Large nanoparticle-induced enhancement of recognition selectivity for Cu ion

A new fluorescent excited state intramolecular proton transfer compound, 2-(2-hydroxy-4-carbaldehydephenyl)benzoxazole (HCPBO), has been synthesized for the detection of Cu²⁺, based on its fluorescence quenching. In molecular monodispersed solution, the recognition selectivity for Cu²⁺ was poor as Co²⁺ and Ni²⁺ gave similar results in fluorescence quenching. However, the nanoparticles of HCPBO, prepared in ethanol-water (1:4, v/v), greatly enhanced the recognition selectivity for Cu²⁺. The mechanism was discussed as energy transfer (ET), energy migration (EM) and the more quantity of formed HCPBO-Cu²⁺ complex than other metal ions in the nanoparticle conditions enhanced the recognition selectivity for Cu²⁺ together.     

A new acridine derivative as a highly selective ‘off-on’ fluorescence chemosensor for Cd in aqueous media

A new acridine fluoroionophore containing two diethanolamine ligands, 4,5-bis(N,N-di (2-hydroxyethyl)iminomethyl)acridine (BHIA), was designed and synthesized based on the fluorophore-spacer-receptor format. And its fluorescent sensing behavior towards metal ions was investigated in buffered aqueous media. The presence of Cd²⁺ induces the formation of a 1:1 ligand/metal complex at neutral pH, which exhibits enhanced emission at 454 nm. The fluorescence intensity is linear with the Cd²⁺ concentration in the range of 1.0 × 10⁻⁶ to 3.0 × 10⁻⁵ M (R = 0.9967). Experimental results show a low interference response towards other metal ions. The selective switch-on fluorescence response of BHIA to Cd²⁺ makes it suitable for sensing of Cd²⁺ in aqueous solution. The detection limit is 1.3 × 10⁻⁷ M. Moreover, the results indicated that BHIA was a reversible chemosensor for Cd²⁺, which makes it attractive for sensing applications.     

深海适冷菌Pseudoalteromonas sp. SM9913胞外多糖对Pb2+和Cu2+的吸附性能研究

采用深海适冷菌Pseudoalteromonas sp. SM9913分泌的胞外多糖（EPS）分别对Pb²⁺和Cu²⁺进行吸附,研究了多糖用量、pH、吸附时间和共存离子对EPS吸附性能的影响及EPS对Pb²⁺和Cu²⁺的吸附热力学.结果表明,EPS对Pb²⁺和Cu²⁺的吸附量随EPS投加量的增加而减小.EPS对Pb²⁺和Cu²⁺的最佳吸附pH分别为4.5～5.5和4.5～6.0. EPS对Cu²⁺的吸附平衡时间为90　min,对Pb²⁺的吸附平衡时间则长达180　min.共存离子Ca²⁺、Mg²⁺、Na⁺、K⁺的加入均降低了EPS对Pb²⁺的吸附量,Ca²⁺、Mg²⁺的加入降低了EPS对Cu²⁺的吸附量,但低浓度的Na⁺和实验范围浓度的K⁺不仅没有降低反而增加了EPS对Cu²⁺的吸附量.Freundlich和Dubinin-Radushkevich方程均能较好地描述SM9913胞外多糖吸附Pb²⁺和Cu²⁺的热力学过程,由Dubinin-Radushkevich方程得到SM9913胞外多糖对Pb²⁺和Cu²⁺的最大吸附量分别为243.3 mg/g (10℃) 和36.7 mg/g (40℃).胞外多糖吸附金属离子前后的红外光谱分析表明,多聚糖中C—O—C、乙酰基和羟基是起主要吸附作用的官能团.     

A highly sensitive and selective colorimetric and off-on fluorescent chemosensor for Cu based on rhodamine B derivative

A new rhodamine B derivative colorimetric and fluorescent sensor (1) was synthesized by condensation reaction of rhodamine B hydrazide and 2,4-dihydroxybenzaldehyde, which showed reversible and highly selective and sensitive recognition toward Cu²⁺ over other examined metal ions. Upon addition of Cu²⁺, sensor 1 exhibits remarkably enhanced absorbance intensity and color change from colorless to pink in DMSO and MeCN aqueous buffer solution or pure MeCN, and shows significant off-on fluorescence accompanied by color changes from colorless to orange in MeCN. The sensor 1 was also successfully applied to the determination of Cu²⁺ in water samples.     

Tuning with pH: The selectivity of a new rhodamine B derivative chemosensor for Fe and Cu

A simple structure, a rhodamine fluorescent derivative, was synthesized easily by a one-step condensation reaction of rhodamine B ethylenediamine and acetylacetone. Its structure was characterized by X-ray crystallography, NMR, MS and IR spectroscopy. As a bi-functional and highly selective “OFF–ON” chemosensor for Fe³⁺ or Cu²⁺, the derivative displayed a selective fluorescence enhancement effect only with Fe³⁺ and an absorption enhancement effect only with Cu²⁺ by modulating the pH value. In an aqueous ethanol medium, Fe³⁺ formed a 1:1 complex with the derivative at pH 6, while Cu²⁺ formed a 1:1 complex at pH 8.5. The limits of detection of the ions were low: 3.9 × 10⁻⁹ and 4.8 × 10⁻⁸ mol L⁻¹. The derivative also functioned as a fluorescence sensor for CT-DNA, in which the Fe³⁺ ion that was used as a bridge between the derivative and DNA forming a ternary complex.     

High sensitive optode for selective determination of Ni based on the covalently immobilized thionine in agarose membrane

A novel Ni²⁺ optode was prepared by covalent immobilization of thionine, 3,7-diamine-5-phenothiazoniom thionineacetate, in a transparent agarose membrane. Influences of various experimental parameters on Ni²⁺ sensing, including the reaction time, the solution pH and the concentration of reagents were investigated. Under the optimized conditions, a linear response was obtained for Ni²⁺ concentrations ranging from 1.00 × 10⁻¹⁰ to 1.00 × 10⁻⁷ mol l⁻¹ with an R² value of 0.9985. The detection limit (3σ) of the method for Ni²⁺ was 9.30 × 10⁻¹¹ mol l⁻¹. The influence of several potentially interfering ions such as Ag⁺, Hg²⁺, Cd²⁺, Zn²⁺, Pb²⁺, Cu²⁺, Mn²⁺, Co³⁺, Cr³⁺, Al³⁺ and Fe³⁺ on the determination of Ni²⁺ was studied and no significant interference was observed. The membrane showed a good durability and short response time with no evidence of reagent leaching. The membrane was successfully applied for the determination of Ni²⁺ in environmental water samples.     

Three-input chemical logic circuits based on a new fluorescent sensor for ATP and Cuin aqueous solution

A new l-lysine derivative featuring an anthracene unit is synthesized and characterized by elemental analysis, ESI-MS, ¹H-NMR, and ¹³C-NMR. It can selectively bind ATP in acidic aqueous solutions, and be used as a highly selective fluorescent chemosensor for Cu²⁺ at neutral pH, resulting in fluorescence quenching. According to these characters, two combinational logic circuits are fabricated on a single molecule with three chemical inputs [H⁺(IN1), OH⁻(IN2), ATP (IN31)] and [H⁺(IN1), OH⁻(IN2), Cu²⁺(IN32)], respectively.     

Synthesis of Bi and Gd doped ZnB2O4 for evaluation as potential materials in luminescent display applications

A series of Bi³⁺ and Gd³⁺ doped ZnB₂O₄ phosphors were synthesized with solid state reaction technique. X-ray diffraction technique was employed to study the structure of prepared samples. Excitation and emission spectra were recorded to investigate the luminescence properties of phosphors. The doping of Bi³⁺ or Gd³⁺ with a small amount (no more than 3 mol%) does not change the structure of prepared samples remarkably. Bi³⁺ in ZnB₂O₄ can emit intense broad-band purplish blue light peaking at 428 nm under the excitation of a broad-band peaking at 329 nm. The optimal doping concentration of Bi³⁺ is experimentally ascertained to be 0.5 mol%. The decay time of Bi³⁺ in ZnB₂O₄ changes from 0.88 to 1.69 ms. Gd³⁺ in ZnB₂O₄ can be excited with 254 nm ultraviolet light and yield intense 312 nm emission. The optimal doping concentration of Gd³⁺ is experimentally ascertained to be 5 mol%. The decay time of Gd³⁺ in ZnB₂O₄ changes from 0.42 to 1.36 ms.     

Electrochemical DNA biosensor for the detection of interaction between di[azino-di(5,6-azafluorene)-κ-NN′]dichlormanganous and DNA

A new Mn(II) complex of MnL₂Cl₂ (L = azino-di(5,6-azafluorene)-κ²-NN′) was synthesized and utilized as an electrochemical indicator for the determination of hepatitis B virus (HBV) based on its interaction with MnL₂Cl₂. The electrochemical behavior of interaction of MnL₂Cl₂ with salmon sperm DNA was investigated on glassy carbon electrode (GCE). In the presence of salmon sperm DNA, the peak current of [MnL₂]²⁺ was decreased and the peak potential was shifted positively without appearance of new peaks. The binding ratio between [MnL₂]²⁺ and salmon sperm DNA was calculated to be 2:1 and the binding constant was 3.72 × 10⁸ mol² L⁻². The extent of hybridization was evaluated on the basis of the difference between signals of [MnL₂]²⁺ with probe DNA before and after hybridization with complementary sequence. Control experiments performed with non-complementary and mismatch sequence demonstrated the good selectivity of the biosensor. With this approach, a sequence of the HBV could be quantified over the range from 1.76 × 10⁻⁸ to 1.07 × 10⁻⁶ mol L⁻¹, with a linear correlation of r = 0.9904 and a detection limit of 6.80 × 10⁻⁹ mol L⁻¹. Additionally, the binding mechanism was preliminarily discussed. The mode of interaction between MnL₂Cl₂ and DNA was found to be primary intercalation binding.     

Some quadrature formulas for functions partially holomorphic with respect to each variable in a Jordan polydomain in C 2 and a complex double integral formula

In this paper, quadrature formulas with remaining term in integral form for functions partially holomorphic with respect to each variable in a Jordan polydomain in C ² and a complex double integral formula are given. For this, we used the Cauchy Integral formula for Jordan polydomain in C ².     

Direct amperometric determination of l-ascorbic acid (Vitamin C) at octacyanomolybdate-doped-poly(4-vinylpyridine) modified electrode in fruit juice and pharmaceuticals

The glassy carbon electrode (GCE) modified with Mo(CN)₈⁴⁻-incorporated-poly(4-vinylpyridine) (PVP/Mo(CN)₈⁴⁻), which has been recently shown to possess several attractive attributes as an efficient electrocatalytic electrode for l-ascorbic acid oxidation and its estimation, is used for l-ascorbic acid estimation directly in orange fruit juice and Celin tablet in a 0.1 M H₂SO₄ acid solution without any special treatment. Constant potential amperometry at 570 mV (saturated calomel electrode, SCE) in stirred solutions is used for this purpose. A good correlation is attained with the official titrametric method. To understand the possible electrocatalytic reaction mechanism for the electro-oxidation of l-ascorbic acid, calibration graphs over the range 1 × 10⁻⁵ to 1 × 10⁻² mol dm⁻³ l-ascorbic acid are compared for the three electrodes, ca. PVP/Mo(CN)₈⁴⁻, undoped PVP, and GCE; the curvature at high ascorbic acid concentration for the PVP/Mo(CN)₈⁴⁻ electrode is explained in terms of Michaelis–Menten (MM) saturation kinetics. The apparent MM constant (K_M), the maximum catalytic current (i_M), the complex decomposition rate constant (k_c), and the heterogeneous modified electrode rate constant (k^′_ME) are calculated from three different approaches. A reasonably high value of ≈1 × 10⁻² cm s⁻¹ is obtained for k^′_ME, indicating efficient l-ascorbic acid mediation at the PVP/Mo(CN)₈⁴⁻ electrode, thus accounting for quite a high sensitivity of this modified film electrode compared to several other modified electrodes.     

Triple positive solutions of a boundary value problem for nonlinear singular second-order differential equations of mixed type with -Laplacian

In this paper, we establish the existence of triple positive solutions of a two-point boundary value problem for the nonlinear singular second-order differential equations of mixed type with a p-Laplacian operator. We also demonstrate that the results obtained can be applied to study certain higher order mixed boundary value problems. Finally, an example is given to demonstrate the use of the main results of this paper.     

Parameterized complexity of candidate control in elections and related digraph problems

There are different ways for an external agent to influence the outcome of an election. We concentrate on “control” by adding or deleting candidates. Our main focus is to investigate the parameterized complexity of various control problems for different voting systems. To this end, we introduce natural digraph problems that may be of independent interest. They help in determining the parameterized complexity of control for different voting systems including Llull, Copeland, and plurality voting. Devising several parameterized reductions, we provide an overview of the parameterized complexity of the digraph and control problems with respect to natural parameters such as adding/deleting only a bounded number of candidates or having only few voters.     

Learning to pour with a robot arm combining goal and shape learning for dynamic movement primitives

When describing robot motion with dynamic movement primitives (DMPs), goal (trajectory endpoint), shape and temporal scaling parameters are used. In reinforcement learning with DMPs, usually goals and temporal scaling parameters are predefined and only the weights for shaping a DMP are learned. Many tasks, however, exist where the best goal position is not a priori known, requiring to learn it. Thus, here we specifically address the question of how to simultaneously combine goal and shape parameter learning. This is a difficult problem because learning of both parameters could easily interfere in a destructive way. We apply value function approximation techniques for goal learning and direct policy search methods for shape learning. Specifically, we use “policy improvement with path integrals” and “natural actor critic” for the policy search. We solve a learning-to-pour-liquid task in simulations as well as using a Pa10 robot arm. Results for learning from scratch, learning initialized by human demonstration, as well as for modifying the tool for the learned DMPs are presented. We observe that the combination of goal and shape learning is stable and robust within large parameter regimes. Learning converges quickly even in the presence of disturbances, which makes this combined method suitable for robotic applications.     

Closed-loop PLM for intelligent products in the era of the Internet of things

With the advent of the information and related emerging technologies, such as RFID, small size sensors and sensor networks or, more generally, product embedded information devices (PEID), a new generation of products called smart or intelligent products is available in the market.Although various definitions of intelligent products have been proposed, we introduce a new definition of the notion of Intelligent Product inspired by what happens in nature with us as human beings and the way we develop intelligence and knowledge. We see an intelligent product as a product system which contains sensing, memory, data processing, reasoning and communication capabilities at four intelligence levels. This future generations of Intelligent Products will need new Product Data Technologies allowing the seamless interoperability of systems and exchange of not only Static but of Dynamic Product Data as well. Actual standards for PDT cover only lowest intelligence of today’s products. In this context, we try to shape the actual state and a possible future of the Product Data Technologies from a Closed-Loop Product Lifecycle Management (C-L PLM) perspective.Our approach is founded in recent findings of the FP6 IP 507100 project PROMISE and follow-up research work. Standards of the STEP family, covering the product lifecycle to a certain extend (PLCS) as well as MIMOSA and ISO 15926 are discussed together with more recent technologies for the management of ID and sensor data such as EPCglobal, OGC-SWE and relevant PROMISE propositions for standards.Finally, the first efforts towards ontology based semantic standards for product lifecycle management and associated knowledge management and sharing are presented and discussed.     

Stability of iterative processes with errors for a system of nonlinear -accretive variational inclusions in Banach spaces

In this paper, by using the concept of (A,η)-accretive mappings and the new resolvent operator technique associated with (A,η)-accretive mappings, we introduce and study a system of general mixed quasivariational inclusions involving (A,η)-accretive mappings in Banach spaces, and construct a new perturbed iterative algorithm with mixed errors for this system of nonlinear (A,η)-accretive variational inclusions in q-uniformly smooth Banach spaces. Our results improve and generalize the corresponding results of recent works.     

A technique for monitoring SO2 in combustion exhausts: Use of a non-Nernstian sensing element in combination with an upstream catalytic filter

Detection of sulfur dioxide (SO₂) at high temperature (600–750 °C) in the presence of some interferents found in combustion exhausts (NO₂, NO, CO₂, CO, and hydrocarbon (C₃H₆)) is described. The detection scheme involves use of a catalytic filter in front of a non-Nernstian (mixed-potential) sensing element. The catalytic filter was a Ni:Cr powder bed operating at 850 °C, and the sensing elements were pairs of platinum (Pt) and oxide (Ba-promoted copper chromite ((Ba,Cu)_xCr_yO_z) or Sr-modified lanthanum ferrite (LSF)) electrodes on yttria-stabilized zirconia. The Ni:Cr powder bed was capable of reducing the sensing element response to NO₂, NO, CO, and C₃H₆, but the presence of NO₂ or NO (“NO_x”, at 100 ppm by volume) still interfered with the SO₂ response of the Pt–(Ba,Cu)_xCr_yO_z sensing element at 600 °C, causing approximately a 7 mV (20%) reduction in the response to 120 ppm SO₂ and a response equivalent to about 20 ppm SO₂ in the absence of SO₂. The Pt–LSF sensing element, operated at 750 °C, did not suffer from this NO_x interference but at the cost of a reduced SO₂ response magnitude (120 ppm SO₂ yielded 10 mV, in contrast to 30 mV for the Pt-(Ba,Cu)_xCr_yO_z sensing element). The powder bed and Pt–LSF sensing element were operated continuously over approximately 350 h, and the response to SO₂ drifted downward by about 7%, with most of this change occurring during the initial 100 h of operation.