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1.
In recent years, the evaluation of healthcare provider performance has become standard for governments, insurance companies, and other stakeholders. Often, performance is compared across providers using indicators in one time period, for example a year. However it is often important to assess changes in the performance of individual providers over time. Such analyses can be used to determine if any providers have significant improvements, deteriorations, unusual patterns or systematic changes in performance. Studies which monitor healthcare provider performance in this way have to date typically been limited to comparing performance in the most recent period with performance in a previous period. It is also important to consider a longer‐term view of performance and assess changes over more than two periods. In this paper, we develop test statistics that account for variable numbers of prior performance indicators, and show that these are particularly useful for assessing consecutive improvements or deteriorations in performance. We apply the tests to coronary artery bypass graft mortality rates in New York State hospitals, and mortality data from Australian and New Zealand intensive care units. Although our applications are to medical data, the new tests have broad application in other areas.  相似文献   

2.
目的:探讨测定血清腺苷脱氨酶(ADA)、游离脂肪酸(FFA)在2型糖尿病患者诊疗中的临床应用价值.方法:比较102例2型糖尿病患者和89例健康对照者及102例2型糖尿病患者中62例血糖控制理想的和40例血糖控制不理想的糖尿病患者的血清ADA、FFA、空腹血糖(FBS)、糖化血红蛋白(HbA1C)水平.结果:2型糖尿病患者的血清ADA、FBS、FFA、HbAlC显著高于对照组(P<0.01),差异有统计学意义,且血清ADA与HbAlC呈显著正相关系(r=0.41,P<0.01);FFA与HbAlC呈显著正相关系(r=0.19,P<0.05);血糖控制不理想的2型糖尿病患者血清ADA、FBS、HbAlC、FFA与血糖控制理想的比较显著升高(P<0.01,P<0.05).结论:血清ADA、FFA测定对评价2型糖尿病患者血糖控制好坏有良好的应用价值.  相似文献   

3.
The factors influencing the priority of access to food and the effects of the priority of access to food on their carcass traits were analyzed for Japanese Black (Wagyu) cattle in a semi-intensive fattening production system. The records of 96 clinically healthy steers and heifers were analyzed. The calves at ∼3 to 4 months of age were allocated to pens with four animals per pen; all four animals in the same pen were of the same sex and of similar body size. The ranking of the animals’ priority of access to food (1st, 2nd, 3rd and 4th), which was determined by the farm manager, was used as an indicator of social dominance in the present study. Four models including sire line, maternal grandsire line and the difference in the animals’ birth dates as fixed effects were used to analyze factors influencing the priority of access to food. Ranking was represented by ordinal scores (highest=4, lowest=1) in Model 1, and the binary scores were assigned in Model 2 (highest=1; 2nd, 3rd and 4th=0), Model 3 (1st and 2nd=1; 3rd and 4th=0) and Model 4 (1st, 2nd and 3rd=1; lowest=0). The results showed that the difference in the animals’ birth dates had a significant effect on the establishment of the priority of access to food in Model 3 (P<0.05), suggesting that animals born earlier may become more dominant in the pen. The maternal grandsire line tended to affect the social rank score in Models 2 and 3 (P<0.10). Our results indicated that the maternal grandsire line may affect the temperament of calves through their mothers’ genetic performance and thereby more aggressive calves may be more dominant and have higher priority of access to food. On the other hand, there was a significant effect of the priority of access to food on beef marbling score (BMS; P<0.05), and the priority of access to food also tended to influence the carcass weight (P=0.09). The highest BMS was observed for animals with the first rank of the priority of access to food (P<0.05), and the higher-ranking animals had the tendency to be heavier carcass than the lower-ranking animals. Our findings emphasized the importance of information about the priority of access to food determined by farmers’ own observation on implementing best management practices in small-scaled semi-intensive beef cattle production systems.  相似文献   

4.
目的:探讨中性粒细胞与淋巴细胞比值(neutrophil to lymphocyte rate,NLR)在急诊老年社区获得性肺炎(community acquired pneumonia,CAP)患者中的应用价值.方法:选择2018年10月到2019年10月首都医科大学宣武医院急诊观察室收治的130例老年CAP患者,检...  相似文献   

5.
摘要 目的:探讨血清D-二聚体(D-D)、尿素氮与肌酐比值(UCR)联合C反应蛋白与白蛋白比值(CAR)对重症肺炎(SP)患者院内死亡的评估价值。方法:选取2019年6月~2022年6月我院收治的101例SP患者,根据是否发生院内死亡分为死亡组和存活组。检测血清D-D和计算UCR、CAR。分析SP患者院内死亡的影响因素,受试者工作特征(ROC)曲线分析血清D-D、UCR、CAR对SP患者院内死亡的评估价值。结果:101例SP患者院内死亡率40.59%(41/101)。死亡组血清D-D、UCR、CAR高于存活组(P均<0.05)。多因素Logistic回归分析显示,年龄增加、肺外并发症≥2个和D-D、UCR、CAR升高为SP患者院内死亡的独立危险因素(P均<0.05)。ROC曲线分析显示,血清D-D、UCR、CAR单独与联合评估SP患者院内死亡的曲线下面积分别为0.781、0.798、0.793、0.929,血清D-D、UCR联合CAR评估SP患者院内死亡的AUC大于各指标单独评估。结论:血清D-D、UCR、CAR升高为SP患者院内死亡的独立危险因素,D-D、UCR联合CAR对SP患者院内死亡的评估价值较高。  相似文献   

6.
J.Michael Gould  S. Izawa 《BBA》1974,333(3):509-524
1. By using dibromothymoquinone as the electron acceptor, it is possible to isolate functionally that segment of the chloroplast electron transport chain which includes only Photosystem II and only one of the two energy conservation sites coupled to the complete chain (Coupling Site II, observed P/e2 = 0.3–0.4). A light-dependent, reversible proton translocation reaction is associated with the electron transport pathway: H2O → Photosystem II → dibromothymoquinone. We have studied the characteristics of this proton uptake reaction and its relationship to the electron transport and ATP formation associated with Coupling Site II.

2. The initial phase of H+ uptake, analyzed by a flash-yield technique, exhibits linear kinetics (0–3 s) with no sign of transient phenomena such as the very rapid initial uptake (“pH gush”) encountered in the overall Hill reaction with methylviologen. Thus the initial rate of H+ uptake obtained by the flash-yield method is in good agreement with the initial rate estimated from a pH change tracing obtained under continuous illumination.

3. Dibromothymoquinone reduction, observed as O2 evolution by a similar flash-yield technique, is also linear for at least the first 5 s, the rate of O2 evolution agreeing well with the steady-state rate observed under continuous illumination.

4. Such measurements of the initial rates of O2 evolution and H+ uptake yield an H+/e ratio close to 0.5 for the Photosystem II partial reaction regardless of pH from 6 to 8. (Parallel experiments for the methylviologen Hill reaction yield an H+/e ratio of 1.7 at pH 7.6.)

5. When dibromothymoquinone is being reduced, concurrent phosphorylation (or arsenylation) markedly lowers the extent of H+ uptake (by 40–60%). These data, unlike earlier data obtained using the overall Hill reaction, lend themselves to an unequivocal interpretation since phosphorylation does not alter the rate of electron transport in the Photosystem II partial reaction. ADP, Pi and hexokinase, when added individually, have no effect on proton uptake in this system.

6. The involvement of a proton uptake reaction with an H+/e ratio of 0.5 in the Photosystem II partial reaction H2O → Photosystem II → dibromothymoquinone strongly suggests that at least 50% of the protons produced by the oxidation of water are released to the inside of the thylakoid, thereby leading to an internal acidification. It is pointed out that the observed efficiencies for ATP formation (P/e2) and proton uptake (H+/e) associated with Coupling Site II can be most easily explained by the chemiosmotic hypothesis of energy coupling.  相似文献   


7.
摘要 目的:研究入院时损伤严重程度评分(ISS)、休克指数联合血清多配体蛋白聚糖-1(Syndecan-1)、血管性假血友病因子(VWF)对多发伤患者创伤性凝血病(TIC)的预测价值。方法:选取2019年1月至2022年12月在上海中医药大学附属普陀医院接受治疗的200例多发创伤患者。根据是否发生TIC分为TIC组(61例)以及非TIC(NTIC)组(139例)。对比两组入院时ISS评分、休克指数及血清Syndecan-1、VWF水平,单因素及多因素Logistic回归分析多发伤患者TIC发病的影响因素,受试者工作特征(ROC)曲线分析入院时ISS评分、休克指数及血清Syndecan-1、VWF对多发伤患者TIC发病的预测价值。结果:200例患者中,总计发生61例TIC患者,发生率是30.50%。TIC组的ISS评分、休克指数、Syndecan-1及VWF水平均较NTIC组更高(P<0.05)。多因素Logistic回归分析发现,低体温、酸中毒、格拉斯哥昏迷评分(GCS)<6分、并发重型颅脑损伤、入院时ISS评分升高、休克指数升高、血清Syndecan-1升高、VWF升高为多发伤患者TIC发病的危险因素。ROC曲线分析入院时ISS评分、休克指数及血清Syndecan-1、VWF等四指标联合应用对于TIC的预测价值最高,其中曲线下面积(AUC)为0.849、灵敏度为0.918、特异度为0.755,均较各项的单独预测效果更好。结论:多发伤患者入院时ISS评分升高、休克指数升高、血清Syndecan-1升高、VWF升高与TIC的发病有关。低体温、酸中毒、GCS<6分、并发重型颅脑损伤、入院时ISS评分升高、休克指数升高为多发伤患者TIC发病的危险因素。入院时ISS评分、休克指数联合血清Syndecan-1、VWF检测对多发伤患者TIC发病具有较高的预测价值。  相似文献   

8.
土壤盐分空间变异特征和地下水埋深状况是指导灌区合理用水和防治土壤盐碱化的重要依据。运用经典统计学和地质统计学方法,结合GIS技术,分析了河套灌区沙壕渠灌域0-20 cm、20-40 cm、40-60 cm土壤EC值的空间变异特征及地下水埋深对土壤盐分分布的影响。结果表明:沙壕渠灌域土壤盐分Cv值在不同灌溉时期和不同土壤深度均大于36%,表现为强变异特征;各灌水时期和不同土壤深度土壤EC值均表现为中等强度的空间自相关性,表层0-20 cm土壤空间自相关程度最高;秋浇前不同层次土壤EC值的空间分布在灌域内从南到北呈增大趋势,秋浇后土壤含盐量的高值区在西北部或东北部;土壤盐分受地下水埋深影响显著,灌域内地下水埋深南深北浅,土壤盐分随地下水埋深的增大而减小,二者之间满足指数关系。因此,应采取合理措施控制地下水埋深,防止区域土壤盐渍化加剧。  相似文献   

9.
目的:研究血小板/淋巴细胞比值(PLR)在老年2型糖尿病(T2DM)患者肾功能损害及病情评估中的应用价值。方法:测定506例T2DM患者及250例健康体检者(对照组)的血常规、血糖、血脂、肝肾功等生化指标,并收集尿液测定尿白蛋白/肌酐比值(ACR)。根据《糖尿病肾病防治专家共识(2014年版)》,将T2DM患者分为DN组(n=279)和非DN组(n=227),并根据ACR将DN组分为微量白蛋白尿组(n=165,30~300 mg/24 h)、大量白蛋白尿组(n=114,≥300 mg/24 h)。比较各组患者临床指标,分析PLR与老年T2DM患者并发DN的相关性。结果:与对照组比较,非DN组、DN组HbAlc、FPG、2h PG、Scr、BUN、PLT、PLR明显升高,LYM明显下降(P0.05);与非DN组比较,微量白蛋白尿组HbAlc、2h PG、Scr、UAER、eGFR明显升高,大量白蛋白尿组HbAlc、FPG、2h PG、Scr、BUN、UAER、eGFR、PLT、PLR明显升高,LYM明显下降(P0.05);与微量白蛋白尿组,大量白蛋白尿组FPG、Scr、BUN、UAER、eGFR、PLT、PLR明显升高,LYM明显下降(P0.05)。多因素logistics回归分析显示HbAlc、PLR是T2DM患者进展为DN的独立危险因素,而eGFR则是保护性因素(P0.05)。HbAlc、eGFR、PLR联合预测T2DM患者并发DN的敏感性、特异性分别为83.1%,特异度为81.9%,均显著高于三个指标单独评估的敏感性、特异性(P0.05)。结论:PLR是老年T2DM患者肾功能损害的独立危险因素,综合HbAlc、eGFR、PLR有助于老年T2DM患者并发DN及病情评估。  相似文献   

10.
摘要 目的:探讨单吸入器三联疗法联合肺早期康复运动训练治疗中重度慢性阻塞性肺疾病(COPD)患者的临床研究。方法:根据随机数字表法,将汕头大学医学院第二附属医院2022年7月-2023年1月间收治的84例中重度COPD患者分为对照组(42例,单吸入器三联疗法治疗)和实验组(42例,对照组的基础上接受肺早期康复运动训练治疗)。观察并对比两组的肺功能指标[用力肺活量(FVC)、第一秒用力呼气容积(FEV1)、FEV1/FVC]、血气分析指标[血氧饱和度(SaO2)、动脉血氧分压(PaO2)、动脉血二氧化碳分压(PaCO2)]、6分钟步行距离(6MWD)、COPD评估测试(CAT)评分、治疗期间急性加重频率、血清炎症因子[肿瘤坏死因子-α(TNF-α)、白介素-6(IL-6)、C反应蛋白(CRP)]。结果:治疗后,实验组FEV1、FVC、FEV1/FVC高于对照组(P<0.05)。治疗后,实验组PaCO2低于对照组,PaO2、SaO2高于对照组(P<0.05)。治疗后,实验组6MWD高于对照组,CAT评分、治疗期间急性加重频率低于对照组(P<0.05)。治疗后,实验组血清TNF-α、IL-6、CRP水平低于对照组(P<0.05)。结论:单吸入器三联疗法联合肺早期康复运动训练治疗中重度COPD患者,可增强运动耐力,提高生活活动能力,减少治疗期间疾病急性加重频率,同时还可改善血气分析和肺功能指标,降低血清炎症因子水平。  相似文献   

11.
BACKGROUND: The prognostic value of serum biomarkers in soft tissue sarcoma (STS) is limited, and its clinical applicability is compromised by a common inability to adjust for important confounders. The aim of this study was to determine the prognostic value of pretreatment biomarkers on disease-specific survival (DSS) adjusted for confounders. METHODS: The study included 818 patients with localized STS. Pretreatment levels of albumin, C-reactive protein, hemoglobin, neutrophils, and lymphocytes were tested individually and combined in prognostic scores: neutrophil/lymphocyte ratio (NLR), Glasgow Prognostic Score (GPS), and Aarhus Composite Biomarker Score (ACBS) which includes all five biomarkers. Patients were randomly split into a test cohort and a validation cohort. The prognostic value of biomarkers on DSS was estimated using crude and adjusted Cox proportional hazard models. The different biomarker scores were compared using Akaike's information criteria. RESULTS: In the test cohort of 403 patients, all biomarkers except lymphocyte count were significant prognostic factors for DSS also after adjusting for confounders. NLR, GPS, and ACBS were independently associated with decreased survival; however, ACBS was significantly superior to NLR (P = .02) and GPS (P = .002). These findings were validated in the randomly assigned validation cohort of 415 patients. In the pooled data of 818 patients, the ACBS performed better than GPS and NLR. ACBS 2 was independently associated with decreased DSS compared to ACBS 0, hazard ratio 2.3[95% confidence interval: 1.5-3.5], P < .001. CONCLUSION: Patients with abnormal values in more than one serum biomarkers had a significant additional risk of dying compared to patients with only one abnormal value. ACBS was validated as an independent prognostic factor that is superior to both NLR and GPS.  相似文献   

12.
目的:探讨中心静脉动脉二氧化碳分压差/氧含量差(Pcv-aCO_2/Ca-cvO_2)变化率在急诊重症监护室(EICU)高乳酸脓毒血症患者病情及预后评估中的临床应用价值。方法:选择2017年1月到2018年9月入住急诊重症监护室的48例高乳酸(乳酸大于4 mmol/h)脓毒血症患者,均按2016年脓毒症指南进行液体复苏治疗。采集复苏前(T0h)和开始复苏后6h(T6h)、24h(T24h)的动脉血、上腔静脉血气分析以及动脉血乳酸浓度。计算并记录各时间点的乳酸,乳酸清除率,中心静脉动脉二氧化碳分压差(Pcv-aCO_2)值,中心静脉动脉二氧化碳分压差/氧含量(Pcv-aCO_2/Ca-cvO_2)值及其变化率。根据治疗24h改良SOFA评分是否改善将患者分为两组,即改良SOFA改善组和未改善组,观察和比较两组间基本临床资料及化验参数,并分析各时间点各参数之间的相关性,以及这些参数能否有效预测高乳酸脓毒血症患者病情危重程度和预后。结果:45例患者纳入最终分析,3例因为24h内死亡或者自动出院脱落。其中,17例24hSOFA改善,28例未改善;20例死亡,25例存活。两组患者复苏前各项一般临床资料指标比较差异均无统计学意义(P0.01)。24hSOFA改善组与未改善组患者Pcv-aCO_2/Ca-cvO_2(T24h)、Pcv-aCO_2/Ca-cvO_2变化率(0-24h)存在组间差异(P0.01)。45例患者的乳酸清除率(0-24h)与Pcv-aCO_2/Ca-cvO_2变化率(0-24h)呈显著相关性(r=0.906,P=0.034)。ROC分析显示Pcv-aCO_2/Ca-vO_2变化率(0-24h)能有效预测24hSOFA评分改善,同其他指标相比,曲线下面积最大(AUROC=0.851),最佳界值是0.307(30.7%),敏感度是76.5%,特异度是92.9%;Pcv-aCO_2/Ca-vO_2变化率(0-24h)也能有效预测脓毒症患者院内死亡,AUROC=0.696,AUROC较24h乳酸值小,但不存在统计学差异,最佳界值是0.181(18.1%),敏感度是65%,特异度是68%。结论:液体复苏前到开始复苏后24h的Pcv-aCO_2/Ca-cvO_2变化率可以有效预测高乳酸脓毒症患者的器官功能改善情况,也能有效预测脓毒症患者院内死亡的发生。  相似文献   

13.
In order to address the complexity of needs of dependent older people, multidimensional and person-centered needs assessment is required. The objective of this review is to describe met and unmet needs of dependent older people, living in the community or in institutions, and the factors associated with those needs. Selection criteria included papers about need asessment which employed the Camberwell Assesment of Need for the Elderly (CANE). A search through MEDLINE, SCOPUS, WOS and CINHAL databases was carried out. Twenty-one articles were finally included. Unmet needs were found more frequently in psychosocial areas (mainly in “company”, “daytime activities” and “psychological distress”) and in institutionalized population. In addition, unmet needs were often associated with depressive symptoms, dependency, and caregiver burden. Discrepancies between self-reported needs and needs perceived by formal and informal caregivers were identified. It is important that professionals and caregivers try to make visible the perspective of older people and their psychological and social needs, particularly when the person is dependent, depressed or cognitively impaired.  相似文献   

14.
摘要 目的:探讨血培养阳性报警时间(TTP)联合降钙素原(PCT)、中性粒细胞/淋巴细胞比值(NLR)对大肠埃希菌血流感染(BSI)患者死亡风险的预测价值。方法:选取2020年1月~2022年6月我院收治的223例大肠埃希菌BSI患者,根据入院后28 d内是否死亡分为死亡组和存活组。收集患者临床资料和血培养TTP,检测PCT、NLR。采用多因素Logistic回归分析大肠埃希菌BSI患者死亡的影响因素。采用受试者工作特征(ROC)曲线分析TTP、PCT、NLR对大肠埃希菌BSI患者死亡风险的预测价值。结果:223例大肠埃希菌BSI患者入院后28 d内死亡率为30.04%(67/223)。死亡组TTP短于存活组,PCT、NLR高于存活组(P均<0.001)。多因素Logistic回归分析显示,年龄增加、入住重症监护病房(ICU)、气管插管/切开、PCT升高、NLR升高为大肠埃希菌BSI患者死亡的独立危险因素,TTP延长为独立保护因素(P<0.05)。ROC曲线分析显示,TTP、PCT、NLR联合预测大肠埃希菌BSI患者死亡的曲线下面积大于各指标单独预测。结论:TTP缩短和PCT、NLR升高与大肠埃希菌BSI患者死亡风险增加相关,TTP、PCT、NLR联合预测大肠埃希菌BSI患者死亡风险的价值较高。  相似文献   

15.
16.
目的:探讨改良血管套接法与血管断端吻合法对断指再植患者断指血运、断指成活以及运动功能的影响。方法:回顾性分析我院于2017年1月到2018年12月期间治疗的107例断指再植患者的临床资料。根据手术方法的不同将患者分为A组(n=55,共断指93指)和B组(n=52,共断指86指),A组给予血管断端吻合法,B组给予改良血管套接法,比较两组患者断指血运、断指成活、运动功能、生活质量及并发症。结果:B组毛细血管充盈时间、患指微循环检测值低于A组,氧饱和度、经皮氧分压则高于A组(P<0.05)。B组断指成活率、断指张力正常率及断指颜色正常率均高于A组(P<0.05)。B组术后1年社会关系领域、生理领域、心理领域以及环境领域的维度评分均高于A组(P<0.05)。B组的肌力、活动度、灵巧度、Carroll量表评分均高于A组(P<0.05)。两组并发症发生率对比未见统计学差异(P>0.05)。结论:与血管断端吻合法相比,断指再植患者采用改良血管套接法,在断指血运、断指成活、运动功能、生活质量方面的改善效果更佳,且不会增加并发症发生率。  相似文献   

17.
摘要 目的:对比分析冷刀系统与宫腔镜下能量系统分别联合芬吗通治疗中重度宫腔粘连疗效。方法:选取2020年1月-2022年1月我院收治的中重度宫腔粘连患者80例为研究对象,分为对照组(n=40)和观察组(n=40)。对照组采用宫腔镜下能量系统联合芬吗通治疗,观察组采用冷刀系统联合芬吗通治疗。对比两组临床指标、临床疗效、月经恢复情况、并发症发生情况。结果:观察组手术时间、术中出血量、手术次数、术后出血量均短/少于对照组(P<0.05)。术后12个月观察组临床疗效(90.00%)显著高于对照组(65.00%)(P<0.05)。术后8~14个月两组的月经恢复情况均改善,观察组月经恢复情况较对照组更优(P<0.05)。观察组术后感染、子宫腺肌病、子宫穿孔、水中毒等并发症的总发生率(7.50%)低于对照组(47.50%)(P<0.05)。结论:冷刀系统联合芬吗通治疗宫腔粘连具有显著疗效,不仅对患者的危害更小,还有利于月经恢复,减少并发症,改善预后。  相似文献   

18.
In experimental situations examining the effectiveness of p(p>1) treatments by comparing treated groups and untreated controls the following question arose: Which experimental arrangement is more appropriate, an arrangement A1 using for the p comparisons only one single control, or an arrangement A2 using for every comparison another control. To answer this question two criteria are formulated. The first criterion takes into consideration the expected numbers of type I and type II errors, and the second criterion the probabilities of type I and of type II errors. According to the first criterion A1 and A2 do not differ, generally. According to the second criterion A1 with the comparison of means of normal distributed variables is better than A2. Pooling of all p controls is better than A2 according to both criteria. A1 is better also according to the often used experimentwise type I error rate. The formulated criteria have some analogy to those of MILLER (1966). It may be possible to use them not only for comparing experimental arrangements but also tests.  相似文献   

19.
《IRBM》2020,41(6):316-320
BackgroundThe aim of our study was to conduct an ad hoc data collection in healthy adults with the intention of extracting individual profiles to study the ability to effectively monitor one's health by extracting relevant indicators. As “each patient is a unique case”, AMISIA (Defi CNRS AUTON project) proposes an integrated approach, combining medical health devices, information technology, and human factors to provide patients, health care actors and family caregivers with both the best incentives and a high degree of monitoring.MethodWe conducted a data collection experiment in Limoges with 61 participants at the Limoges University. Data were biographic elements, socio-economic profiles, cognitive performance (Corsi test results), a psychological battery (anxiety, fatigue, sleep), posture and gait measurement with 4 Imus and a Wii-balance board, and finally physical activity during a week at home (Armband sensors).ResultsFor the Corsi virtual walking test, the median memory span for Group A was significantly less (p<0.001) than for Group B. Step count and active energy expenditure were significantly higher in Group B (p<0.05). A multiple regression analysis showed that gender, active energy expenditure, fatigue and tendency to play video games account for 41% of the memory span variance.ConclusionWe have shown that encouraging physical activity can be based on the knowledge of many parameters, such as weight, age, gender and other bio-psycho-social parameters that must also be included in the model.  相似文献   

20.
Use of rigorous equilibration kinetics to evaluate rate constants for the Fe(CN)6 4- reduction of horse-heart cytochrome c in the oxidized form, cyt c (III), has shown that limiting kinetics do not apply with concentrations of Fe(CN)6 4- (the reactant in excess) in the range 2-10 x 10(-4) M, I = 0.10 M (NaCl). The reaction conforms to a first-order rate law in each reactant, and at 25 degrees C, pH 7.2 (Tris), it is concluded that K for association prior to electron transfer is less than 200 M-1. From previous studies at 25 degrees C, ph 7.0 (10(-1) M phosphate), I = 0.242 M (NaCl), a value K = 2.4 x 10(3) M-1 has been reported. Had such a value applied, some or all of the redox inactive complexes Mo(CN)8 4-, Co(CN)6 3-, Cr(CN)6 3-, Zr(C2O4)4 4- present in amounts 5-20 x 10(-4) M would have been expected to associate at the same site and partially block the redox process. No effect on rats was observed. With the reductants Fe(CN)5(4-NH2-py)3- and Fe(CN)5(imid)3-, reactions proceeded to greater than 90% completion and rate laws were again first order in each reactant. Rate constants (M-1 sec-1) at 25 degrees C, pH 7.2 (Tris), I = 0.10 M (NaCl), are Fe(CN)6 4- (3.5 x 10(4)), Fe(CN)5(4-NH2py)3- (6.7 x 10(5), and Fe(CN)5(imid)3- (4.2 x 10(5). Related reactions in which cyt c(II) is oxidized are also first order in each reactant, Fe(CN)6 3- (9.1 x 10(6)), Fe(CN)5(NCS)3- (1.3 x 10(6)), Fe(CN)5(4-NH2py)2- (3.8 x 10(6) at pH 9.4), and Fe(CN)5(NH3)2- (2.75 x 10(6) at ph 8). Redox inactive Co(CN)6 3- (1.0 x 10(-3) M) has no effect on the reaction of Fe(CN)6 3- which suggests that a recent interpretation for the Fe(CN)6 3- oxidation of cyt c(II), I = 0.07 M, may also require reappraisal.  相似文献   

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