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INTRINSIC NMR ISOTOPE SHIFTS OF CYCLOOCTANONE AT LOW TEMPERATURE (저온에서의 싸이클로옥타논에 대한 고유동위원소 효과)

  • Jung, Miewon
    • Analytical Science and Technology
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    • v.7 no.2
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    • pp.213-224
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    • 1994
  • Several isotopomers of cyclooctanone were prepared by selective deuterium substitution. Intrinsic isotope effects on $^{13}C$ NMR chemical shifts of these isotopomers were investigated systematically at low temperature. These istope effects were discussed in relation to the preferred boat-chair conformation of cyclooctanone. Deuterium isotope effects on NMR chemical shifts have been known for a long time. Especially in a conformationally mobile molecule, isotope perturbation could affect NMR signals through a combination of isotope effects on equilibria and intrinsic effects. The distinction between intrinsic and nonintrinsic effects is quite difficult at ambient temperature due to involvement of both equilibrium and intrinsic isotope effects. However if equilibria between possible conformers of cyclooctanone are slowed down enough on the NMR time scale by lowering temperature, it should be possible to measure intrinsic isotope shifts from the separated signals at low temperature. $^{13}C$ NMR has been successfully utilized in the study on molecular conformation in solution when one deals with stable conformers or molecules were rapid interconversion occurs at ambient temperature. The study of dynamic processes in general requires analysis of spectra at several temperature. Anet et al. did $^1H$ NMR study of cyclooctanone at low temperature to freeze out a stable conformation, but were not able initially to deduce which conformation was stable because of the complexity of alkyl region in the $^1H$ NMR spectrum. They also reported the $^1H$ and $^{13}C$ NMR spectra of the $C_9-C_{16}$ cycloalkanones with changing temperature from $-80^{\circ}C$ to $-170^{\circ}C$, but they did not report a variable temperature $^{13}C$ NMR study of cyclooctanone. For the analysis of the intrinsic isotope effect with relation to cylooctanone conformation, $^{13}C$ NMR spectra are obtained in the present work at low temperatures (up to $-150^{\circ}C$) in order to find the chemical shifts at the temperature at which the dynamic process can be "frozen-out" on the NMR time scale and cyclooctanone can be observed as a stable conformation. Both the ring inversion and pseudorotational processes must be "frozen-out" in order to see separate resonances for all eight carbons in cyclooctanone. In contrast to $^1H$ spectra, slowing down just the ring inversion process has no apparent effects on the $^{13}C$ spectra because exchange of environments within the pairs of methylene carbons can still occur by the pseudorotational process. Several isotopomers of cyclooctanone were prepared by selective deuterium substitution (fig. 1) : complete deuterium labeling at C-2 and C-8 positions gave cyclooctanone-2, 2, 8, $8-D_4$ : complete labeling at C-2 and C-7 positions afforded the 2, 2, 7, $7-D_4$ isotopomer : di-deuteration at C-3 gave the 3, $3-D_2$ isotopomer : mono-deuteration provided cyclooctanone-2-D, 4-D and 5-D isotopomers : and partial deuteration on the C-2 and C-8 position, with a chiral and difunctional case catalyst, gave the trans-2, $8-D_2$ isotopomer. These isotopomer were investigated systematically in relation with cyclooctanone conformation and intrinsic isotope effects on $^{13}C$ NMR chemical shifts at low temperature. The determination of the intrinsic effects could help in the analysis of the more complex effects at higher temperature. For quantitative analysis of intrinsic isotope effects, the $^{13}C$ NMR spectrum has been obtained for a mixture of the labeled and unlabeled compounds because the signal separations are very small.

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A study of Brachytherapy for Intraocular Tumor (안구내 악성종양에 대한 저준위 방사선요법에 관한 연구)

  • Ji, Gwang-Su;Yu, Dae-Heon;Lee, Seong-Gu;Kim, Jae-Hyu;Ji, Yeong-Hun
    • The Journal of Korean Society for Radiation Therapy
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    • v.8 no.1
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    • pp.19-27
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    • 1996
  • I. Project Title A Study of Brachytherapy for intraocular tumor II. Objective and Importance of the project The eye enucleation or external-beam radiation therapy that has been commonly used for the treatment of intraocular tumor have demerits of visual loss and in deficiency of effective tumor dose. Recently, brachytherapy using the plaques containing radioisotope-now treatment method that decrease the demerits of the above mentioned treatment methods and increase the treatment effect-is introduced and performed in the countries, Our purpose of this research is to design suitable shape of plaque for the ophthalmic brachytherapy, and to measure absorbed doses of Ir-192 ophthalmic plaque and thereby calculate the exact radiation dose of tumor and it's adjacent normal tissue. III. Scope and Contents of the project In order to brachytherapy for intraocular tumor, 1. to determine the eye model and selected suitable radioisotope 2. to design the suitable shape of plaque 3. to measure transmission factor and dose distribution for custom made plaques 4. to compare with the these data and results of computer dose calculation models IV. Results and Proposal for Applications The result were as followed. 1. Eye model was determined as a 25mm diameter sphere, Ir-192 was considered the most appropriate as radioisotope for brachytherapy, because of the size, half, energy and availability. 2. Considering the biological response with human tissue and protection of exposed dose, we made the plaques with gold, of which size were 15mm, 17mm and 20mm in diameter, and 1.5mm in thickness. 3. Transmission factor of plaques are all 0.71 with TLD and film dosimetry at the surface of plaques and 0.45, 0.49 at 1.5mm distance of surface, respectively. 4. As compared the measured data for the plaque with Ir-192 seeds to results of computer dose calculation model by Gary Luxton et al. and CAP-PLAN (Radiation Treatment Planning System), absorbed doses are within ${\pm}10\%$ and distance deviations are within 0.4mm Maximum error is $-11.3\%$ and 0.8mm, respectively. As a result of it, we can treat the intraocular tumor more effectively by using custom made gold plaque and Ir-192 seeds.

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Cumulative Risk Assessment of Organophosphorus Pesticides in the Diet (식품을 통한 유기인계농약류의 동시노출위해성평가)

  • 이효민;한지연;윤은경;김효미;황인균;최동미;이강봉;원경풍;송인상
    • Journal of Food Hygiene and Safety
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    • v.16 no.1
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    • pp.21-26
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    • 2001
  • Risk assessment traditionally are conducted on individual chemicals; however, humans are exposed to multiple chemicals in daily life. The organophosphorus (OP) pesticides are considered in a single risk assessment because they act by a common mechanism of toxicity, and there is likely to be expose to multiple OP pesticides simultaneously or sequentially. The OP pesticides act by inhibiting the enzyme acetylcholinesterasc (AChE) and have available extensive database. AChE is widely distributed throughout the body, most importantly in the nervous system. Inhibition of AChE results in accumulation of acetylcholine in the nervous system that results in clinical signs of cholinergic toxicity, including increased salivation and lacrimation, nausea and vomiting, muscle fasciculation, lethargy and fatigue, among others. To conduct an exposure assessment for pesticides in the diet, we need to know the food consumption patterns of the populations, and the pesticide residue levels in the foods that are consumed. This study was conducted to identify cumulative dietary risk due to multiple OP pesticides that can be exposed through various foods. Total 22 food samples including cereals, vegetables and fruits were collected randomly two times from food markets in several sites (4 cities). The subjected foods were selected by regarding of highly consumed foods to general Korean people. The 12 OP pesticides including Acephate, Azinphos-methyl, Chlorpyrifos, and Diazinon were monitored. For the exposure assessment, general adult group of 60 kg body weight was regarded as target population and food consumption data suggested by Lee et al. (2000) were used as consumed value of individual food. Analyses of samples for OP pesticides have been carried out according to the multiclass multiresidue analysis method and acephate and methamidophos analysis method of Korea Food Code. In general the levels of OP pesticides found in the food samples were very low or not detected.

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Introducing Strip Cropping for Decreasing the Damage of the Continous Corn Cultivation (옥수수 연작지에서 Fall panicum의 발생과 연작 피해 방지를 위한 대상작의 도입효과)

  • Lim, Keun-Bal;Lee, Hyun-Jun;Ahn, Byung-Suk;Sung, Byung-Ryul;Shin, Jae-Sun
    • Journal of The Korean Society of Grassland and Forage Science
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    • v.25 no.2
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    • pp.97-104
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    • 2005
  • This experiment was conducted to introduce strip croppings fur decreasing the damage of the continuous com cultivation at the experimental field of Grassland and Forage Crops division, National Livestock Research Institute from 1999 to 2000. Introduced mps for strip cropping to the continuously com cultivated field were red clover (RC), alfalfa(AL), and mixture of grass md legume. Fall panicum(FP), which is one of warm season's weeds was focused on its emerged quantity in com field changed by the level of soil water content and degree of the continuous corn cultivation. The ranges of yearly gained forage fresh yields including weeds like mainly FP were 119.4 ${\~}$ 169.6 in the continuous cultivation with com and rye and 64.9 ${\~}$ 83.3 ton / ha in the corn mono-cropping. Meanwhile, the percentages of pure com in continuous com cultivation plot were only $31-38\%$. This was for the mainly emergence of FP in the continuously com cultivated field. The ranges of average fresh yield of emerging FP were 45.6${\~}$63.4 ton/ ha in the continuously com cultivated field which were over the ranges of yields of rye, 28.2 ${\~}$ 41.6 ton/ ha. The dry matter yields of red clover, alfalfa and mixture with grass and legume introduced for strip cropping were 10.2, 10.6 and 10.6 ton / ha, respectively and these were about the 1/4 average fresh com yield. After strip cropping of red clover, alfalfa and mixture with grass and legume, the yields of corn increased to 56, 82, 88 and 79 ton / ha, respectively and com yield was much better in the alfalfa strip cropping.

Estimation of Glomerular Filtration Rate from Plasma Creatinine and Height in Children (소아에서 신장과 혈장 Creatinine 농도를 이용한 사구체여관율 측정)

  • Kim, Jeong-Lan;Park, Yong-Hoon;Hah, Jeong-Ok
    • Journal of Yeungnam Medical Science
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    • v.5 no.1
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    • pp.93-100
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    • 1988
  • In clinical practice, creatinine clearance(Ccr) remains the most commonly used laboratory assessment of glomerular function despite methodological and technical problems of urine collection. Schwartz et al. in 1976, reported that an accurate estimate of glomerular filtration rate(GFR) could be obtained from the simple determinations of plasma creatinine(Pcr) and body length(L) : GFR($m{\ell}/min/1.73m^2$=k L(cm)/Pcr(mg/$100m{\ell}$), (k=constant). The subject of this study were ill children admitted to our pediatric department from July, 1985 to June, 1987 and they were divided into three groups; group I, from 1 to 5 years old, group II, from 6 to 10 years old, group III. from 11 to 15 years old. The results were as following ; 1) Measured creatinine clearance($Ccr_M$, $m{\ell}/min/1.73m^2$) were $109.73{\pm}9.97$ in group I, $108.26{\pm}9.02$ in group II, $96.20{\pm}4.72$ in group III and $105.48{\pm}5.23$ in all age group. 2) Measured k($k_M$) obtained from $Ccr_M=k$ Ht/Pcr were $0.49{\pm}0.03$ in group I, $0.48{\pm}0.02$ in group II, $0.43{\pm}0.02$ in group III, and $0.47{\pm}0.02$ in all age group.(Ht ; height) 3) Linear equations and correlation coefficients between Ht/Pcr(x) and Ccr(y) were y=0.822x-65.63(r=0.99) in group I, y=0.61x-23.46(r=0.72) in group II, y=0.18x+54.44(r=0.54) in group III and y=0.58x-22.13(r=0.81) in all age group. 4) $Ccr_E$ was again estiamted from linear equations between Ht/Pcr and $Ccr_M$ and $k_E$ was calculated with Ht/Pcr and $Ccr_E$ were $0.48{\pm}0.01$ in group I, $0.49{\pm}0.01$in group II, $0.43{\pm}0.01$ in group III and $0.47{\pm}0.00$ in all age group. 5) Consistant values of $k_E$ and $k_M$ were highly significant as 95~97.5% in group I and II, 90~95% in group III and 97.5~99% in all age group. In summary, we could estimate GFR with height, plasma creatinine and measured k($k_M$) according to the age in easy and rapid way.

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Studies on Feed Intake and Nutrient Utilization of Sheep under Two Housing Systems in a Semi-arid Region of India

  • Bhatta, Raghavendra;Swain, N.;Verma, D.L.;Singh, N.P.
    • Asian-Australasian Journal of Animal Sciences
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    • v.17 no.6
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    • pp.814-819
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    • 2004
  • An investigation was carried out to study the effect of two housing systems on feed intake and nutrient utilization of sheep in a semi-arid region of India. Two types of housing managements were adopted. The first was a shed- 20'${\times}$10' structure with all the four sides of 6' chain link fencing with central height of 10'. The roof was covered with asbestos sheets, with mud floorings. The second was an open corral- 20'${\times}$10' open space with all the four sides covered with 6' chain link fencing. Thirty-four (32 ewes and 2 rams) sheep were grazed together on a 35 ha plot of native range. All the sheep were grazed as a flock from 08:00 to 17:00 h during the yearlong study. The flock was divided into two groups (16 ewes+1 ram) in the evening and housed according to two housing systems (Shed and Open Corral). Three digestion trials were conducted during three defined seasons of monsoon, winter and summer seasons to determine the effect of housing on nutrient intake and utilization. Blood samples were collected in three seasons for the estimation of hemoglobin and glucose. Dry and wet bulb temperatures were recorded at 06:00 A.M. and 09:00 P.M. using suitable thermometers both inside the shed and in the open corral and temperature humidity index (THI) was calculated. There was significant (p<0.05) difference in the THI between shed and open corral in all the seasons, indicating that the shed was always warmer compared to open corral. The daily dry matter intake (DMI, g/d) was 965, 615 and 982 in sheep housed under shed and 971, 625 and 1,001 in those housed in open corral during monsoon, winter and summer season, respectively. These differences were however non-significant (p>0.05). The digestibility of DM was 45.92, 45.13 and 50.30 in sheep housed under shed and 43.64, 45.02 and 55.02 in sheep housed in open corral during monsoon, winter and summer seasons, respectively. There was no significant (p>0.05) difference in the digestibility of nutrients in sheep maintained under shed and in open corral. Blood Hb concentration was 13.97, 14.13 and 13.15 in sheep housed under shed and 15.27, 13.63 and 14.82 in those kept in open corral, whereas blood glucose concentration was 59.67, 59.70 and 52.33 in sheep under shed and 61.00, 61.00 and 57.83 in open corral, during monsoon, winter and summer, respectively. There was also no significant effect of housing on the body weight changes, wool yield and survivability in ewes. Although housing had no significant effect on nutrient intake, their utilization and blood parameters, there was significant effect on the physiological responses and energy expenditure of sheep maintained under the two housing systems (Bhatta et al., 2004). It can be concluded from this study that the housing systems didn't have any significant effect on the nutrient intake and utilization of native breed like Malpura, which were well adapted to the hot semi-arid conditions of India. However, while deciding provisions for housing of different breeds of sheep (both crossbred and native) parameters like physiological responses, energy expenditure, health conditions and overall economics of the systems should be taken into consideration.

A Comparison of Illness Behavior among Patients with Somatoform Disorders, Depressive Disorders and Psychosomatic Disorders (신체형장애, 우울장애 및 정신신체장애 환자들간의 질병행동의 비교)

  • Koh, Kyung-Bong;Ki, Sun-Wan
    • Korean Journal of Psychosomatic Medicine
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    • v.5 no.2
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    • pp.185-194
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    • 1997
  • A comparison was made regarding illness behavior among patients with somatoform disorders, depressive disorders and psychosomatic disorders. The subjects consisted of out-patients with somatoform disorders(N=52), depressive disorders(N=52) and psychosomatic disorders(N=51). illness behavior was assessed by illness Behavior Assessment Schedule and the questionnaire about help-seeking behavior. The patients with somatoform disorders and psychosomatic disorders more often affirmed the presence of somatic disease, were more likely to have phobia of disease, had more preoccupation with ideas of disease and more frequently shopped around oriental clinics than the patients with depressive disorders. The patients with somatoform disorders more often attributed its cause to physical factors, less often attributed the origin of affective disturbance to psychological causes, showed Less depression and irritability, and were less likely to accept psychiatric treatment recommended by other physicians than depressive patients. The patients with somatoform disorders were more likely to report having been told that they suffered from a mild illness than those with psychosomatic disorders. The patients with somatoform disorders with psychological problems tended to inhibit expression of their emotion. Female patients with somatoform disorders more often affirmed the presence of psychological disorder and attributed its cause to psychological factors than male ones. These results suggest that in illness behavior, patients with somatoform disorders are different from depressive patients, whereas the former patients are similar to psychosomatic patients except the discrepancy between therapists and patients regarding evaluation of their symptoms. Thus, it is emphasized that first, therapists need to approach patients with somatoform disorders somatically with understanding of their underlying need to deny psychological problems, followed by either psychological or biopsychosocial approach.

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Saponins of Korean Ginseng Panax ginseng C.A. Meyer (Part III) -Saponins of ginseng by the cultivating locations, sampling seasons, plant parts, growing stages and the processings- (한국인삼(韓國人蔘)의 Saponin에 관(關)한 연구(硏究)제3보(第三報) -산지별(産地別), 부위별(部位別), 재배기간별(栽培期間別) 인삼(人蔘) 및 가공중(加工中) Saponin함량(含量)에 관(關)하여-)

  • Cho, Sung-Hwan
    • Applied Biological Chemistry
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    • v.20 no.2
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    • pp.188-204
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    • 1977
  • The studies on the saponins of Korean ginseng, Panax ginseng C.A. Meyer, were performed according to the cultivating locations, sampling seasons, plant parts, and growing stages. The changes in saponin content in the course of manufacturing Red ginseng and Ginseng extract were observed. In this paper, a new method for the determination of the total and the individual saponin glucosides was proposed and applied to the samples under study. The method employing Digital Densitorol DMU-33C (Toyo electric Co., Japan) followed the separation of the saponins by means of a preparative thin layer chromatography. The saponin contents and their fractional distribution were summarized as follows: 1. The average concentrations(% plant dry weight) of semi-purified saponins in the roots of Korean ginseng planted in the various locations were 5.0%(Keumsan), 6.0% (Kimpo), and 5.4% (Pocheon), respectively. 2. There were 3.3% saponins in White ginseng(Rhizome) and 12.7% saponins in Ginseng tail (Fibrous root). 3. Regarding the year of growth, the contents of saponins were 90.3mg (2-year-old ginseng), 254.4mg (3-year-old ginseng), 404.2mg (4-year-old ginseng). 999.6mg (5-year-old ginseng), and 1377.1mg (6-year-old ginseng) respectively, and the saponin factions containing panaxatriol as an aglycone increased. 4. Thin layer chromatography revealed that Red ginseng yielded many saponins which Shibata et al. designated as $ginsenoside-Rb_1$ (22.1%), $-Rb_2(15.4%)$, -Rc(12.6%), -Re (15.7%), and $-Rg_1$, (9.3%). 5. 29.9% of crude saponins were isolated from ethanolic extract of Panax ginseng fibrous root and their extraction yield was 94.2% of fibrous root saponin.

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Detection of Irrigation Timing and the Mapping of Paddy Cover in Korea Using MODIS Images Data (MODIS 영상자료를 이용한 관개시기 탐지와 논 피복지도 제작)

  • Jeong, Seung-Taek;Jang, Keun-Chang;Hong, Seok-Yeong;Kang, Sin-Kyu
    • Korean Journal of Agricultural and Forest Meteorology
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    • v.13 no.2
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    • pp.69-78
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    • 2011
  • Rice is one of the world's staple foods. Paddy rice fields have unique biophysical characteristics that the rice is grown on flooded soils unlike other crops. Information on the spatial distribution of paddy fields and the timing of irrigation are of importance to determine hydrological balance and efficiency of water resource management. In this paper, we detected the timing of irrigation and spatial distribution of paddy fields using the Moderate Resolution Imaging Spectroradiometer (MODIS) sensor onboard the NASA EOS Aqua satellite. The timing of irrigation was detected by the combined use of MODIS-based vegetation index and Land Surface Water Index (LSWI). The detected timing of irrigation showed good agreement with field observations from two flux sites in Korea and Japan. Based on the irrigation detection, a land cover map of paddy fields was generated with subsidiary information on seasonal patterns of MODIS enhanced vegetation index (EVI). When the MODISbased paddy field map was compared with a land cover map from the Ministry of Environment, Korea, it overestimated the regions with large paddies but underestimated those with small and fragmented paddies. Potential reasons for such spatial discrepancies may be attributed to coarse pixel resolution (500 m) of MODIS images, uncertainty in parameterization of threshold values for discarding forest and water pixels, and the application of LSWI threshold value developed for paddy fields in China. Nevertheless, this study showed that an improved utilization of seasonal patterns of MODIS vegetation and water-related indices could be applied in water resource management and enhanced estimation of evapotranspiration from paddy fields.

Evaluation of Sperm Penetration Ability according to Various Morphological Characteristics of Spermatozoa (정자의 여러가지 형태학적 특징에 따른 정자 침투능의 평가)

  • Kim, J.H.;Jung, K.W.;Lew, Y.O.;Kwon, D.J.;Lim, Y.T.;Kim, J.H.;Nha, D.J.;Lee, J.W.
    • Clinical and Experimental Reproductive Medicine
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    • v.21 no.1
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    • pp.31-41
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    • 1994
  • Morphological estimation of human spermatozoa is complicated by the fact that there is great natural variation in shape. This natural variation in shapes makes it difficult to say which forms are associated with infertility and which are normal variations. Possibly post coital test or in vitro cervical mucus penetration tests will help to clarify this question by showing which sperm are capable of penetration. The purpose of this investigation was performed to assess distribution of various morphological abnormalities according to the ability of sperm to penetrate cervical mucus. The sperm-mucus penetration using hen's egg white as substituting mucus for human cervical mucus was done in 45 fertile men with normal semen analysis and 122 infertile men with abnormal seminal parameters more than one. The female partners of 122 infertile couples showed normal results in the female fundamental test for fertility. Conventional semen analysis was evaluated according to the WHO standard normal(l980). The detailed classification of the abnormal sperm was made according to David et al(l975). The vitality of the sperm samples determined by eosin yellow-nigrosin stainig according to the method of Eliasson(l977). Results were as follw; 1. The patients had significantly lower total sperm count, motility (%), normal morphology (%), viability and total functional sperm fractions(TFSF) than fertile donors. 2. The mean value of sperm penetration distance of the patients(28.69${\pm}$11.02mm) showed significantly lower than fertile donors(37.33${\pm}$5.49mm). And 43/45 fertile donors(95.5%) as well as 57/122 patients(46.7%) had over 30mm in sperm penetration distance respectively. While 2/45 fertile donors(4.5 %) and 65/122 patient(53.3%) had under 30mm in sperm penetration distance respectively. 3. The morphological abnormalities in fertile donors were significantly lower 23.04${\pm}$5.83% (head = 12.89${\pm}$4.98, neck=6.11${\pm}$3.83%, and tail=3.43${\pm}$2.65%), compared to 36.03${\pm}$14. 40% in patients(head = 15.98 8.60%, neck 11.20${\pm}$6.56% and tail=8.70${\pm}$6.55%). Also, 3 types of sperm abnormalities including head, neck and tail were significantly lower in patient than fertile donors, respectively. Both the patients and fertile donors showed higher distribution of sperm with abnormal head than abnormal neck and tail. 4. The mean morphological abnormalities(SP>30mm) of the patients(30.68 11.64%; head = 15.95${\pm}$9.35%, neck=8.14${\pm}$4.21 %, tail=6.56${\pm}$5.64%) were significantly lower compared to patients(40.72${\pm}$15.01 %; head=16.02${\pm}$7.69%, neck 13.89${\pm}$7.82%, tail=1O.58${\pm}$6.75%) under 30mm in sperm penetration distance. Also, both groups over 30mm and under 30mm in sperm penetration showed distance higher distribution of sperm with abnormal head than abnormal neck and tail. The morphological abnormalities of head did not show significant difference but abnormal neck and tail were significant difference between the over 30mm and under 30mm group in sperm penetration distance.

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