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    • v.41 no.4
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    • pp.374-378
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    • 2014
  • Background Angioleiomyoma, a vascular leiomyoma, is a rare, benign smooth-muscle tumor that originates in the tunica media of vessels. It occurs anywhere in the body, most frequently in the lower extremities. Methods We reviewed the medical records of 16 patients who were treated for angioleiomyoma between 2000 and 2012. The clinical features of angioleiomyoma and the correlation between symptoms and pathological subtypes were investigated. Results There were 9 males and 6 females. Ages of the patients ranged from 21 to 61. Pain was the primary symptom in 44% of the patients. Tumors were smaller than 2.0 cm in all dimensions and were located in the face in 4 patients, whereas 5 lesions occurred in the upper extremities and the remaining 7 in the lower extremities. Three histologic subtypes were identified: solid, venous, and cavernous. The subtypes did not correlate with the clinical symptoms. Conclusions Angioleiomyoma appears to be a rare tumor that occurs in the face and the extremities. The tumor usually occurs in middle age. A differential diagnosis of this tumor is difficult, but the tumor should be considered in the diagnosis of painful subcutaneous masses. Ultrasonography and magnetic resonance imaging can be helpful in the diagnosis of angioleiomyoma. These tumors can be successfully treated with simple excision, with a low recurrence rate.

Management of Cerebrospinal Fluid Leak after Traumatic Cervical Spinal Cord Injury (경추 손상 후 뇌척수액 유출에 대한 관리)

  • Lee, Soo Eon;Chung, Chun Kee;Jahng, Tae-Ahn;Kim, Chi Heon
    • Journal of Trauma and Injury
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    • v.26 no.3
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    • pp.151-156
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    • 2013
  • Purpose: Traumatic cervical SCI is frequently accompanied by dural tear and the resulting cerebrospinal fluid (CSF) leak after surgery can be troublesome and delay rehabilitation with increasing morbidity. This study evaluated the incidence of intraoperative CSF leaks in patients with traumatic cervical spinal cord injury (SCI) who underwent anterior cervical surgery and described the reliable management of CSF leaks during the perioperative period. Methods: A retrospective study of medical records and radiological images was done on patients with CSF leaks after cervical spine trauma. Results: Seven patients(13.2%) were identified with CSF leaks during the intraoperative period. All patients were severely injured and showed structural abnormalities on the initial magnetic resonance image (MRI) of the cervical spine. Intraoperatively, no primary repair of dural tear was attempted because of a wide, rough defect size. Therefore, fibrin glue was applied to the operated site in all cases. Although a wound drainage was inserted, it was stopped within the first 24 hours after the operation. No lumbar drainage was performed. Postoperatively, the patients should kept their heads in an elevated position and early ambulation and rehabilitation were encouraged. None of the patients developed complications related to CSF leaks during admission. Conclusion: The incidence of CSF leaks after surgery for cervical spinal trauma is relatively higher than that of cervical spinal stenosis. Therefore, one should expect the possibility of a dural tear and have a simple and effective management protocol for CSF leaks in trauma cases established.

Tumor volume/metabolic information can improve the prognostication of anatomy based staging system for nasopharyngeal cancer? Evaluation of the 8th edition of the AJCC/UICC staging system for nasopharyngeal cancer

  • Jeong, Yuri;Lee, Sang-wook
    • Radiation Oncology Journal
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    • v.36 no.4
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    • pp.295-303
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    • 2018
  • Purpose: We evaluated prognostic value of the 8th edition of the American Joint Committee on Cancer/International Union for Cancer Control (AJCC/UICC) staging system for nasopharyngeal cancer and investigated whether tumor volume/metabolic information refined prognostication of anatomy based staging system. Materials and Methods: One hundred thirty-three patients with nasopharyngeal cancer who were staged with magnetic resonance imaging (MRI) and treated with intensity-modulated radiotherapy (IMRT) between 2004 and 2013 were reviewed. Multivariate analyses were performed to evaluate prognostic value of the 8th edition of the AJCC/UICC staging system and other factors including gross tumor volume and maximum standardized uptake value of primary tumor (GTV-T and SUV-T). Results: Median follow-up period was 63 months. In multivariate analysis for overall survival (OS), stage group (stage I-II vs. III-IVA) was the only significant prognostic factor. However, 5-year OS rates were not significantly different between stage I and II (100% vs. 96.2%), and between stage III and IVA (80.1% vs. 71.7%). Although SUV-T and GTV-T were not significant prognostic factors in multivariate analysis, those improved prognostication of stage group. The 5-year OS rates were significantly different between stage I-II, III-IV (SUV-T ≤ 16), and III-IV (SUV-T > 16) (97.2% vs. 78% vs. 53.8%), and between stage I, II-IV (GTV-T ≤ 33 mL), and II-IV (GTV-T > 33 mL) (100% vs. 87.3% vs. 66.7%). Conclusion: Current anatomy based staging system has limitations on prognostication for nasopharyngeal cancer despite the most accurate assessment of tumor extent by MRI. Tumor volume/metabolic information seem to improve prognostication of current anatomy based staging system, and further studies are needed to confirm its clinical significance.

Ultrasound-guided Distance Measurements of Vertebral Structures for Lumbar Medial Branch Block (초음파 유도하에서의 요추부 후관절 내측지 차단술을 위한 주요 척추 구조물의 거리 측정)

  • Moon, Jin Cheon;Shim, Jae Kwang;Jo, Kwang Yun;Yoon, Kyung Bong;Kim, Won Oak;Yoon, Duck Mi
    • The Korean Journal of Pain
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    • v.20 no.2
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    • pp.111-115
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    • 2007
  • Background: Selective diagnostic blocks of the medial branches of the dorsal primary ramus are usually performed under the guidance of fluoroscopic or computed tomography. Recently, however, ultrasound guidance has been suggested as an altemative method. In this study, the distances between the vertebral structures were measured and compared with the values measured using magnetic resonance imaging (MRI) to assess the clinical feasibility of using ultrasound-guided block in Korean patients. Methods: Five male and 15 female patients were enrolled in this study. The target point of the medial branch block in our study was the groove at the base of the superior articular process, We measured the depth from the skin to the target point at the transverse process (d-TP) and to the most superficial point of the superior articular process (d-AP). Results: The d-TP and d-AP values measured under ultrasound guidance were concordant with the values measured using MRI. Conclusions: The images of the bony landmarks obtained under ultrasound examination could be useful for ultrasound-guided lumbar medial branch block.