68 resultados para Mixed valent diruthenium(II,III)

em Chinese Academy of Sciences Institutional Repositories Grid Portal


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Three new cage-like mixed-valent polyoxovanadates [Ni(1,10'-phen)(3)](2)[V10O26] 1, [Zn(2,2'-biPY)(3)](3)[V15O36Cl](.)3H(2)O (2) and [Co(2,2'-biPY)(3)](3)[V15O36Cl](.)3H(2)O (3) have been hydrothermally synthesized for the first time and characterized by elemental analyses, IR, EPR spectra, TG analyses and single crystal X-ray diffraction. The polyoxoanion of I exhibits an interesting empty ellipsoidal [V-2(IV) V-8(V) O-26](4-) 'host' shell, while the oxo vanadium clusters of 2 and 3 possess a spherical [V-8(IV) V-7(V) O36Cl](6-) cage with a Cl- ion encapsulated. The structure-directing role of organic templates (1,10'-phen and 2,2'-bipy) on the formation of the polyoxoanion structures is discussed.

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Indium(III) hexacyanoferrate(II/III) (InHCF) supported on graphite powder was prepared using the in situ chemical deposition procedure and subsequently dispersed into methyltrimethoxysilane-derived gels to yield a conductive graphite organosilicate composite. The composite was used as the electrode material to fabricate a three-dimensional InHCF-modified electrode. InHCF acts as a catalyst, graphite powder ensures conductivity by percolation, the silicate provides a rigid porous backbone and the methyl groups endow hydrophobicity and thus limit the wetting section of the modified electrode. The chemically modified electrode can electrocatalyze the oxidation of thiosulfate, and exhibits a good repeatability of surface-renewal by simple mechanical polishing, as well as simple preparation, good chemical and mechanical stability.

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In this study, electrode responses to a large number of electroactive species with different standard potentials at the molybdenum oxide-modified carbon fibre microdisk array (CFMA) electrode were investigated. The results demonstrated that the electrochemical behavior for those redox species with formal potentials more positive than similar to 0.0 V at the molybdenum oxide-modified CFMA electrode were affected by the range and direction of the potential scan, which were different from that at a bare CFMA electrode. If the lower limit of the potential scan was more positive than the reduction potential of the molybdenum oxide film, neither the oxidation nor the reduction peaks of the redox species tested could be observed. This indicates that electron transfer between the molybdenum oxide film on the electrode and the electroactive species in solution is blocked due to the existence of a high resistance between the film and electrolyte in these potential ranges. If the lower limit of the potential scan was more negative than the reduction potential of the molybdenum oxide film (similar to - 0.6 V), the oxidation peaks of these species occurred at the potentials near their formal potentials. In addition, the electrochemical behavior of these redox species at the molybdenum oxide-modified CFMA electrode showed a diffusionless electron transfer process. On the other hand, the redox species with formal potentials more negative than similar to - 0.2 V showed similar reversible voltammetric behaviors at both the molybdenum oxide-modified CFMA electrode and the bare electrode. This can be explained by the structure changes of the film before and after reduction of the film. In addition we also observed that the peak currents of some redox species at the modified electrode were much larger than those at a bare electrode under the same conditions, which has been explained by the interaction between these redox species and the reduction state of the molybdenum oxide film. (C) 2000 Elsevier Science Ltd. All rights reserved.

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A compact non-stoichiometric molybdenum (VI, V) oxide of blue film was grown on carbon fiber (CF) microelectrode surface be cycling the potential between + 0.2V and - 0.70V in a freshly prepared Na2MoO4 solution containing 5 x 10(-3) mol/L H2SO4. The quantity-of the oxide is controlled by the charge passing the electrode. The electrochemical pretreatment of CF microelectrode not only mises the deposition velocity of molybdenum oxide on CF surface, but also improves greatly the cyclic voltammetric behavior of the molybdenum oxide film prior to the electrodeposition. The cathodic processes are believed to yield the hydrogen molybdenum oxide bronzes HxMoO3(0 < x < 2), or substoichiometric lower molybdenum oxides with the formula MoO3-y(0 < y < 1). The anodic response results from the reversible oxidation of molybdenum bronze/Mo(V) centers [or perhaps Mo(IV) in more reduced coatings], to Mo(VI). Further information was gained about the chemical composition and valent state of Mo from XPS and SEM.

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The crystal structures, electronic spectra, and Cu2p XPS of Cu(III) complexes Na4H[Cu(H2TeO6)(2)]. 17H(2)O and Na4K[Cu(HlO(6))(2)]. 12H(2)O have been described. The characterizations of a Cu(III) atom in a complex are as follows: (i) In a square-planar coordination, the average bond length of Cu-O is 0.183 nm, shorter than the 0.190-0.200 nm found for a Cu(II) complex. (2) The ''blue shift'' occurs for d-d transitions in the electronic spectrum of the Cu(III) complex compared to those of its related Cu(II) complex, resulting from the higher valence state. (3) Cu(III) compounds with CuO4 square-planar coordination are expected to be diamagnetic whereas Cu(II) compounds to be paramagnetic. (4) Comprehensive investigations on Cu2p XPS show that the binding energy of Cu2p(3/2) of a pure Cu(III) compound is about 2.0 eV higher than that of its corresponding Cu(II) compound: the shake-up satellites do not appear in the Cu2p XPS for a pure diamagnetic Cu(III) compound, the same as found for a diamagnetic Ni(II) compound: the FWHM of the signal of Cu2p XPS may become broader for Cu(III) compound because its core hole's lifetime shortens due to the higher valence state of copper. (C) 1995 Academic Press, Inc.

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A blue, conductive, compact, mixed-valent Mo(VI, V) oxide film was grown on carbon fiber (CF) microelectrode surface by cycling the potential between +0.20 and -0.70 V vs. SCE in a fresh prepared Na2MoO4 solution (pH = 2, H2SO4). The thickness of the oxid

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A glassy carbon electrode coated with an electrodeposited film of mixed-valent cobalt oxide/cyanocobaltate (Co-O/CN-Co) enabled hydrazine compounds to be catalytically oxidized at the greatly reduced overpotential and in a wide operational pH range (pH 2.0-7.0). Electrocatalytic activity at the Co-O/CN-Co modified electrode was evaluated with respect to solution pH, film thickness, supporting electrolyte ions, potential scan rate, operating potential, concentration dependence and other variables. The Co-O/CN-Co film electrode was completely compatible with a conventional reversed-phase liquid chromatographic (RP-LC) system. Practical RP-LC amperometric detection (RP-LCEC) of hydrazines was performed. A dynamic linear response range over three orders of magnitude and a detection limit at the pmol level were readily obtained. The Co-O/CN-CO film electrode exhibited excellent electrocatalytic stability in the flowing streams.

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本文利用单向SDS-PAGE方法对十八株Frankia菌的全细胞可溶性蛋白进行了图谱分析。Frankia菌蛋白图谱不受菌令的影响。不同交叉接种组的Frankia菌具有不同的蛋白图谱,同一交叉接种组内的菌株也有所羞。十八株菌分为三大类七个亚类,第I类包括赤场、杨梅香蕨木和美洲茶内生菌;第II类包括木麻黄内生菌,第III类包括胡颓子和沙棘内生菌。利用同功酶图谱的差异性对Frankia菌进行分类识别是一种非常有效的方法,不同的Frankia菌株具有不同的同功酶(过氧化物酶和酯酶)图谱。根据图谱之间的相似性,可以将二十株Frankia菌分成三组;即赤杨组,木麻黄组和胡颓子组,这与其它分类结果基本符合,只是细枝木麻黄菌株CcO1的过氧化物酶图谱与其它菌株完全不同。从同种根瘤中分离的内生菌具有不同的同功酶图谱,进一步证实了遗传结构不完全相同的菌株可以同时共生于同种根瘤内,同时根据二种同功酶的电泳分布率,说明了Frankia菌株遗传信息的广泛分布性。

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鹿角蕨(Platycerium wallichii Hook.)是鹿角蕨科鹿角蕨属植物,为国家二级保护植物。该植物主要分布在云南西南部盈江县那邦坝,在当地用作跌打药。有关鹿角蕨属的系统关系存在一些假设,关于鹿角蕨属植物化学成分及生物活性的研究未见报道。从鹿角蕨(Platycerium wallichii Hook.)叶95%乙醇提取物中,我们分离得到了七个已知化合物。根据理化常数及波谱数据 (IR、UV、MS及NMR),其结构分别鉴定为:(I)β一谷甾醇、(II)胡萝卜甙、 (III)2-propenoic acid,3一[(2R, 3S)-2,3-dihydro-2- (4-hydroxy-3-methoxyphenyl) -3- (hydroxymethyl) -7-mnethoxy-5-benzofuranyll -、(Ⅳ)松脂素-4’-0-β -D-葡萄糖甙、(v)松腊素、(Ⅵ)2,5_二羟基苯甲酸甲酯、(Ⅶ)槲皮素3-0-β -半乳糖甙。七个成分均为首次从该种植物中获得。 我们对鹿角蕨(Platvcerium wallichii Hook.)能育叶部分以及基生叶部分的乙醇提取物进行了镇痛试验和抗炎试验,试验表明鹿角蕨(Platvcerium wallichii Hook.)的叶有弱镇痛作用。

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从狗脊(Woodwardia japonica (L. f.) Sm.)中分离得到六个化合物,经解析,分别鉴定为:山柰素-3-O-α-L-(4-O-乙酰基)鼠李糖基-7-O-α-L-鼠李糖甙(I)、山柰素-3-O-α-L-鼠李糖基-7-O-α-L-鼠李糖甙(II)、狗脊蕨酸 (III)、β-谷甾醇 (IV)、胡萝卜甙 (V),β-谷甾醇-3-O-α-L-(6-O-正十六酰基)葡萄糖甙(VI)。MS-MS检测并鉴定化合物一个:β-谷甾醇-3-O-α-L-(6-O-正十五酰基)葡萄糖甙(VII)。以上化合物均系首次从该植物中获得,化合物VI、VII为新化合物。另有六个化合物,未能分离得到化合物单体,经解析,可以确定其中五个化合物的结构物,分别为:山柰素-7-O-α-L-鼠李糖甙(VIII-I)、山柰素-3-O-α-L-(3,4-O-2乙酰基)鼠李糖甙(VIII-II)、山柰素-3-O-α-L-鼠李糖甙(VIII-IV)、山柰素-3-O-α-L-(3-O-乙酰基)鼠李糖甙(VIII-V)、山柰素-3-O-α-L-(4-O-乙酰基)鼠李糖甙(VIII-VI)。

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通量测量点的能量收支总是表现出不平衡,即使在地势平坦、植被分布均一、稀疏植被下垫面的情况下也有约30%的能量失衡状况。能量平衡闭合 (EBC) 问题在验证涡度相关系统质量方面,得到了广泛的关注。实验在内蒙古草原3个地点,通过涡度相关系统附近移动能量平衡系统的测定手段,采用能量平衡余项法和最小二乘 (OLS) 线性回归法,研究了土壤热通量、净辐射及可供能量空间变异对能量平衡闭合的影响。 结果显示,EBC 在三个研究点的平均余项为8~19 W m-2,OLS 斜率为0.83~0.96。EBC 在土壤湿润情况的站点要高于干旱站点。 土壤热通量的空间变异三站点平均为白天48 W m-2 (占同时间 Rn 的13%),夜间15 W m-2 (34%),平均29 W m-2 (24%)。通过8个工作站的测量,这个变异会造成9% (从0.93到1.01) 的 OLS 斜率差别。夜间的能量平衡不闭合可以由土壤热通量的空间变异解释。如果在本研究的的三个草原站点上忽略了土壤热通量,则会造成较大的余项 (峰值时110 W m-2) 产生,从而使 OLS 斜率增大23%。特别是通量板埋置在地面以下30 mm处时,上层的土壤热储部分占到全部土壤热通量的50%,这不仅影响到 EBC 的大小,更起到调节土壤热通量与“真实的波形” 相一致的作用。如果该部分热储被忽略掉,EBC 余项会增加60 W m-2,OLS 斜率也会变化 (减少) 9%。用大尺度多点测量与涡度塔附近的小尺度测定相比较,后者表现出稍高的闭合率,即 OLS 斜率增加4%。 相对于土壤热通量,净辐射的空间变异较小,三站点平均为白天17 W m-2 (5%),夜间7 W m-2 (13%),平均 12 W m-2 (5%)。可以引起3% (从0.88到0.91) 的 OLS 斜率差异。研究结果还表明,风速校正应该在 Q7.1 净辐射仪中应用,校正后的结果与 CNR1 的结果在白天有吻合较好,但在其它时段仍有较大差异,特别是在夜间,风速校正基本不起作用,使得两种仪器间差异达20 W m-2。比较表明,风速校正可以提高白天 Rn 的6%,仅降低夜间0.3%。因此,无论是用余项法还是用 OLS 线性回归法,在比较使用不同仪器的站点间的闭合状况时 (本研究的结果适用于草地 Q7.1 与 CNR1 间的比较),可以用9:00-15:00 h 时段的数据进行比较,这样可以避免因使用不同仪器的差异所造成的影响。用该时段的数据进行比较,仪器间的差异余项法小于6 W m-2,OLS 法小于3%。 受可供能量空间变异影响,三个站点平均 EBC 的不确定性为白天66 W m-2 (19%),夜间23 W m-2 (50%),平均42 W m-2 (36%);或者改变 OLS 斜率11%。用最大值和最小值来衡量,EBC 最大不确定性,正午时在站点 I、II 和 III 中分别为81,114和91 W m-2。故在探讨能量平衡和能量平衡闭合问题时,必须充分考虑到这种不确定性,否则会产生偏差,或者得出错误结论。 研究还表明,即使考虑到白天所有可供能量的最大不确定性,仍然不能使能量平衡闭合。中午 (12:00 h),站点 I,II 和 III 仍然有14±15,48±12和47±14 W m-2 的失衡不能够归因于可供能量的空间不确定性。因此,其它影响因素也需进行细致的探讨。 在两站点不同测量深度土壤热通量结果的差异性比较实验中,无论在站点 I 还是 III,均表现出一致的结论,即随通量板布置深度加深,其测量结果会越高,与浅层布置的相比,差别可高达150 W m-2。深层土壤热通量的计算仍是个难题,需进一步研究。 在不同植被结构对净辐射测定影响的实验中发现,随刈割强度增加,一天中大部分时间净辐射均减少。正午依次为413,395和388 W m-2。无论正午还是全天合计,重度刈割地点的净辐射均比不刈割对照处理少6%,而且,在整个生长季也少6%,约合40,000 W m-2。测量高度不同,不同处理间对测定结果影响不同:刈割处理中,由于下垫面较均一,结果相差不显著;而对照则表现出较高的差异,用两配对样本T检验表明差异达到极显著 (P<0.000,9:30-15:00 h data)。当使用不同新旧程度的 domes 时,对净辐射结果会产生明显的影响。新 domes 的测量结果白天明显高,晚上明显低,使用了11个月的旧 domes,峰值时,白天低估25 W m-2,晚上高估10 W m-2。说明该差异在进行能量平衡闭合计算时,不能忽略。而全用新的和全用旧的进行比较,晚上仅有2-3 W m-2差异。 考虑生态系统中非生物因子对干扰条件下生物多样性动态和功能的影响,有助于更精确地阐明生物多样性-稳定性功能的关系。为此,设计了一个单因子刈割实验——内蒙古地区一种广泛存在的土地利用方式。主要目的是研究不同强度刈割影响下,微气候变量特别是能量平衡各分量和群落结构的变化及二者的关系。连续4年刈割,占第一位的优势种明显由低矮半灌木冷蒿 (Artemisia frigida) 取代了高大丛生禾草克氏针茅 (Stipa kylovii)。重度刈割下,针茅的盖度、生物量和丛重,群落叶面积、绿色生物量、凋落物量和群落高度一致低于轻度刈割/不刈割处理。微气候由于群落特征的这些变化也呈规律性变化。与对照相比,重度刈割降低了生长季土壤含水量的47.5%,但中午和日均土壤表面温度分别增加了7.4和1.2 °C,并且增加地表下2 cm土壤温度日较差 (日最高与最低温度之差) 4.2 °C。刈割处理由于凋落物少、反射强而表现出较低的净辐射,但土壤热通量显著提高,表现为土层加热和冷却快。因此,重度刈割处理较对照降低了可供能量8%,约合52,000 W m-2 。不同刈割强度间来看,NPP 或 LAI 与土壤热通量和净辐射的比值 (G/Rn) 以及波文比 (H/LE) 间呈负相关。重度刈割处理感热通量显著提高,但潜热通量在处理间差异不显著,表明未刈割处理虽然冠层伸展大,但是并没有导致更大的水分亏缺。未刈割处理增加了抵抗物种改变的能力,而刈割处理在连续一年一割的第四年显著增加了物种数,可能与因刈割影响而导致的群落结构与微气候的改变有关。本研究表明,未刈割处理可以减轻高温干旱季节的高温和干旱胁迫,表现出对环境变化的高抵抗性。未刈割处理的凋落物层和较高的垂直结构所形成的遮荫,可以形成一个阻挡蒸发的篱笆,这是维持其水分的保证。因此,为了恢复退化草原生态系统功能,需要修复能导致微气候变化的植物群落结构,否则难以成功。 本研究立足于原创性的实验研究,在中国特有的自然草原生态系统上开展,结合不同温度梯度的三地区涡度相关系统进行了能量平衡闭合的移动比较实验,以及结合常用土地利用方式的定点能量平衡实验。在翔实的数据基础上,为涡度相关方法的陆地表面能量平衡失衡问题提供了解释。增加了对两个主要能量流——土壤热通量和净辐射空间变异规律的认识,研究对于能量平衡和湍流通量相关研究是有价值的。在三个代表性地区首次利用多个净辐射仪和土壤热通量板的结果与三个标准的涡度相关系统进行了比较,这类量化失衡原因的相关研究应受到高度重视并进一步拓展,以提高对能量失衡的认识,进而推进水热和碳循环研究向更深层次发展。

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植物的生境在时间和空间上都是异质性的,即使在很小的尺度上这种异质性也是存在的。克隆生长使得克隆植物在理论上更适应利用异质性环境,本文以几种克隆植物为对象,采用实验生态学方法,着重从生理生态特性、信号物质传导方面探讨克隆植物对异质性环境的适应对策。 以匍匐茎克隆植物野草莓(Fragaria vesca)为对象,研究了不同海拔梯度种群(1800m和3900m)对光照和养分资源斑块性分布生境的响应。研究结果显示:与资源的空间同质性处理(I) 和(II) 相比, 资源的空间异质性处理(III) 和(IV) 两个种群野草莓的近端、远端和整个克隆片段的生物量和分株数均获得显著增加。经历低光高养近端分株与经历高光低养的远段分株相连时,相比与低光高养的同质生境,来自两个海拔的种群分配更多的生物量到根;经历高光低养近端分株与经历低光高养远端分株相连时,相比于高光低养的同质生境,来自两个海拔的种群分配更少的生物量到根,类似的生物量分配格局在远端分株也被观察到。相比于高光低养同质性生境,当与低光高养远端分株相连时经历高光低养近端分株有更大的叶面积;相比于高光低养同质性生境,当与低光高养近端分株相连时经历高光低养远端分株有更大叶面积。实验结果表明, 资源交互斑块性生境中野草莓发生了克隆内分工。通过克隆内分工, 克隆植物能有效的利用异质性分布的资源, 缓解资源交互斑块性分布对克隆植物生长的不利影响。 以匍匐茎克隆植物蛇莓(Duchesnea indica)为对象, 研究其在高光照低水分斑块和低光照高水分斑块组成的资源交互斑块性生境中的克隆内分工。结果显示,当生长于高光照低水分(HL)条件下近端分株(basal ramets)与生长于低光照高水分(LH)条件下的远端分株(apical ramets)之间的匍匐茎连接时,近端分株根冠比显著下降,而远端分株根冠比显著增加,近端分株叶面积和远端分株总根长显著增加;当与低光照高水分条件下的远端分株相连时,近端分株叶片光合速率和叶绿素含量也相应增加。此外,克隆分株间资源交互传输显著提高蛇莓的生长表现(生物量和分株数)。因此,在光、水资源交互斑块性环境中克隆植物蛇莓分株在生物量分配、资源获取器官形态和生理特性方面发生了环境诱导的功能特化。这种对局部丰富资源的趋富特化在一定的程度上增强了克隆分株对资源的吸收利用能力,克隆内资源共享有助于缓解资源交互性斑块生境对克隆植物生长的不利影响,有效地提高克隆植物在其生境中存活与定居能力。 一个盆栽实验被采用以便调查克隆整合对经受局部沙埋的根状茎克隆植物沙生苔草(Carex praeclara)的影响,结果显示随着沙埋深度的增加,切断分株间的根状茎连接将显著降低经受沙埋处理分株的存活。当克隆植物经历局部沙埋时,切断分株间根状茎连接对其克隆生长(生物量、分株数和叶片数量)有显著负影响。耗-益(cost-benefit)分析显示,当与经历沙埋处理的远端分株相连时,近端分株的生长表现没有遭受任何负面影响。与经历沙埋处理远端分株相连时,近端分株的光合能力随沙埋深度的增加而增加。分株间的源-汇反馈调节机制所导致的补偿性反应减缓了局部沙埋对克隆植物生长的负效应。因此,克隆整合有助于提高经历局部沙埋克隆植物的存活,克隆植物在沙化地区植被恢复与重建方面具有重要意义。 克隆植物分株间的匍匐茎或根状茎连接不仅可以传输水分、矿质养分、光合产物,而且还可以传输信号物质。以根状茎克隆植物黑褐苔草(Carex alrofusca)为对象,采用盆栽实验研究外源茉莉酸诱导克隆片段相连分株间信号物质传导。结果显示,相比中龄和老龄分株,幼年分株对1mM茉莉酸诱导有显著反应。茉莉酸引起幼年分株叶片浓缩单宁含量显著增加,同时其叶片可溶性碳水化合物和氮含量降低。茉莉酸诱导后,幼年分株被昆虫咬食叶面积比率显著下降。因此匍匐茎或根状茎传也是克隆植物分株间信号物质传导重要通道,克隆植物通过分株间的风险扩散策略增强了对幼嫩植物组织器官的保护,这对克隆植物的存活或生长具有重要意义。

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本发明是一种利用水产加工下脚料制备生物柴油的方法。包括下列步骤: (1)将清洗后的鱼加工下脚料蒸煮至100~120℃,然后加入有机溶剂,搅拌、过滤得溶液I;(2)按溶液I体积的20~50%加磷酸水溶液于溶液I中,得溶液II,再加入与溶液II同体积的水;进行酸洗水洗,通过多羟基吸水性树脂柱脱水得溶液III;(3)在溶液III中加入碱性催化剂与无水乙醇进行转酯化反应,得溶液IV;(4)将溶液IV静置,除去下层甘油层后,对生成的混合脂肪酸乙酯层进行水洗,除去残留的催化剂、乙醇和其它水溶性成分得生物柴油。本发明的优点是:充分利用现有的鱼加工下脚料,减少污染,提高企业经济效益,为水产加工废弃物的利用和生物能源的发展开辟了一条新路。

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More than 10 species within the freshwater fish genus Sinoncyclocbeilus adapt to caves and show different degrees of degeneration of eyes and pigmentation. Therefore, this genus can be useful for studying evolutionary developmental mechanisms, role of natural selection and adaptation in cave animals. To better understand these processes, it is indispensable to have background knowledge about phylogenetic relationships of surface and cave species within this genus. To investigate phylogenetic relationships among species within this genus, we determined nucleotide sequences of complete mitochondrial cytochrome b gene (1140 bp) and partial ND4 gene (1032 bp) of 31 recognized ingroup species and one outgroup species Barbodes laticeps. Phylogenetic trees were reconstructed using maximum parsimony. Bayesian, and maximum likelihood analyses. Our phylogenetic results showed that all species except for two surface species S. jii and S. macrolepis clustered as five major monophyletic clades (I, II, III, IV, and V) with strong supports. S. jii was the most basal species in all analyses, but the position of S. macrolepis was not resolved. The cave species were polyphyletic and occurred in these five major clades. Our results indicate that adaptation to cave environments has occurred multiple times during the evolutionary history of Sinocyclocheilus. The branching orders among the clades I, II, III, and IV were not resolved, and this might be due to early rapid radiation in Sinocyclocheilus. All species distributed in Yunnan except for S. rhinocerous and S. hyalinus formed a strongly supported monophyletic group (clade V), probably reflecting their common origins. This result suggested that the diversification of Sinocyclocheilus in Yunnan may correlate with the uplifting of Yunnan Plateau. © 2005 Published by Elsevier Inc.