Studies of electron-transfer and charge-transfer coupling processes at a liquid/liquid interface by double-barrel micropipet technique

Investigation of a heterogeneous electron-transfer (ET) reaction at the water/1,2-dichloroethane interface employing a double-barrel micropipet technique is reported. The chosen system was the reaction between Fe(CN)(6)(3-) in the aqueous phase (W) and ferrocene in 1,2-dichloroethane (DCE). According to the generation and the collection currents as well as collection efficiency, the ET-ion-transfer (IT) coupling process at such an interface and competing reactions with the organic supporting electrolyte in the organic phase can be studied. In addition, this technique has been found to be an efficient method to distinguish and measure the charge-transfer coupling reaction between two ions (IT-IT) processes occurring simultaneously at a liquid/liquid interface. On this basis, the formal Gibbs energies of transfer of some ions across the W/DCE interface, such as NO3-, NO2-, Cl-, COO-, TBA(+), IPAs+, Cs+, Rb+, K+, Na+, and Li+, for which their direct transfers are usually difficult to obtain because of the IT-IT coupling processes, were quantitatively evaluated.

Electrochemical recognition of alkali metal ions at the micro-water 1,2-dichloroethane interface using a calix[4]arene derivative

In this paper, a calix[4]arene derivative, 5,11,17,23-butyl-25,26,27,28-tetra-(ethanoxycarbonyl)-methoxy-calix[4]arene (L), is investigated as a host to recognize alkali metal ions (Li+, Na+, K+, Rb+ and Cs+) at the interface between two immiscible electrolyte solutions (ITIES). Well-defined cyclic voltammograms are obtained at the micro- and nano-water \ 1,2-dichloroethane (W \ DCE) interfaces supported at micro- and nano-pipets.

Facilitated ion transfer across the micro-liquid /liquid interface supported at the tip of a silanized micropipette

Glass micropipettes with silanized inner walls can be filled with an organic solvent for voltammetric measurements in an aqueous solution. This arrangement was employed to investigate systematically the mechanism of facilitated potassium ion transfer by an ionophore dibenzo-18-crown-6 (DB18C6) across a micro-water/1.2-dichloroethane(W/DCE) interface supported at the tip of a silanized micropipette. Our experimental results verify that this facilitated ion transfer across the liquid/liquid interface did occur by an interfacial complexation-dissociation process (TIC-TID mechanism). The ratio of the diffusion coefficient of DB18C6 to that of its complexed ion in the DCE phase was calculated to be 1.74 +/- 0.07.

Fabrication of a metal particle array based on a self-assembled template from a two-armed polymer

A two-armed polymer with a crown ether core self-assembles to produce macroporous films with pores perpendicularly reaching through the film down to the substrate. A possible assembling mechanism is discussed. The pore size can be conveniently adjusted by changing the solution concentration. These through-hole macroporous films provide a template for fabricating an array of Cu nanoparticle aggregates.

Alkali metal ions transfer across a water/1,2-dichloroethane interface facilitated by a novel monoaza-B15C5 derivative

In this paper, a novel monoaza-B15C5 derivative, N-(2-tosylamino)-isopentyl-monoaza-15-crown-5 (L), is used as an ionophore to facilitate alkali metal cations transfer across a water/1,2-dichloroethane (W/DCE) interface. Well-defined voltammetric behaviors are observed at the polarized W/DCE interfaces supported at micro- and nano-pipets except Cs+. The diffusion coefficient of this ionophore in the DCE phase is calculated to be equal to (3.3+/-0.2) x 10(-6) cm(2) s(-1). The experimental results indicate that a 1:1 (metal: ionophore) complex is formed at the interface with a TIC/TID mechanism. The selectivity of this ionophore towards alkali ions follows the sequence Na+ > Li+ > K+ > Rb+ > Cs+. The logarithm of the association constants (log beta(1)(0)) of the LiL+, NaL+, KL+ and RbL+ complexes in the DCE phase are calculated to be 10.6, 11.6, 9.0 and 7.1, respectively. The kinetic parameters are determined by steady-state voltammograms using nanopipets. The standard rate constants (k(0)) for Li+, Na+, K+ and Rb+ transfers facilitated by L are 0.54+/-0.05, 0.63+/-0.09, 0.51+/-0.04 and 0.46+/-0.06 cm s(-1), respectively. The pH values of aqueous solution have little effect on the electrochemical behaviors of these facilitated processes. The results predicate that this new type of ionophore might be useful to fabricate electrochemical sensor of sodium ion.

Study of facilitated potassium ion transfer across a water vertical bar 1,2-dichloroethane interface using different phase volume ratio systems

A study of potassium ion transfer across a water \ 1,2-dichloroethane (W \ DCE) interface facilitated by dibenzo-18-crown-6 (DB18C6) with various phase volume ratio systems is presented. The key point was that a droplet of aqueous solution containing a redox couple, Fe(CN)(6)(3-)/Fe(CN)(6)(4-), with equal molar ratio, was first attached to a platinum electrode surface, and the resulting droplet electrode was then immersed into the organic solution containing a hydrophobic electrolyte to construct a platinum electrode/aqueous phase/organic phase system. The interfacial potential of the W \ DCE within the series could be externally controlled because the specific compositions in the aqueous droplet make the Pt electrode function like a reference electrode as long as the concentration ratio of Fe(CN)(6)(3-)/Fe(CN)(6)(4-) remains constant. In this way, a conventional three-electrode potentiostat can be used to study the ion transfer process at a liquid \ liquid (L \ L) interface facilitated by an ionophore with variable phase volume ratio (r = V-o/V-w). The effect of r on ion transfer and facilitated ion transfer was studied in detail experimentally. We also demonstrated that as low as 5 x 10(-8) M DB18C6 could be determined using this method due to the effect of the high phase volume ratio.

Investigation of ion transfer across the micro-water/nitrobenzene interface facilitated by a fullerene derivative

A functionalized fullerene derivative containing a monoaza-18-crown-6 moiety was investigated by facilitated ion (such as Li+, Na+, K+, NH4+, Mg2+, and Ca2+) transfer across the micro-water/nitrobenzene interface supported at the tip of a micropipet. The current responses were detected by cyclic voltammetry and Osteryoung square wave voltammetry, which demonstrated that the facilitated ion transfer does occur by an interfacial complexation-dissociation process. The diffusion coefficient of this compound in nitrobenzene was approximately (5.90 +/- 0.04) x 10(-7) cm(2) s(-1), which is 1 order of magnitude less than other common ionophores due to the large size of the molecule. The selectivity of this molecule toward the metal ions followed the sequence Na+ > Li+ > K+ > NH4+ > Ca2+ similar to Mg2+. In addition, this compound was also easy to form film at the water/nitrobenzene interface to inhibit the simple ion transfer of tetramethylammonium ion. However, the adsorption of this ionophore has less influence on the facilitated metal ion transfer.

Investigation of proton transfer across the water/1,2-dichloroethane interface by o-phenanthroline using glass micro/nano-pipets and cyclic voltammetry

Facilitated proton transfer across the water/1,2-dichloroethane (DCE) interface supported on the tips of micro- and nano-pipets by o-phenanthroline (Phen) was studied by using cyclic voltammetry. The formed micro- and nano-liquid/liquid interfaces functioned as micro- and nano-electrodes under certain experimental conditions. The dependence of the half-wave potentials on the aqueous solutions acidities was studied and the ratio of association constants between Phen and proton in the aqueous and DCE phases was calculated by the method proposed by Matsuda et al.. The standard rate constant (k(0)) and the transfer coefficient (alpha) evaluated by using nano-pipets were equal to 0.183 +/- 0.054 cm/s and 0.70 +/- 0.09, respectively.

Fabrication of agar-gel microelectrodes and their application in the study of ion transfer across the agar-water 1,2-dichloroethane interface

In this paper, we describe a simple procedure to make agar-gel microelectrodes by filling micropipettes. These microelectrodes were used to study K+ transfer across the agar-water \ 1,2-dichloroethane interface facilitated by dibenzo-18-crown-6 (DB18C6), and the transfer of tetraethylammonium (TEA(+)). The results observed were similar to those obtained at micro-liquid \ liquid interfaces. The effect of various amounts of agar in the aqueous phase was optimized and 3% agar was chosen based on the potential window and solidification time. The different shapes of micro-agar-gel electrodes were prepared in a similar way. The fabricated agar-gel microelectrodes obey the classical micro-disk steady-state current equation, which is different from the behavior of a normal micropipette filled with aqueous solution without silanization. (C) 2001 Elsevier Science B.V. All rights reserved.

XPS STUDY ON RARE-EARTH PHTHALOCYANINE COMPLEXES

The rare earth monophthalocyanine complexes, LnPcCl and LnPc(OAc)2 (Ln = Tb, Ho, Tm, Lu, Pc=Phthalocyanine, OAc = Acetate), were synthesized. The electronic structures of the complexes have been studied by means of XPS. The experimental results of binding energies for the complexes indicate that the bonds of the complexes have a certain covalent character depending on L-->Ln charge transfer. This L-->Ln charge transfer process of phythalocyanine complexes differs from that of crown ether complexes. Both coordination and substitution are included in the former case, but only coordination in the latter. Phthalocyanine ring is an electrophilic group and its electronegativity is large. So, the O1s binding energies of coordinating oxygen atoms of acetate in LnPc(OAc)2 are larger than those of Ln(OAc)3. The magnitude of valent charge delocalized from ligand onto metal atom is dependent on electronegativity, coordination number, valence state and so on. Because coordination number of Ln in LnPc(OAc)2 is larger than that in LnPcCl and electronegativity of Clin LnPcCl is larger than that of O in LnPc(OAc)2, the Ln4d5/2 binding energies of LnPc (OAc)2 are less than those of LnPcCl.

cDNA cloning and gene expression pattern following bacterial challenge of peroxinectin in Chinese shrimp Fenneropenaeus chinensis

Peroxinectin, a cell-adhesive hemoperoxidase that binds superoxide dismutase and mediates blood cells adhesion and migration in invertebrate, is believed to play an important role in cellular immune reaction. In this study, we reported a new peroxinectin gene homologue from Chinese shrimp Fenneropenaeus chinensis. Based on expressed sequence tags (ESTs) of haemocyte cDNA library, we cloned a 2,611 bps full-length cDNA of peroxinectin gene homologue encoded 801 amino acids. Motif scanning of the predicted polypeptide revealed a peroxidase domain and an integrin binding motif (Lys-Gly-Asp, KGD). Peroxinectin gene expressed constitutively in haemocyte as determined by quantitative real-time RT-PCR, the expression level varied following bacterial challenge. These findings suggested that peroxinectin expression is susceptible to exterior stimulus and maintains at a high expression level during bacterial infection.

Identification and characterization of a Cystatin gene from Chinese mitten crab Eriocheir sinensis

Cystatins are a superfamily of proteins as reversible inhibitor of cysteine proteinases which play essential roles in a spectrum of physiological and immunological processes In this study, a novel member of Cystatin superfamily was identified from Chinese mitten crab Enocheir sinensis (designated EsCystain) by expressed sequence tag (EST) analysis and rapid amplification of cDNA ends (RACE) approaches The full-length cDNA of EsCystatin was of 1486 bp, consisting of a 5'-terminal untranslated region (UTR) of 92 bp, a 3' UTR of 1034 bp with a polyadenylation signal sequence AATAAA and a polyA tail, and an open reading frame (ORF) of 360 bp encoded a polypeptide of 120 amino acids with the theoretical isoelectric point of 548 and the predicted molecular weight of 13 39 kDa. A signal Cystatin-like domain (Gly(25) to Lys(112)) was found in the putative amino acid sequences of EsCystatin Similar to other Cystatins, the conserved central Q(70)VVSG(74) motif was located in the Cystatin-like domain of EsCystatin But EsCystatin lacked of signal peptide and disulphide bond. The EsCystatin exhibited homology with the other known Cystatins from invertebrates and higher vertebrates, and it was clustered into Cystatin family 1 in the phylogenetic tree. The mRNA transcripts of EsCystain were mainly expressed in hemolymph, gill, hepatopancreas, gonad and muscle, and also marginally detectable in heart After Listonella anguillarum challenge, the relative expression level of EsCystatin in hemolymph was down-regulated to 0 6-fold (P < 0.05) at 3 h post-challenge. Subsequently, it was up-regulated to 3.0-fold (P < 0.01)at 24 h Afterwards. EsCystatin mRNA transcripts suddenly decreased to original level. After Pichia pastoris GS115 challenge, its mRNA expression level in hemolymph was up-regulated to the peak at 3 h (2 8-fold of that in blank (P < 0 01)) The cDNA fragment encoding the mature peptide of EsCystatin was recombined and expressed in Escherichia coli Rosetta-gami (DE3). The recombinant EsCystatin displayed a promoter inhibitory activity against papain When the concentration of EsCystatin protein was of 300 mu g mL(-1), almost 89% of papain activity could be inhibited. These results collectively suggested that EsCystatin was a novel member of protein in Cystatin family, was a potent inhibitor of papain and involved in immune response versus invading microorganisms. (C) 2010 Elsevier Ltd All rights reserved.

Seismic profiles across the middle Tan-Lu fault zone in Laizhou Bay, Bohai Sea, eastern China

The stratigraphic architecture, structure and Cenozoic tectonic evolution of the Tan-Lu fault zone in Laizhou Bay, eastern China, are analyzed based on interpretations of 31 new 2D seismic lines across Laizhou Bay. Cenozoic strata in the study area are divided into two layers separated by a prominent and widespread unconformity. The upper sedimentary layer is made up of Neogene and Quaternary fluvial and marine sediments, while the lower layer consists of Paleogene lacustrine and fluvial facies. In terms of tectonics, the sediments beneath the unconformity can be divided into four main structural units: the west depression, central uplift, east depression and Ludong uplift. The two branches of the middle Tan-Lu fault zone differ in their geometry and offset: the east branch fault is a steeply dipping S-shaped strike-slip fault that cuts acoustic basement at depths greater than 8 km, whereas the west branch fault is a relatively shallow normal fault. The Tan-Lu fault zone is the key fault in the study area, having controlled its Cenozoic evolution. Based on balanced cross-sections constructed along transverse seismic line 99.8 and longitudinal seismic line 699.0, the Cenozoic evolution of the middle Tan-Lu fault zone is divided into three stages: Paleocene-Eocene transtension, Oligocene-Early Miocene transpression and Middle Miocene to present-day stable subsidence. The reasons for the contrasting tectonic features of the two branch faults and the timing of the change from transtension to transpression are discussed. Crown Copyright (C) 2008 Published by Elsevier Ltd. All rights reserved.

三种海水经济鱼类早期发育生物学的研究

海水经济鱼类的养殖在我国已经形成第四次海水养殖浪潮，经济效益显著，有力地推动了我国海水养殖的产业结构调整和可持续发展。然而在海水养殖发展过程中也存在着诸多问题，尤其是早期发育阶段的高死亡率，严重制约了我国海水养殖产业的稳定和健康发展。 海水鱼类养殖的关键为高质量，高存活率苗种的生产和培育，由于鱼类种类繁多，生物多样性丰富，对应实际的繁育技术，尤其是新品种的开发，必须要做出相应的调整。这就要求我们必须对每一种鱼类早期发育有所了解，并将形态和组织上的数据用于指导生产。 本文通过显微观察和组织学研究，主要描述和研究了我国北方三种重要的海水经济鱼类(条斑星鲽、杂交鲆、条石鲷)的早期发育生物学，并结合实际生产进一步阐明关键期的产生原因，机理以及采用相应的对策。具体结果如下： 1.条斑星鲽：作为冷温性鲆鲽鱼类，条斑星鲽早期发育过程的特征主要有： ① 条斑星鲽受精卵无油球，卵子呈半浮性；不同步卵裂现象提前，发生在第三次卵裂；卵裂期裂球大小差异大。孵化过程较长，在水温8 ± 0.3℃，盐度33的条件下，经9 d孵化。条斑星鲽胚胎发育的不同时期对温度的敏感性不同，其中原肠期对温度比较敏感。 ②在8-10℃，盐度33的条件下，8-9 dph开口摄食。且开口时，其吻前端出现有一点状黑褐色素，构成了条斑星鲽仔鱼“开口期”的重要标志。卵黄囊于消失。在后期仔鱼末期，背鳍和臀鳍上形成特有的黑褐色条斑带。 ③杯状细胞首先出现在咽腔后部和食道前段，胃腺和幽门盲囊出现于29 dph，变态期始于30dph。在条斑星鲽早期发育过程中，观察到其直肠粘膜层细胞质出现大量嗜伊红颗粒，为仔鱼肠道上皮吸收的蛋白质。 ④首先淋巴化的免疫器官是头肾，然后是胸腺和脾脏，这与大部分硬骨鱼类不同。条斑星鲽除头肾和脾脏外，胸腺实质也形成MMCs。其中以脾脏形成MMCs最为丰富，形态多样。 2. 杂交鲆：为同属的牙鲆和夏鲆间的远缘杂交种，其发育过程的特点为： ① 在温度为15.4～16.0℃，杂交鲆胚胎从受精到孵化所需的时间为76 h左右，胚孔关闭前期，胚胎先出现视囊及克氏囊，而后形成体节。孵出前胚体在卵膜内环绕不到1周。 ② 孵化后消失。杂交鲆群体变态间隔长(34-60 dph)，且变态高峰期出现的冠状幼鳍不明显(与母本牙鲆相比)，数量为7-8根。 ③组织学观察发现，其消化系统中胃腺出现较晚，且胃腺发育过程缓慢(与母本牙鲆相比)。甲状腺滤泡增生不明显，颜色较浅，数量较少。杂交鲆在早期发育过程中，并没有出现鳔原基。 3. 条石鲷作为岩礁性的暖水性鱼类，早期发育过程也较为特殊，包括外形以及内部的器官结构。主要特点有： ① 受精卵：受精卵卵黄上具有龟裂结构，为鱼卵的分类特征之一。 ② 初孵仔鱼：初孵仔鱼背鳍膜上的黑色素，从体背面向背鳍膜边缘移动，到3dph仔鱼基本消失，此为本种仔鱼发育所特有的特点。 ③ 后期仔鱼和稚鱼：肠道肌肉层加厚明显，仔稚鱼胃肠排空率急剧上升，死亡率增加，通过改善常规的投饵方式部分解决了这个死亡高峰的问题。在幼鱼初期，牙齿融合为骨喙，为石鲷科鱼类的特征。 ④胸腺上皮分泌细胞：类似的现象同样在虹鳟鱼中发现，但是虹鳟鱼胸腺上皮分泌细胞不如条石鲷的丰富，同样也不如条石鲷的排列整齐，而是零星分布在胸腺上皮与咽腔接触的表面。除了正常的造血器官—脾脏和头肾外，肝脏、胰腺和鳔等多种组织等也出现MMCs，此现象在硬骨鱼类不多见，一般发生在软骨鱼类。