Control of spiral breakup by an alternating advective field

The control of spiral breakup due to Doppler instability is investigated. It is found that applying an alternating advective field with suitable amplitude and period can prevent the breakup of spiral waves. Further numerical simulations show that the growing meandering behavior of a spiral tip caused by decreasing the excitability of the medium can be efficiently suppressed by the alternating advective field, which inhibits the breakup of spiral waves eventually.     

An elegant method to study an isolated spiral wave in a thin layer of a batch Belousov-Zhabotinsky reaction under oxygen-free conditions

A method to prepare a uniform thin layer of a batch Belousov-Zhabotinsky (BZ) reaction under oxygen-free conditions for the study of an isolated spiral wave is presented. After a first layer of gel soaked with the BZ solution has been delivered into the reactor, a single spiral wave was initiated, and finally the remaining reactor volume was filled with gel and BZ medium. The completely filled reactor is sealed gas-tightly, yielding oxygen-free, and thus more controlled, reaction conditions. A systematic study of the behaviour of an isolated spiral wave in a ferroin-catalyzed BZ reaction under batch conditions has been performed. Recipes for BZ media that support a slowly rotating meandering spiral were developed. In cases of extremely low excitability (i.e., relative large stimuli are required to induce a propagating wave), the number of petals in the trajectory of a spiral tip decreased due to aging of the reaction system. Since oxygen-free conditions are necessary for the study of the dynamics in three-dimensional excitable media, and the wave velocities of a spiral are sufficiently low, the developed chemical recipes are suitable for studies of the behaviour of scroll waves in three-dimensional systems by optical tomography.     

Drift of spiral waves controlled by a polarized electric field

The drift behavior of spiral waves under the influence of a polarized electric field is investigated in the light that both the polarized electric field and the spiral waves possess rotation symmetry. Numerical simulations of a reaction-diffusion model show that the drift velocity of the spiral tip can be controlled by changing the polarization mode of the polarized electric field and some interesting drift phenomena are observed. When the electric field is circularly polarized and its rotation follows that of the spiral, the drift speed of the spiral tip reaches its maximal value. On the contrary, opposite rotation between the spiral and electric field locks the drift of the spiral tip. Analytical results based on the weak deformation approximation are consistent with the numerical results. We hope that our theoretical results will be observed in experiments, such as the Belousov-Zhabotinsky reaction.     

Super‐Soft and Super‐Elastic DNA Robot with Magnetically Driven Navigational Locomotion for Cell Delivery in Confined Space

Soft organisms such as earthworms can access confined, narrow spaces, inspiring scientists to fabricate soft robots for in vivo manipulation of cells or tissues and minimally invasive surgery. We report a super‐soft and super‐elastic magnetic DNA hydrogel‐based soft robot (DNA robot), which presents a shape‐adaptive property and enables magnetically driven navigational locomotion in confined and unstructured space. The DNA hydrogel is designed with a combinational dynamic and permanent crosslinking network through chain entanglement and DNA hybridization, resulting in shear‐thinning and cyclic strain properties. DNA robot completes a series of complex magnetically driven navigational locomotion such as passing through narrow channels and pipes, entering grooves and itinerating in a maze by adapting and recovering its shape. DNA robot successfully works as a vehicle to deliver cells in confined space by virtue of the 3D porous networked structure and great biocompatibility.     

Chemical wave studies in the bromate–pyrocatechol beads system

We studied the chemical wave activity of the pyrocatechol‐acidic bromate system in the presence of ferroin‐loaded beads. The wave activity lasted for more than 24 h while meandering spirals continued for up to 10 h. Rigid and meandering spiral waves were investigated. We have analyzed the wave propagation speed and spiral tip trajectory versus the initial concentrations of all reagents as well as the age of the solution. Wave velocity depends on [H⁺] and [BrO] concentrations by the relationship v=k[H⁺]^1/2[BrO]^1/2, which is in agreement with other studies. This system is ideal to study wave activity and spiral waves as it does not produce precipitates under the studied conditions. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 198–203, 2011     

Aggregation behavior of MPEG‐PCL diblock copolymers in aqueous solutions and morphologies of the aggregates

Poly(ethylene glycol)‐b‐polycaprolactone (MPEG‐PCL) diblock copolymers were synthesized via a ring‐opening polymerization of ε‐CL monomers with MPEG as an initiator. Their solubilities and apparent critical micelle concentrations (CMC) in aqueous solution were investigated as well as the determination of the micellar hydrodynamic diameter using dynamic light scattering (DLS). As PCL block length increased, the solubility and CMC decreased while diameters of micelles increased. The gel–sol transition behaviors were investigated using a vial tilting method. Aqueous solutions of copolymers undergo a gel to sol transition with increase in temperature when their polymer concentrations are above a critical gel concentration (CGC). The CGC of the copolymers and gel–sol transition temperature are influenced by the PCL chain length. The tapping mode AFM was performed by imaging the freeze‐dried deposits from the copolymer solutions on mica to investigate a process from free chains to micelles and to gel. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3406–3417, 2006     

硫杂蒽酮镍（II）配合物与DNA的作用研究

合成了O-（硫杂蒽酮-[2]-基）-氧乙酸镍（II）配合物。通过元素分析,IR, DTA-TG谱对其结构进行了表征。研究表明：配体羧羰基脱质子后与镍离子配位,配合物中含有一定量的配位水。同时以紫外可见光谱、荧光光谱、园二色谱,电化学方法和凝胶电泳方法研究了该配合物与DNA的作用。结果表明,该配合物能在生理条件下比配体和金属离子更有效地切割质粒DNA,自由基捕捉剂的加入不影响配合物的切割活性。该配合物使DNA溶液的紫外吸收强度和园二色吸收强度降低,DNA的存在可使该配合物的氧化还原活性降低。与溴化乙锭和DNA的竞争反应说明,该配合物主要以嵌入方式与DNA结合。     

Anchoring Transition Induced by Gelation in a Liquid Crystal System

We report a novel type of anchoring transition (ANT) in a liquid crystal driven by the physical gelation of the system. The ANT manifests as anomaly in the thermal behaviour of the dielectric permittivity. Data from X‐ray studies suggest that ANT is caused by the ability of the gel fibres to compete with the substrate‐driven orientation conditions. It is further found that the molecular reorientation is possible only in cases where the gel is weak, the difference between weak and strong gels being established by rheological measurements.     

Control and coupling of spiral waves in excitable media

We report the complex dynamics of spiral waves observed in the ferroin-catalyzed BZ reaction. The reaction is run in an open unstirred reactor (CFUR) with the catalyst immobilized on a polysulfone membrane. The catalyst-loaded membrane is placed between two well stirred compartments which are fed with solutions of sulfuric acid/malonic acid/bromide and sulfuric acid/bromate, respectively. An electrical field perpendicular to the membrane can be applied via Pt-ring electrodes or, alternatively, via transparent electrodes made of ITO-coated glass. In the field-free case relatively simple target and spiral patterns are observed in the membrane. If an alternating electrical field is applied the spiral core drifts through the membrane. The actual trajectory of the spiral tip depends on the amplitude and frequency of the applied electrical field. If the perturbation parameters are chosen properly the wave fronts break up and new spiral cores emerge under the influence of the alternating field. Complex spatio-temporal patterns may be induced which are reminiscent of "spiral-chaos". After switching off the perturbation the system returns to its previous, "simple" behaviour. Our experimental observations are confirmed by model calculations based on the Barkley model of spiral waves. The technique of using modulated excitability to control the dynamics of spiral waves is further extended to the coupling of two spirals in two CFURs. We present numerical simulations based on two identical excitable reaction-diffusion (RD) systems which are mutually coupled. The coupling is based on the observation of an arbitrarily chosen point inside each of the RD systems: If a chemical wave passes the point of optical observation in system 1 an electric field is applied to system 2 and vice versa. Thus, a local observation made in one system is transformed in a global perturbation of the second CFUR. We report the observation of CFUR states where the two spiral waves are spatially and temporally coupled to each other.     

Negative-tension instability of scroll waves and winfree turbulence in the oregonator model

Excitable media support self-organized scroll waves which can be unstable and give rise to three-dimensional wave chaos. Winfree turbulence of scroll waves results from the negative-tension instability of scroll waves; it plays an important role in the cardiac tissue where it may lead to ventricular fibrillation. By numerical simulations of the Oregonator model, we show that this instability and, thus, the Winfree turbulence may also be observed in the Belousov-Zhabotinsky reaction. The region in the parameter space, where the instability takes place, is determined, and a relationship between the negative-tension instability and the meandering behavior of spiral waves is found. The application of global periodic forcing to control such turbulence in the Oregonator model is discussed.     

Suppression of Spiral Waves by Generating Self-exciting Target Wave

A new scheme is proposed to suppress stable and meandering spiral waves in excitable media by generating a self-exciting target wave in a local area. An arbitrary selected grid in the media is sampled, and the sampled signal is fed back into a local area in the media. Numerical simulation results confirm its effectiveness when the scheme is introduced into anisotropic (the diffusion coefficient is perturbed vs. time and/or space) and isotropic media. Results also show the scheme's robustness to spatiotemporal noise.     

Light‐Modulated Intermittent Wave Groups in a Diffusively Fed Reactive Gel

Inspired by the biological growth that takes place in time‐varying external fields such as light or temperature, we design an open reaction‐diffusion system in order to investigate growth dynamics. The system is composed of the Belousov–Zhabotinsky (BZ) oscillatory reaction coupled with a copolymer gel consisting of NIPAAm and a photosensitive ruthenium catalyst. When subject to a unidirectional flow of the BZ reactants, the system displays groups of chemical waves whose structure depends upon the period and amplitude of illumination. Simulations of a modified six‐variable Oregonator model exhibit all the complex wave groups found in our experiments. Studying this growth structure may aid in understanding the influence of periodic environmental variation on complex growth processes in living systems.     

A Photoinduced Reversible Phase Transition in a Dipeptide Supramolecular Assembly

Tunable supramolecular assembly has found various applications in biomedicine, molecular catalysis, optoelectronics, and nanofabrication. Unlike traditional covalent conjugation, non‐covalent introduction of a photoswitchable moiety enables reversible photomodulation of non‐photosensitive dipeptide supramolecular assembly. Under light illumination, a long‐lived photoacid generator releases a proton and mediates the dissociation of dipeptide‐based organogel, thereby resulting in sol formation. Under darkness, the photoswitchable moiety entraps a proton, resulting in gel regeneration. Furthermore, accompanying the isothermal recycled gel–sol transition in a spatially controlled manner, renewable patterns are spontaneously fabricated. This new concept of light‐controlled phase transition of amino acid‐based supramolecular assemblies will open up the possibility of wide applications.     

Temperature‐induced spontaneous sol–gel transitions of poly(D,L‐lactic acid‐co‐glycolic acid)‐b‐poly(ethylene glycol)‐b‐poly(D,L‐lactic acid‐co‐glycolic acid) triblock copolymers and their end‐capped derivatives in water

The spontaneous hydrogel formation of a sort of biocompatible and biodegradable amphiphilic block copolymer in water was observed, and the underlying gelling mechanism was assumed. A series of ABA‐type triblock copolymers [poly(D,L ‐lactic acid‐co‐glycolic acid)‐b‐poly(ethylene glycol)‐b‐poly(D,L ‐lactic acid‐co‐glycolic acid)] and different derivatives end‐capped by small alkyl groups were synthesized, and the aqueous phase behaviors of these samples were studied. The virgin triblock copolymers and most of the derivatives exhibited a temperature‐dependent reversible sol–gel transition in water. Both the poly(D,L ‐lactic acid‐co‐glycolic acid) length and end group were found to significantly tune the gel windows in the phase diagrams, but with different behaviors. The critical micelle concentrations were much lower than the associated critical gel concentrations, and an intact micellar structure remained after gelation. A combination of various measurement techniques confirmed that the sol–gel transition with an increase in the temperature was induced not simply via the self‐assembly of amphiphilic polymer chains but also via the further hydrophobic aggregation of micelles resulting in a micelle network due to a large‐scale self‐assembly. The coarsening of the micelle network was further suggested to account for the transition from a transparent gel to an opaque gel. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1122–1133, 2007     

Photopolymerized organo‐silica hybrid monolithic columns: Characterization of their performance in capillary liquid chromatography

Porous hybrid organo‐silica monoliths have been prepared inside pretreated 100 μm id UV transparent fused‐silica capillaries using simultaneous sol‐gel transition and polymerization of 3‐(methacryloyloxy)propyl trimethoxysilane in the presence of toluene as a porogen. The sol‐gel reaction was catalyzed by hydrochloric acid while various photoinitiators including azobisisobutyronitrile, 2,2‐dimethoxy‐2‐phenylacetophenone, and Irgacure 819 were used for the photopolymerization carried out under irradiation with UV light at a wavelength of 254 or 365 nm. The chromatographic performance of photopolymerized monolithic columns in RP liquid chromatographic mode was assessed with respect to the following metrics: column efficiency, methylene and steric selectivity, effect of silanol groups, van Deemter plot, permeability, and pore size distribution. Columns with an efficiency of up to 77 000 plates/m for benzene has been achieved at a flow velocity of 0.47 mm/s. The performance of photopolymerized hybrid monolithic column was compared to the performance of columns prepared via thermally initiated polymerization.     

Effects of poloxamer on the gelation of silk sericin

Effects of the concentration of poloxamer 407, temperature, and the concentration of sericin on the gelation of silk sericin (SS) were studied. Gelation of SS was accelerated with an increase in poloxamer concentration and temperature. The sol‐gel transition of SS became irreversible with respect to the temperature in the presence of poloxamer, whereas the sol‐gel transition of SS itself was reversible. Infrared (IR) and circular dichroism (CD) spectra show that the conformational change of SS in the presence of poloxamer was accelerated from random coil to β‐structure. X‐ray diffraction and differential scanning calorimetry (DSC) show that the crystalline structure of poloxamer in the mixture was affected by the presence of SS and that its melting temperature was shifted to lower temperature with increasing SS content, indicating an interaction between poloxamer and SS through hydrogen and hydrophobic bondings.     

Vibrational dynamics and stability of the high-pressure chain and ring phases in S and Se

The high-pressure phases of group-VI elements sulfur and selenium in their spiral chain and ring structures are examined by in situ Raman and x-ray diffraction techniques combined with first principles electronic structure calculations. The S-II, S-III, Se-I, and Se-VII having spiral chain structures and S-VI with a molecular six-member ring structure are studied in a wide P-T range. The square spiral chain structure of S-III and Se-VII is characterized by seven Raman modes that harden with increasing pressure. The calculations reproduce the observed frequencies and allow the authors to make the mode assignment. The "p-S" and "hplt" phases of sulfur reported by previous Raman studies are identified as S-II and S-III with the triangular and square spiral chain structures, respectively. The phase relations obtained by the x-ray and Raman measurements show that the high-pressure high-temperature phases of sulfur, observed by x-ray, can be induced by laser illumination at room temperature.     

Thermal Efficiency of Solar Steam Generation Approaching 100 % through Capillary Water Transport

Solar‐driven interfacial water evaporation yield is severely limited by the low efficiency of solar thermal energy. Herein, the injection control technique (ICT) achieves a capillary water state in rGO foam and effectively adjusts the water motion mode therein. Forming an appropriate amount of capillary water in the 3D graphene foam can greatly increase the vapor escape channel, by ensuring that the micrometer‐sized pore channels do not become completely blocked by water and by exposing as much evaporation area as possible while preventing solar heat from being used to heat excess water. The rate of solar steam generation can reach up to 2.40 kg m^?2 h^?1 under solar illumination of 1 kW m^?2, among the best values reported. In addition, solar thermal efficiency approaching 100 % is achieved. This work enhances solar water‐evaporation performance and promotes the application of solar‐driven evaporation systems made of carbon‐based materials.     

Thermomechanical properties and phase structure of epoxy/silica nano‐hybrid materials constructed from a linear silicone oligomer

Epoxy‐grafted silicone oligomer (ESO), which has a linear silicone chain in the backbone moiety, was synthesized from a trifunctional alkoxysilane via a sol–gel reaction. Characterization of ESO was performed with ¹H and ²⁹Si NMR, Fourier transform infrared, and gel permeation chromatography. The number‐average molecular weight of ESO was 3300. By adding the silicone oligomer as the inorganic source in the curing process of the epoxy resin, novel epoxy/silica hybrid materials were prepared. It was observed by transmission electron microscope that fine silica‐rich domains of about 5‐nm diameter were uniformly dispersed in the cured epoxy matrix. Thermomechanical properties of the hybrid materials were also investigated. The storage modulus in the rubbery region and the peak area of the tan δ curve at the glass‐transition region increased and decreased, respectively, with the hybridization of the silica network. The mobility of the epoxy network chains should be considerably suppressed by the hybridization with the silica network. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1631–1639, 2005