Unveiling the redox electrochemistry of 1D,urchin-like vanadium sulfide electrodes for high-performance hybrid supercapacitors

Exploring novel versatile electrode materials with outstanding electrochemical performance is the key to the development of advanced energy conversion and storage devices.In this work,we aim to construct new-fangled one-dimensional(1D)quasi-layered patronite vanadium tetrasulfide(VS_(4))nanostructures by using different sulfur sources,namely thiourea,thioacetamide,and L-cysteine through an ethyleneaminetetraacetic-acid(EDTA)-mediated solvothermal process.The as-prepared VS4exhibits several unique morphologies such as urchin,fluffy nanoflower,and polyhedron with appropriate surface areas.Among the prepared nanostructures,the VS_(4)-1@NF nanostructure exhibited excellent electrochemical properties in 6 M KOH solution,and we explored its redox electrochemistry in detail.The asprepared VS_(4)-1@NF electrode exhibited battery-type redox characteristics with the highest capacity of280 C g^(-1)in a three-electrode assembly.Moreover,it offered a capacity of 123 F g^(-1)in a hybrid twoelectrode set-up at 1 A g^(-1)with the highest specific energy and specific power of 38.5 W h kg^(-1)and750 W kg^(-1),respectively.Furthermore,to ensure the practical applicability and real-world performance of the prepared hybrid AC@NF//VS_(4)-1@NF cell,we performed a cycling stability test with more than 5,000galvanostatic charge–discharge cycles at 2 A g^(-1),and the cell retained around 84.7%of its capacitance even after 5,000 cycles with a CE of 96.1%.

The Fabrication and SERS Performance of Multi-layer Hollow Au-Ag Alloy Nano Urchins Structure-based SERS Fiber Probe

Novel hollow Au Ag alloy nano urchins were synthesized via Ag seeds growth method,and self-assembly coated on the wall and end-tip of silica fiber for fiber probe fabrication.The nano urchins homogeneously distributed on fiber surface because of fiber silanization.The sizes and tip sharpness of the nano-urchins could be controlled by Ag seeds.The elements distribution analysis indicated there was high Ag content in tip-top for better surface enhance Raman scattering performance.The detectable concentration could be as low as 10-8 M using crystal violet molecules as analyte.Moreover,the fiber probes were stable in air,due to Au in the alloy.This fiber probe could be used for low content single molecular analysis.

Urchin-like CoCu Bimetallic Nanocomposites for Catalytic Hydrogenolysis of Glycerol to Propanediols

Bimetallic CoCu nanocomposites were synthesized in polyol by using Ru as heterogeneous nucleation agent and stearic acid as surfactant, and their catalytic properties were investi- gated by hydrogenolysis of glycerol to propanediols. It was found that the surfactant could induce Co nanocrystals to form nanowires as structure-directing agent, while it＇s ineffective for Cu because only spherical Cu particles were produced under the same condition. When Co2＋ and Cu2＋ coexist in polyol, Cu2＋ is firstly reduced and forms the spherical particles, and then the Cu particles afford surface for the subsequential reduction of Co2＋ and growth of Co nanocrystals to form the nanorods, obtaining the urchin-like CoCu nanocomposites. The catalytic performance in selective hydrogenolysis of glycerol to propanediols proposed that the CoCu urchin-like nanocomposites was superior to the Co nanowires possibly due to that the synergistic effect between Co and Cu component promoted conversion of glyc- erol and obtained the higher propanediol yields based on the specific surface areas of the catalysts.

Sea Urchin Spines as a Model-System for Permeable,Light-Weight Ceramics with Graceful Failure Behavior. Part I. Mechanical Behavior of Sea Urchin Spines under Compression

The spines of pencil and lance urchins Heterocentrotus mammillatus and Phyllacanthus imperialis were studied as a model of light-weight material with high impact resistance.The complex and variable skeleton construction ('stereom') of body and spines of sea urchins consists of highly porous Mg-bearing calcium carbonate.This basically brittle material with pronounced single-crystal cleavage does not fracture by spontaneous catastrophic device failure but by graceful failure over the range of tens of millimeter of bulk compression instead.This was observed in bulk compression tests and blunt indentation experiments on regular,infiltrated and latex coated sea urchin spine segments.Microstructural characterization was carried out using X-ray computer tomography,optical and scanning electron microscopy.The behavior is interpreted to result from the hierarchic structure of sea urchin spines from the rnacroscale down to the nanoscale.Guidelines derived from this study see ceramics with layered porosity as a possible biomimetic construction for appropriate applications.

Higher Dietary Arachidonic Acid Levels Improved the Growth Performance, Gonad Development, Nutritional Value, and Antioxidant Enzyme Activities of Adult Sea Urchin(Strongylocentrotus intermedius)

The gonads of sea urchins(Strongylocentrotus intermedius) are characterized by high levels of arachidonic acid(ARA, 20:4 n-6) and eicosapentaenoic acid(EPA, 20:5 n-3). However, to our knowledge, little information is available regarding the physiological response of adult sea urchins to dietary ARA. In the present study, four dietary feeds were formulated with graded ARA(0, 0.5%, 1%, and 2% dry diet). Each diet was randomly allocated to three cages during a 56-day feeding experiment. The results showed that the sea urchin weight gain rate(WGR) and the gonadosomatic index(GI) significantly increased as ARA was equal to or above 1.0% of dry diet(P < 0.05). The activities of superoxide dismutase(SOD), catalase(CAT), and total anti-oxidative capacity(T-AOC) were the highest in the coelomic fluid of sea urchins that were fed diets with 1% ARA. The total essential amino acid(TEAA) and its ratio to total non-essential amino acid(TNEAA) showed a similar tendency to WGR and GI as dietary ARA increased, and the highest TEAA and TEAA/TNEAA were observed in the gonads of sea urchins that were fed diets with 1% ARA. Levels of ARA and ARA/EPA of the gonads increased while n-3/n-6 polyunsaturated fatty acid(PUFA) decreased with the increase of dietary ARA(P < 0.05). EPA in the gonads of experimental animals fed with formulated feeds showed no significant differences(P> 0.05), but was significantly lower than those fed with kelp(P < 0.05). These results suggested that relatively higher levels of ARA(1% dry diet) significantly promoted growth, gonad development, activities of antioxidant enzymes, as well as nutritional values(TEAA, TEAA/TNEAA, and PUFA) of adult S. intermedius.

Effects of UV-B radiation on fitness related behaviors of the sea urchin Strongylocentrotus intermedius

Ozone depletion induced by anthropogenic gases has been increasing the transmission of solar ultraviolet-B radiation(UV-B, 280–315 nm) through the atmosphere, which may impact the fitness of marine invertebrates in intertidal and shallow waters. To our knowledge, however, the responses of fitness related behaviors to UV-B radiation at different intensities have been rarely studied in marine invertebrates. For the first time, the present study investigated the eff ects of exposure of one hour to UV-B radiation at different intensities on foraging behavior, Aristotle's lantern reflex and righting behavior of the sea urchin Strongylocentrotus intermedius. Exposure of one hour to UV-B radiation at 10 μW/cm^2 significantly reduced foraging behavior. An intensity dependent eff ect of exposure to UV-B radiation was found in the duration of the Aristotle's lantern reflex. Exposure to UV-B radiation at 20 μW/cm^2 for one hour significantly reduced the duration of the Aristotle's lantern reflex, but 10 μW/cm^2 did not. There was no significant diff erence of righting response time among sea urchins exposed to 0, 10 and 20 μW/cm^2 for one hour. To test potential carryover ef fects, the behavioral traits were re-measured three days later. We found significant carryover eff ects of UV-B radiation on foraging time and righting response time, but not on the duration of the Aristotle's lantern reflex. The present study indicates that a brief exposure of one hour to UV-B radiation can significantly aff ect the duration of Aristotle's lantern reflex, righting response time and foraging behavior of a sea urchin, although the immediate impacts and carryover eff ects were highly trait dependent. This study provides new information into the behavioral responses of marine invertebrates to exposure to UV-B radiation. Future studies should be carried out to investigate long-term carryover eff ects of UV-B radiation on behavioral and physiological fitness related traits.

Sea urchin‐like NiMoO_(4) nanorod arrays as highly efficient bifunctional catalysts for electrocatalytic/photovoltage‐driven urea electrolysis

Developing multifunctional electrocatalysts with high catalytic activity,longterm stability,and low cost is essential for electrocatalytic energy conversion.Herein,sea urchinlike NiMoO_(4) nanorod arrays grown on nickel foam has been developed as a bifunctional electrocatalyst for urea oxidation and hydrogen evolution.The NiMoO_(4)‐200/NF catalyst exhibits efficient activity toward hydrogen evolution reaction with a low overpotential of only 68 mV in 1.0 mol/L KOH to gain a current density of 10 mA cm^(–2).The NiMoO_(4)‐300/NF catalyst exhibits a prominent oxygen evolution reaction(OER)catalytic activity with an overpotential of 288 mV at 50 mA cm^(–2),as well as for urea oxidation reaction with an ultralow potential of 1.36 V at 10 mA cm^(–2).The observed difference in electrocatalytic activity and selectivity,derived by temperature variation,is ascribed to different lattice oxygen contents.The lattice oxygen of NiMoO_(4)‐300/NF is more than that of NiMoO_(4)‐200/NF,and the lattice oxygen is conducive to the progress of OER.A urea electrolyzer was assembled with Ni‐MoO_(4)‐200/NF and NiMoO_(4)‐300/NF as cathode and anode respectively,delivering a current density of 10 mA cm^(–2)at a cell voltage of merely 1.38 V.The NiMoO_(4)nanorod arrays has also been successfully applied for photovoltage‐driven urea electrolysis and hydrogen production,revealing its great potential for solar‐driven energy conversion.

Sea Urchin Spines as a Model-System for Permeable,Light-Weight Ceramics with Graceful Failure Behavior.Part Ⅱ.Mechanical Behavior of Sea Urchin Spine Inspired Porous Aluminum Oxide Ceramics under Compression

Sea urchin spines were chosen as a model system for biomimetic ceramics obtained using starch-blended slip casting. Porous alumina ceramics with cap-shaped layers with different alternating porosities were found to have superior fracture behavior under bulk compression compared to ceramics with uniform porosity.They fail in a cascading manner,absorbing high amounts of energy during extended compression paths.The porosity variation in an otherwise single phase material mimicks the architectural microstructure design of sea urchin spines of Heterocentrotus mammillatus,which are promising model materials for impact protection.

Assessment of negative phototaxis in long-term fasted Glyptocidaris crenularis:a new insight into measuring stress responses of sea urchins in aquaculture

A cost-effective method was designed to measure the behavioral response of negative phototaxis to high-intensity illumination in the sea urchin Glyptocidaris crenularis. Ninety sea urchins were randomly and equally divided into two aquaculture environment groups： a fasted group, which was starved during the experiment, and a fed group. After 10 months, the total mortality of each group was recorded. Then, 15 sea urchins were randomly selected from each group and behavioral responses to high-intensity illumination were investigated for each sea urchin. After the behavioral experiment, body measurements of the trial sea urchins were taken. The results reveal that food deprivation significantly affected test diameter （P〈0.01）, body weight （P〈0.01）, gonad weight （P〈0.0I）, and gut weight （P〈0.01）. Furthermore, food deprivation also affected negative phototaxis behaviors of time to rapid spine movement （P〈0.01）, time to the 1 cm position （P〈0.05）, and walking distance in 300 s （P〈0.01）, but not time to body reaction （P〉0.05）. The mortality rates of fasted and fed urchins were 6.7% and 0%, respectively. The present study provides evidence that food deprivation has a significant effect on phenotypic traits and behavioral responses to high-intensity illumination in the sea urchin G. crenularis. With this method, environmental stressors can be easily detected by measuring proper optional indicators. This study provides a new insight into measuring stress responses of sea urchins in aquaculture. However, further studies should be carried out to understand more environmental factors and to compare this potential behavioral method with immune, physiological, and epidemiological approaches.

Isolation of Immune-Relating 185/333-1 Gene from Sea Urchin(Strongylocentrotus intermedius) and Its Expression Analysis

The 185/333 gene family involved in the immune response of sea urchin.One 185/333 c DNA was isolated from Strongylocentrotus intermedius,and named as Si185/333-1.Its full-length c DNA was 1246 bp in length with a 906 bp open reading frame encoding a protein of 301 aa.The molecular weight of the deduced protein was approximately 33.1 k D with an estimated PI of p H 6.26.Si185/333-1 had high identities(70%–86%) to most of Sp185/333.An extraordinary identity of 92% was found between Si185/333-1 and Sp185/333 C5 alpha(ABR22474).Moderate identities(63%–64%) were displayed between Si185/333-1 and He185/333.Si185/333-1 had similar structure to Sp185/333.A signal-peptide,a gly-rich region and a his-rich region were found in its secondary structure.RGD motif was found in gly-rich region at position 116–118aa.There was no transmembrane region in Si185/333-1.The element pattern of Si185/333-1 is different from any available pattern that identified in Sp185/333.Si185/333-1 clustered together with pattern C Sp185/333 in phylogenetic tree.The Si185/333-1 m RNA could be detected in tissues including peristomial membrane,coelomocytes,muscle of Aristotles lantern,gut and tube feet,with the highest expression level detected in peristomial membrane and a relatively low expression in ovary and testis.The temporal expression of Si185/333-1 in peristomial membrane and coelomocytes were up-regulated after bacterial,β-D-glucan and ds RNA challenges,reaching the maximum at 12 h post-stimulation.The up-regulation was more obvious in coelomocytes,and bacterial challenge triggered the highest response.These results proved that 185/333-1 gene was involved in the immune defense of S.intermedius,while more studies were necessary for its function in S.intermedius immunity.

Odor-Active Volatile Compounds from the Gonads of the Sea Urchin <i>Mesocentrotus nudus</i>in the Wild in Miyagi Prefecture, Tohoku, Japan

Background and Aims: Mesocentrotus nudus is commercially harvested from shallow rocky bottoms in northern Japan. The gonads are targeted as an edible product. The objective of this study was to identify odor-active volatile organic compounds (VOCs) from the gonads of adult M. nudus collected at a fishing ground in Miyagi Prefecture, Tohoku, Japan. Methods and Results: Gas chromatography-mass spectrometry analysis and gas chromatography-sniffing techniques identified 42 compounds categorized as alcohols, aldehydes, aromatic hydrocarbons, esters, halomethanes, hydrocarbons, ketones, sulfur-containing compounds, and nitrogen-containing compounds. GC-sniffing analysis characterized four compounds with preferable odors of sea urchin gonads;limonene, propyl acetate, acetone, dibromochloromethane. On the other hand, the analysis characterized three compounds with unpreferable odors;methyl mercaptane, dimethyl sulfide, and s-methyl thioacetate. Several VOCs from the gonads were derived from seaweeds, terrestrial plants, and fish flesh as food because M. nudus is omnivorous. Conclusion: This is the first study to identify VOCs from edible sea urchin gonads in the wild in Japan. These VOC data comprise a typical standard in order to evaluate a higher quality of sea urchin gonads.

Development of the Sea Urchin Arbacia Punctulata in the Presence of the Environmental Toxin Sodium Hypochlorite

Sodium hypochlorite (NaOCl) or bleach, found in effluent from wastewater treatment plants, can act as an environmental toxin. The sea urchin Arbacia punctulata is a common subject of embryological toxicity tests due to its sensitivity to environmental pollutants. Using concentrations of NaOCl that mimic those found in treated wastewater (0.11 ppm, 0.06 ppm, and 0.03 ppm) we observed minimal affects on early larval development, though most larvae took longer to develop at higher NaOCl concentration. There was a significant difference in the percentage of non-normal plutei based on concentration (P = 0.038) and significant interaction between the percent of each morphology and NaOCl concentration (P = 0.0027). The most significant change in non-normal plutei was in the retarded (shortened skeletal rods) malformation which increased in frequency with NaOCl concentration (P = 0.001). There was a significant reduction in skeletal length in both normal and retarded plutei (P < 0.05) as NaOCl increased.

Correlation analyses of covering and righting behaviors to fitness related traits of the sea urchin Glyptocidaris crenularis in different environmental conditions

Complex marine benthic environments shape a number of ecologically important behaviors in sea urchins, including covering and righting behaviors. The present study correlated covering and righting behaviors to a series of fi tness-related traits in sea urchins. Righting response time of Glyptocidaris crenularis was signifi cantly positively correlated with body size, but signifi cantly negatively correlated with food consumption. Covering behavior was not signifi cantly correlated with test diameter, test height or body weight, but covering response time was negatively correlated with body weight. A signifi cantly negative correlation was found between righting response time and covering response time. Glyptocidaris crenularis showed a signifi cantly positive correlation in covering response time with and without exposure to poured sand, but no signifi cance in covering ability(number of shells used to cover). The present study provides new insight into internal mechanisms and evolutionary drives of covering and righting behaviors of sea urchins.

Surgical Removal of Numerous Foreign Bodies from the Foot Caused by Sea Urchin Spines

Injury from sea urchin spines is not rare, especially during summer holidays in the sea side. Failure to remove these spines or inability to remove them completely can lead to long-term squeal of pain and impaired function. Treatment methods include alternative medicine, LASER and surgery. We describe the surgical removal of 102 sea urchin spines from the foot of a 36-year-old man. The wounds healed completely. Although, he initially complained of a mild discomfort on weight bearing, the symptoms disappeared 2 weeks later.

Kinetics Study on Photocatalytic Degradation of Methyl Orange Catalyzed by Sea Urchin-Like Cu2O

Sea urchin-like cuprous oxide with hollow glass microsphere as core was prepared using sodium sulfite as the reducing agent and sodium acetate-acetic acid as buffer solution in copper sulfate solution. Methyl orange was selected as degradation target for photocatalytic experiments. The photocatalytic activities were investigated by visible spectro- photometer. Photocatalytic kinetics parameters were studied by the Langmuir-Hinshelwood model and Arrhenius formula. It was observed that the sea urchin-like morphology dramatically improved the photocatalytic activity of cuprous oxide. The photo-degradation belongs to the first-order reaction and the maximum degradation rate could reach 94.37%. The activation energy and pre-exponential factor are 41.18 KJ·mol-1 and 1.07 × 106, respectively. After seven times recycling, the sample still showed high photo-catalytic efficiency and stability.

Not Only for the Sake of Charity——A Chinese facility for protection of street urchins

In whatever country and for whatever period of human history, it is those lofty aspirations cherished by the human race that have motivated people to go in for charity. The Chinese culture that dates back to thousands of years ago has always called for charity. Numerous ancient maxims testify to this established fact—"extending the same care you give your own elders and children to others’ elders and children," "helping a needy person on hand is worthier than worshipping a god in a faraway land,"

5%Ag掺杂对MNO_(2)纳米棒和海胆微球形貌及其甲苯氧化性能的影响

采用水热法制备了MNO_(2)纳米棒和海胆微球,并原位掺杂5%Ag制备了Mn-Ag复合氧化物,利用SEM、XRD、BET、Raman等表征技术对其结构进行表征,并考察不同催化剂对甲苯的去除性能。结果表明:(NH_(4))_(2)S_(2)O_(8)的掺入量会对MNO_(2)的形貌产生影响,当其掺入量为2.28 g时,形成MNO_(2)纳米棒,当其掺入量为6.84 g时,形成MNO_(2)海胆微球;MNO_(2)纳米棒掺杂5%的Ag后,形貌未发生变化,但当MNO_(2)海胆微球掺杂5%Ag时,表面的纳米线较MNO_(2)海胆微球有所增长,且出现了缠绕现象,形成了空心鸟巢状结构;5%Ag掺杂后,对MNO_(2)纳米棒和MNO_(2)海胆微球的晶型未产生影响,均为α-MNO_(2),但5%Ag-MNO_(2)纳米棒出现了Mn2O_(3)的衍射峰;MNO_(2)海胆微球较MNO_(2)纳米棒的比表面积、孔径和孔容均增大,且Ag的掺杂进一步提高了MNO_(2)海胆微球的比表面积、孔径和孔容;MNO_(2)海胆微球比MNO_(2)纳米棒具有更好的甲苯去除性能,且5%Ag掺杂后,MNO_(2)海胆微球对甲苯的去除性能达到最好。

3D urchin like V-doped CoP in situ grown on nickel foam as bifunctional electrocatalyst for efficient overall water-splitting

Cobalt phosphide (CoP) is considered to be a potential candidate in the field of electrocatalysis due to its low-cost, abundant resources and high electrochemical stability. However, there is a great space for further improvement of its electrocatalytic performance since its charge transfer rate and catalytic activity have not reached a satisfactory level. Herein, we design and fabricate a three dimensional urchins like V-doped CoP with different amounts of V-doping on nickel foam electrode. The V-doped CoP/NF electrode with optimized amounts of V-doping (10%) exhibits outstanding hydrogen evolution reaction (HER) performance under universal-pH conditions and preeminent oxygen evolution reaction (OER) performance in alkaline media. Notably, the assembled water-splitting cell displays a cell voltage of only 1.53 V at 10 mA·cm−2 and has excellent durability, much better than many reported related bifunctional catalysts. The experiment results and theoretical analysis revealed that vanadium atoms replace cobalt atoms in CoP lattice. Vanadium doping can not only raise the density of electronic states near the Fermi level enhancing the conductivity of the catalyst, but can also optimize the free energy of hydrogen and oxygen-containing intermediates adsorption over CoP, thus promoting its catalytic activity. Moreover, the unique nanostructure of the catalyst provides the various shortened channels for charge transfer and reactant/electrolyte diffusion, which accelerates the electrocatalytic process. Also, the in situ growth strategy can improve the conductivity and stability of the catalyst.

Carbon-coated Fe2O3 hollow sea urchin nanostructures as high-performance anode materials for lithium-ion battery

Fe2O3 has become a promising anode material in lithium-ion batteries (LIBs) in light of its low cost, high theoretical capacity (1007 mA h g^−1) and abundant reserves on the earth. Nevertheless, the practical application of Fe2O3 as the anode material in LIBs is greatly hindered by several severe issues, such as drastic capacity falloff, short cyclic life and huge volume change during the charge/discharge process. To tackle these limitations, carbon-coated Fe2O3 (Fe2O3@MOFC) composites with a hollow sea urchin nanostructure were prepared by an effective and controllable morphology-inherited strategy. Metal-organic framework (MOF)-coated FeOOH (FeOOH@-MIL-100(Fe)) was applied as the precursor and self-sacrificial template. During annealing, the outer MOF layer protected the structure of inner Fe2O3 from collapsing and converted to a carbon coating layer in situ. When applied as anode materials in LIBs, Fe2O3@MOFC composites showed an initial discharge capacity of 1366.9 mA h g^−1 and a capacity preservation of 1551.3 mA h g^−1 after 200 cycles at a current density of 0.1 A g^−1. When increasing the current density to 1 A g^−1, a reversible and high capacity of 1208.6 mA h g^−1 was obtained. The enhanced electrochemical performance was attributed to the MOF-derived carbon coating layers and the unique hollow sea urchin nanostructures. They mitigated the effects of volume expansion, increased the lithium-ion mobility of electrode, and stabilized the as-formed solid electrolyte interphase films.

Advanced rechargeable lithium-ion batteries based on bendable ZnCo2O4-urchins-on-carbon-fibers electrodes

A novel class of ZnCo2O4-urchins-on-carbon-fibers matrix has been designed, characterized, and used to fabricate high-performance energy storage devices. We obtained a reversible lithium storage capacity of 1180 mA＇h/g even after 100 cycles, demonstrating the highreversible capacity and excellent cycle life of the as-prepared samples. Tested as fast-charging batteries, these electrodes exhibited a considerable capacity of 750 mA＇h/g at an exceptionally high rate of 20 C （18 A/g）, with an excellent cycle life （as long as 100 cycles）, which are the best high-rate results reported at such a high charge^discharge current density for ZnCo2O4-based anode materials in lithium rechargeable batteries. Such attractive properties may be attributed to the unique structure of the binder-free ZnCo2O4-urchins-on-carbon-fibers matrix. Full batteries were also developed by combining the ZnCo2O4 anodes with commercial LiCoO2 cathodes, which showed flexible/wearable and stable features for use as very promising future energy storage units.