• Title/Summary/Keyword: Transition state imbalance

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Kinetics and Mechanism of the Pyridinolysis of Bis(2,6-dimethylphenyl) Chlorophosphate in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.12
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    • pp.4179-4184
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    • 2011
  • The nucleophilic substitution reactions of bis(2,6-dimethylphenyl) chlorophosphate (5), containing the four ortho-methyl substituents, with X-pyridines are investigated kinetically in MeCN at $65.0^{\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a breakpoint at a X = 3-Cl. Unusual positive ${\rho}_X$ (= +5.40) and negative ${\beta}_X$ (= -0.83) values are obtained with the weakly basic pyridines. The pyridinolysis rate of 5 is hundreds times slower compared to that of bis(phenyl) chlorophosphate because of the steric hindrance of the four ortho-methyl substituents in the two phenyl rings. Ion-pair mechanism is proposed and positive ${\rho}_X$ and negative ${\beta}_X$ values are substantiated by an imbalance of the transition state.

Metabolic Imbalance between Glycolysis and Mitochondrial Respiration Induced by Low Temperature in Rice Plants (벼 냉해의 초기 기작으로서 생체막과 세포질 사이의 대사 불균형)

  • Lee, Keun-Pyo;Boo, Yong-Chool;Jung, Jin
    • Applied Biological Chemistry
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    • v.43 no.4
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    • pp.236-240
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    • 2000
  • Correlations between mitochondrial respiration, glycolysis activity and overall growth activity of rice (Oryza sativa: cv. Dasan) seedlings during low temperature exposure were studied in order to provide insights into the underlying mechanism for the primary phase of chilling injury in plants. Among cellular membranes involved in energy metabolism, only the mitochondrial inner membrane showed not only physical phase transition at ca. $13^{\circ}C$, as monitored by ESR spin label, but also functional phase transition at the same temperature, as assessed by cytochrome c oxidase activity. The main regulatory enzyme of glycolysis, phosphofructokinase, in situ did not suffer phase transition of its activity at least in the $4{\sim}27^{\circ}C$ range. Low temperature caused a significant accumulation of glucose 6-phosphate (G6P) and fructose 6-phosphate (F6P), which disappeared almost completely on rewarming of the seedlings. Temperature profiles of the steady state levels of G6P and F6P revealed the inflection point appearing at around phase transition temperature of the mitochondrial membrane. The results conform to our previous proposition on the mechanism for the early stage events of chilling injury that the accumulation of glycolytic metabolites in cells due to metabolic imbalance at low temperature gives rise to an excess supply of electrons during rewarming period, which, in turn, results in overproduction of active oxygen in mitochondria.

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Kinetics and Mechanism of the Addition of Anilines to β-Nitrostilbenes in Acetonitrile

  • Sung, Dae-Dong;Kang, Sang-Soo;Lee, Jong-Pal;Jung, Dae-Il;Ryu, Zoon-Ha;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.28 no.10
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    • pp.1670-1674
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    • 2007
  • Addition reactions of anilines (XC6H4NH2) to β-nitrostilbene (YC6H4CH=C(NO2)C6H4Y') have been investigated in acetonitrile at 30.0 oC. The magnitude of βX values (=0.11-0.34) indicates relatively earlier transition state for additions with anilines than with benzylamines. The signs of ρY and ρY' are positive with Δρ = ρY?ρY' = 0.04, demonstrating a TS imbalance with a negative charge development on the Cβ in the TS. The signs of cross-interaction constants ρXY (<0), ρXY' (<0) and ρYY' (>0) are consistent with bond forming and breaking processes. The relatively weak normal kinetic isotope effects involving deutarated nucleophiles, kH/kD>1, suggest an early, hydrogen-bonded, 4-member cyclic TS.

The Nutrition Survey, Nutrition Surveillance and Nutrition Status in China

  • Fengying, Zhai;Dongmei, Yu
    • Proceedings of the KSCN Conference
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    • 2005.10a
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    • pp.20-32
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    • 2005
  • With the prosperous economy, the status of diet and nutrition among the urban and rural Chinese population has been improved significantly. This paper will focuses on three main surveys in China. (1)'Food and Nutrition Surveillance System in China': Phase I focused on analysis of previous data. Phase II was a pilot survey initiated in Beijing, Hebei, Heilongjiang, Ningxia, Zhejiang, Guangzhou, and Sichuan in 1990. (2) 'The China Health and Nutrition Survey' is an ongoing longitudinal project covered 8(9) provinces in 1991,1993,1997,2000. This paper will analysis the adults aged 18 45 of 1991, 1993, 1997, and 2000. (3) Survey on the status of nutrition and health of the Chinese (2002) is an across sectional study covered 31 provinces, autonomous region and the municipalities. The data was used to analyze the status of food consumption and dietary nutrients intake of Chinese population. In the past ten years, the prevalence of malnutrition and nutrition deficiency has been continuously decreased. The consumptions of animal products, milk, and edible oil have been increased, while the dairy and legume products consumption decreased. The unbalance was showed with a downward trend in cereals, vegetables and fruits consumption and a significant increase in animal products and oil intake among urban people. Dietary pattern of some subjects went away to 'high energy density' diet. The deficiency of calcium, retinal and ascorbic acid etc, especially in the rural areas still exist. China is undergoing a remarkable, but undesirable, rapid transition towards a stage of the nutrition transition characterized by high rates of DR NCDs in a very short time. China is facing the dual challenges of nutrition deficiency and nutrition imbalance. The results can help to understand the dietary structure and the status of nutrition among Chinese people over the past years. It will provide the basis for formulating relevant state policies.

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A Study on Recruitment Structure of Construction Workforce Through Surveying Wages in the Construction Industry (건설업 임금실태 조사를 통한 건설인력의 취업구조에 관한 연구)

  • Won Kyung-yeon;Park Tae-keun
    • Proceedings of the Korean Institute Of Construction Engineering and Management
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    • 2004.11a
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    • pp.246-249
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    • 2004
  • While the recovery of local construction industry is picking up steam, and the number of the employed in the construction industry is on the increase, workforce supply is out of balance in its quality as well as quantity, and with economic crisis facing the country, construction and recruitment methods are in transition. In addition, rising demand in skilled workforce and a workforce in short supply have expedited wage rises and have brought broad effects on construction including productivity and construction time. Such imbalance in construction workforce supply also causes various structural changes by category. This research compares and analyzes data on annual wages of construction workforce, analyzes the state of construction workforce supply, understands recruitment structure in accordance with workforce supply conditions, and looks over characteristic changes in recruitment structure. With reflections drawn from these, this paper suggests responsive measures to future construction circumstances - changes to wages of construction workforce - as well as prospects of future construction workforce supply and measures designed for stable medium and long-term workforce supply.

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Diagnosis of Vegetation for the Ecological Rehabilitation of Streams - The Case of the Namhan River - (하천의 생태적 복원을 위한 식생학적 진단 - 남한강을 중심으로 -)

  • Myung, Hyun;Kwon, Sang-Zoon;Kim, Chang-Hwan
    • Journal of the Korean Institute of Landscape Architecture
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    • v.30 no.5
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    • pp.98-106
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    • 2002
  • This study was designed to present a river model with the aim of restoring the ecosystem and improving the landscape along the urban rivers on the basin of the Namhanl river, a core life channel for the National Capital regin. The revelation of botanical status, transition trend and correlation of plants might lead to providing the urban river restoration projects and ecological river formation projects with basic data for a model of ideal aquatic ecology and landscape. The outcomes of this study could be summed up as follows: 1. The plant communities of river flora found on the basin of the Namhan river could be categorized largely into 39 plant communities 2. Most diverse plants were distributed in the rivers lower reaches such as Unsim-ri where the protected zone of Paldang reservoir for city water borders the body of Jodae swamp where natural streams flow nearby. 3. One of the greatest threats to the biomass of the River Namhan is that the communities of such invasive alien plants as Panicum dichotomiflorum and Ambrosia artemisiifolia var. elatior dominate most parts of the area, a fact that has resulted in a reduced variety of plants and will, sooner or later, be likely to cause an ecological imbalance in the hitherto healthy Aquatic plant life. It is highly advisable to gradually diversify the species of trees and to return the plants bark to their original state since, besides the naturalized plants, plantations afforested with Erigeron canadensis and Erigeron annuus stocks in buckwheat field, Robinia Pseudo-accacia in riverside forest, Pinus rigida in terrestrial forest on the river basin and Larix leptolepis are anticipated to act as interceptors of normal migrations of the fluvial and terrestrial ecosystems. Finally, it seems also desirable to continue to explore the relationship between fluvial and terrestrial ecologies with the purpose of building up a model of natural streams in urban areas based on the surveyed factors for plant life, soil and landscape and, moreover, on the forecasting for overall influences derived from the rotation upon the ecosystem.

Recent Findings on the Role of Epigenetic Regulators in the Small-cell Lung Cancer Microenvironment (소세포폐암의 미세환경에서 후성학적 조절인자의 역할에 대한 최신 연구 동향)

  • Min Ho Jeong;Kee-Beom Kim
    • Journal of Life Science
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    • v.34 no.7
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    • pp.520-530
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    • 2024
  • Tumor suppressor genes (TSGs) play a crucial role in maintaining cellular homeostasis. When the function of these genes is lost, it can lead to cellular plasticity that drives the development of various cancers, including small-cell lung cancer (SCLC), which is known for its aggressive nature. SCLC is primarily driven by numerous loss-of-function mutations in TSGs, often involving genes that encode epigenetic regulators. These mutations pose a significant therapeutic challenge as they are not directly targetable. However, understanding the molecular changes resulting from these mutations might provide insights for developing tumor intervention strategies. We propose that despite the heterogeneous genomic landscape of SCLC, the effects of mutations in patient tumors converge on a few critical pathways that drive malignancy. Specifically, alterations in epigenetic regulators lead to transcriptional dysregulation, pushing mutant cells toward a highly plastic state that makes them immune evasive and highly metastatic. This review will highlight studies showing how an imbalance of epigenetic regulators with opposing functions leads to the loss of immune recognition markers, effectively hiding tumor cells from the immune system. Additionally, we will discuss the role of epigenetic regulators in maintaining neuroendocrine features and how aberrant transcriptional control promotes epithelial-to-mesenchymal transition during tumor development. Although these pathways seem distinct, we emphasize that they often share common molecular drivers and mediators. Understanding the connection among frequently altered epigenetic regulators will provide valuable insights into the molecular mechanisms underlying SCLC development, potentially revealing preventive and therapeutic vulnerabilities for SCLC and other cancers with similar mutations.