Self-Templating Copolymerization to Produce Robust Conductive Nanocoatings Based on Conjugated Polymer Brushes with Implementable Memristive Characteristics.

An effective synthesis of conductive polymer brushes, i.e., self-templating surface-initiated copolymerization (ST-SICP), is developed. It proceeds through copolymerization of pendant thiophene groups in the precursor multimonomer poly(3-methylthienyl methacrylate) (PMTM) brushes with free 3-methylthiophene (3MT) monomers leading to PMTM-co-P3MT brushes. This approach leads to improved conformational freedom of generated conjugated poly(thiophene)-based chains and their higher share in the brushes with respect to conjugation of pendant thiophene groups only. As a result, best performing conjugated PMTM-co-P3MT brushes demonstrate high ohmic conductivity in both out-of-plane and in-plane direction. Furthermore, thanks to the covalent anchoring as well as intra- and intermolecular connections, highly stable and mechanically robust nanocoatings are produced which can survive mechanical cleaning and long-term storage under ambient conditions. Grafting of ionic poly(sodium 4-styrenesulfonate) (PSSNa) in between PMTM-co-P3MT chains brings new properties to such binary mixed brushes that can operate as thin-film memristive coating with switchable conductance. It is worth mentioning that the crucial synthetic steps, i.e., grafting of precursor PMTM brushes by surface-initiated organocatalyzed atom transfer radical polymerization (SI-O-ATRP) and PSSNa chains by surface-initiated photoiniferter-mediated polymerization (SI-PIMP) are conducted under ambient conditions using only microliter volumes of reagents providing methodology that can be considered for use beyond the laboratory scale.

Functionalization of Ti64 via Direct Laser Interference Patterning and Its Influence on Wettability and Oxygen Bubble Nucleation.

The nucleation of bubbles on solid surfaces is an important phenomenon in nature and technological processes like electrolysis. During proton-exchange membrane electrolysis, the nucleation and separation of the electrically nonconductive oxygen in the anodic cycle plays a crucial role to minimize the overpotential it causes in the system. This increases the efficiency of the process, making renewable energy sources and the "power-to-gas" strategy more viable. A promising approach is to optimize gas separation by surface functionalization in order to apply a more advantageous interface to industrial materials. In this work, the connection between the wettability and bubble nucleation of oxygen is investigated. For tailoring the wettability of Ti64 substrates, the direct laser interference patterning method is applied. A laser source with a wavelength of 1064 nm and a pulse duration of 12 ps is used to generate periodic pillar-like structures with different depths up to ∼5 µm. The resulting surface properties are characterized by water contact angle measurement, scanning electron microscopy, confocal microscopy, and X-ray photon spectroscopy. It was possible to generate structures with a water contact angle ranging from 20° up to nearly superhydrophobic conditions. The different wettabilities are validated based on X-ray photon spectroscopy and the different elemental composition of the samples. The results indicate that the surface character of the substrate adapts depending on the surrounding media and needs more time to reach a steady state for deeper structures. A custom setup is used to expose the functionalized surfaces to oxygen-oversaturated solutions. It is shown that a higher hydrophobicity of the structured surface yields a stronger interaction with the dissolved gas. This significantly enhances the oxygen nucleation up to nearly 350% by generating approximately 20 times more nucleation spots, but also smaller bubble sizes and a reduced detachment rate.

Electrochemical determination of thiethylperazine using semi-graphitized carbon nanofibers-MnO nanocomposite.

A new voltammetric method is proposed for high sensitive thiethylperazine (THP) determination, using a glassy carbon electrode modified with semi-graphitized carbon nanofibers/MnO nanocomposite (eCNF/MnO/GC). To the best of our knowledge, this is the first electrochemical assay of THP  determination, and the first use of the eCNF/MnO as the electrode modifier. The proposed method using eCNF/MnO/GC is characterized by high repeatability and sensitivity of measurements, with the linearity of THP in the range from 0.05 to 2.2 µmol L-1. The lowest detection limit achieved on the eCNF/MnO/GC electrode for 30 s of preconcentration was 6.3 nmol L-1 THP in 0.05 mol L-1 acetate buffer of  pH 5.6. The proposed method was successfully applied to highly sensitive THP determination in complex matrices, such as tablets and plasma with good recovery (98-103%). The RSD value obtained for THP measurement at a concentration of 0.1 µmol L-1 was 1.3%. Amperometric measurements of THP under the flow injection conditions were also performed to indicate the possibility of its fast and accurate determination (103% and 95% for unmodified and modified electrode, respectively), with the duration of single analysis of approx. 30 s.

Influence of Heat Treatment of Electrospun Carbon Nanofibers on Biological Response.

The main aim of this study is to investigate the effect of fragmentation of electrospun carbon nanofibers (eCNFs) obtained at different temperatures, i.e., at 750 °C, 1000 °C, 1500 °C, 1750 °C and 2000 °C on the cellular response in vitro. In order to assess the influence of nanofibers on biological response, it was necessary to conduct physicochemical, microstructural and structural studies such as SEM, XPS, Raman spectroscopy, HRTEM and surface wettability of the obtained materials. During the in vitro study, all samples made contact with the human chondrocyte CHON-001 cell lines. The key study was to assess the genotoxicity of eCNFs using the comet test after 1 h or 24 h. Special attention was paid to the degree of crystallinity of the nanofibers, the dimensions of the degradation products and the presence of functional groups on their surface. A detailed analysis showed that the key determinant of the genotoxic effect is the surface chemistry. The presence of nitrogen-containing groups as a product of the decomposition of nitrile groups has an influence on the biological response, leading to mutations in the DNA. This effect was observed only for samples carbonized at lower temperatures, i.e., 750 °C and 1000 °C. These results are important with respect to selecting the temperature of thermal treatment of eCNFs dedicated for medical and environmental functions due to the minimization of the genotoxic effect of these materials.

Cobalt-platinum nanomotors for local gas generation.

Bimetallic Co-Pt nanorods exhibit an enhanced capacity for the production of gas from liquid-phase chemicals. Based on the systematic structural and magnetic characterization we discuss potential applications of these hybrid nanostructures for localized fuel generation in microdevices. Experimental proof of the feasibility for controlling the rate of catalytic reaction via external magnetic stimuli is shown. This unique functionality makes these hybrids promising candidates for optimizing the energy conversion rate in microfluidics fuel cells.

Versailles Project on Advanced Materials and Standards interlaboratory study on intensity calibration for x-ray photoelectron spectroscopy instruments using low-density polyethylene.

We report the results of a Versailles Project on Advanced Materials and Standards interlaboratory study on the intensity scale calibration of x-ray photoelectron spectrometers using low-density polyethylene (LDPE) as an alternative material to gold, silver, and copper. An improved set of LDPE reference spectra, corrected for different instrument geometries using a quartz-monochromated Al Kα x-ray source, was developed using data provided by participants in this study. Using these new reference spectra, a transmission function was calculated for each dataset that participants provided. When compared to a similar calibration procedure using the NPL reference spectra for gold, the LDPE intensity calibration method achieves an absolute offset of ∼3.0% and a systematic deviation of ±6.5% on average across all participants. For spectra recorded at high pass energies (≥90 eV), values of absolute offset and systematic deviation are ∼5.8% and ±5.7%, respectively, whereas for spectra collected at lower pass energies (<90 eV), values of absolute offset and systematic deviation are ∼4.9% and ±8.8%, respectively; low pass energy spectra perform worse than the global average, in terms of systematic deviations, due to diminished count rates and signal-to-noise ratio. Differences in absolute offset are attributed to the surface roughness of the LDPE induced by sample preparation. We further assess the usability of LDPE as a secondary reference material and comment on its performance in the presence of issues such as variable dark noise, x-ray warm up times, inaccuracy at low count rates, and underlying spectrometer problems. In response to participant feedback and the results of the study, we provide an updated LDPE intensity calibration protocol to address the issues highlighted in the interlaboratory study. We also comment on the lack of implementation of a consistent and traceable intensity calibration method across the community of x-ray photoelectron spectroscopy (XPS) users and, therefore, propose a route to achieving this with the assistance of instrument manufacturers, metrology laboratories, and experts leading to an international standard for XPS intensity scale calibration.

Gradient of zinc content in core-shell zinc ferrite nanoparticles - precise study on composition and magnetic properties.

A broad spectrum of applications of magnetic nanoparticles leads to the need for the precise tuning of their magnetic properties. In this study, a series of magnetite and zinc-ferrite nanoparticles were successfully prepared by modified high-temperature synthesis in a controlled gas atmosphere. Nanoparticles with different zinc to iron ratios and pure Fe3O4 were obtained. The structure of the nanoparticles was studied by transmission electron microscopy and Mössbauer spectroscopy. These revealed the single domain character of the nanoparticles and the influence of the synthesis temperature and zinc to iron ratio on their shape and size. Chemical structure was characterized by inductively coupled plasma optical emission spectroscopy, energy dispersive X-ray spectroscopy and thermogravimetric analysis. X-ray photoelectron spectroscopy coupled with an argon gas cluster ion beam (Ar-GCIB) allowed the study of subsequent layers of the nanoparticles without altering their chemical structure. This revealed the presence of a carbon layer on all nanoparticles consisting of capping agents used in the synthesis and revealed the core-shell character of the zinc ferrite particles. In addition, different types of zinc infusions in the nanoparticle structure were observed when using different Zn/Fe ratios. Finally, magnetic studies performed by means of vibrating sample magnetometry proved the superparamagnetic behavior of all the samples.

Tuning of the Seebeck Coefficient and the Electrical and Thermal Conductivity of Hybrid Materials Based on Polypyrrole and Bismuth Nanowires.

The growing demand for clean energy catalyzes the development of new devices capable of generating electricity from renewable energy resources. One of the possible approaches focuses on the use of thermoelectric materials (TE), which may utilize waste heat, water, and solar thermal energy to generate electrical power. An improvement of the performance of such devices may be achieved through the development of composites made of an organic matrix filled with nanostructured thermoelectric materials working in a synergetic way. The first step towards such designs requires a better understanding of the fundamental interactions between available materials. In this paper, this matter is investigated and the questions regarding the change of electrical and thermal properties of nanocomposites based on low-conductive polypyrrole enriched with bismuth nanowires of well-defined geometry and morphology is answered. It is clearly demonstrated that the electrical conductivity and the Seebeck coefficient may be tuned either simultaneously or separately within particular Bi NWs content ranges, and that both parameters may be increased at the same time.

Memristive properties and synaptic plasticity in substituted pyridinium iodobismuthates.

This study explores the impact of organic cations in bismuth iodide complexes on their memristive behavior in metal-insulator-metal (MIM) type thin-layer devices. The presence of electron-donating and electron withdrawing functional groups (-CN, -CH3, -NH2, and -N(CH3)2) on pyridinium cations induces morphological alterations in crystals, thus influencing the electronic or ionic conductivity of devices comprising sandwiched thin layers (thickness = 200 nm ± 50) between glass/ITO as bottom electrode (∼110 nm) and copper (∼80 nm) as the top electrode. It was found that the current-voltage (I-V) scans of the devices reveal characteristic pinched hysteresis loops, a distinct signature of memristors. The working voltage windows are significantly influenced by both the types of cation and the dimensionality of ionic fragments (0D or 1D) in the solid-state form. Additionally, the temperature alters the surface area of the I-V loops by affecting resistive switching mechanisms, corresponding log-log plots at three temperatures (-30 °C, room temperature and 150 °C) are fully studied. Given that a memristor can operate as a single synapse without the need for programming, aligning with the requirements of neuromorphic computing, the study investigates long-term depression, potentiation, and spike-time-dependent plasticity-a specific form of the Hebbian learning rule-to mimic biologically synaptic plasticity. Different polar pulses, such as triangle, sawtooth, and square waveforms were employed to generate Hebbian learning rules. The research demonstrates how the shape of the applied pulse series, achieved by overlapping pre- and post-pulses at different time scales, in association with the composition and dimensionality of ionic fragments, lead to changes in the synaptic weight percentages of the devices.

Mesoporous Silica MCM-41 from Fly Ash as a Support of Bimetallic Cu/Mn Catalysts for Toluene Combustion.

The main outcome of this research was to demonstrate the opportunity to obtain a stable and well-ordered structure of MCM-41 synthesized from fly ash. A series of bimetallic (Cu/Mn) catalysts supported at MCM-41 were prepared via grinding method and investigated in catalytic toluene combustion reaction to show the material's potential application. It was proved, that the Cu/Mn ratio had a crucial effect on the catalytic activity of prepared materials. The best catalytic performance was achieved with sample Cu/Mn(2.5/2.5), for which the temperature of 50% toluene conversion was found to be 300 °C. This value remains in line with the literature reports, for which comparable catalytic activity was attained for 3-fold higher metal loadings. Time-on-stream experiment proved the thermal stability of the investigated catalyst Cu/Mn(2.5/2.5). The obtained results bring a valuable background in the field of fly ash utilization, where fly ash-derived MCM-41 can be considered as efficient and stable support for dispersion of active phase for catalyst preparation.

Interfacial blending in co-axially electrospun polymer core-shell fibers and their interaction with cells via focal adhesion point analysis.

Electrospun polymer scaffolds have gained prominence in biomedical applications, including tissue engineering, drug delivery, and wound dressings, due to their customizable properties. As the interplay between cells and materials assumes fundamental significance in biomaterials research, understanding the relationship between fiber properties and cell behaviour is imperative. Nevertheless, altering fiber properties introduces complexity by intertwining mechanical and surface chemistry effects, challenging the differentiation of their individual impacts on cell behaviour. Core-shell fibers present an appealing solution, enabling the control of mechanical properties of scaffolds, flexibility in material and drug selection, efficient encapsulation, strong protection of bioactive drugs against harsh environments, and controlled, prolonged drug release. This study addresses a key challenge in core-shell fiber design related to the blending effect between core and shell polymers. Two types of fibers, PMMA and core-shell PC-PMMA, were electrospun, and thorough analyses confirmed the desired core-shell structure in PC-PMMA fibers. Surface chemistry analysis revealed PC diffusion to the PMMA shell of the core-shell fiber during electrospinning, subsequently prompting an investigation of the fiber's surface potential. Conducting cellular studies on osteoblasts by super-resolution confocal microscopy provided insights into the direct influence of interfacial polymer blending and, consequently, altered fiber surface and mechanical properties on cell focal adhesion points, bridging the gap between material attributes and cell responses in core-shell fibers.

Flexible and Thermally Insulating Porous Materials Utilizing Hollow Double-Shell Polymer Fibers.

The global climate change is mainly caused by carbon dioxide (CO2) emissions. To help reduce CO2 emissions and conserve thermal energy, sustainable materials based on flexible thermal insulation are developed to minimize heat flux, drawing inspiration from natural systems such as polar bear hairs. The unique structure of hollow double-shell fibers makes it possible to achieve low thermal conductivity in the material while retaining exceptional elasticity, allowing it to adapt to insulation systems of any shape. The layered system of porous mats reaches a thermal conductivity coefficient of 0.031 W∙m⁻¹âˆ™K⁻¹ and enables to reduce the heat transfer. The results achieved using scanning thermal microscopy (SThM) correlate with the simulated heat flow in the case of individual fibers. This research study brings new insights into the energy efficiency of domestic environments, thereby addressing the growing demand for sustainable and high-performance insulation materials for saving energy loss and reducing pollution footprint.

Comparison of pesticide adsorption efficiencies of zeolites and zeolite-carbon composites and their regeneration possibilities.

The presence of pesticides in our environment is a consequence of intensive industrial and civilizational development, necessitating the search for effective and safe methods to remove them. We suggest utilizing zeolite X and a zeolite-carbon composite, obtained through the chemical transformation of fly ash, as pesticide sorbents. To increase the sorption efficiency of 2,4-dichlorophenoxyacetic acid (2,4-D), 2-methyl-4-chlorophenoxyacetic acid (MCPA), carbendazim, and simazine, we functionalized the zeolite materials with cationic (hexadecyltrimethylammonium) and nonionic (Triton X-100) surfactants. We used transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric/differential thermal analysis (TG/DTA) and point of zero charge (pHpzc) analysis to characterize the functionalized sorbent materials. Our results indicate that cationic surfactants significantly enhance the adsorption of 2,4-D and MCPA. In contrast, carbendazim and simazine exhibit maximum sorption on the unmodified zeolite-carbon composite. The sorption mechanism is intricate, with physical sorption predominating, primarily due to electrostatic interactions between the protonated binding sites of the adsorbents and the negatively charged pesticide molecules. Regeneration tests demonstrated that ethanol is the most effective in regenerating zeolite-carbon composite with adsorbed MCPA and 2,4-D, while thermal regeneration was not possible. Adsorbents with simazine and carbendazim can be regenerated using both thermal and ethanol methods, but the thermal regeneration of zeolite with adsorbed simazine is more efficient. Utilizing functionalized zeolite materials obtained from industrial waste, such as fly ash, could provide an efficient way to remove pesticides from the environment.

Magnetoresistive Properties of Nanocomposites Based on Ferrite Nanoparticles and Polythiophene.

In the presented study, we have synthesized six nanocomposites based on various magnetic nanoparticles and a conducting polymer, poly(3-hexylthiophene-2,5-diyl) (P3HT). Nanoparticles were either coated with squalene and dodecanoic acid or with P3HT. The cores of the nanoparticles were made of one of three different ferrites: nickel ferrite, cobalt ferrite, or magnetite. All synthesized nanoparticles had average diameters below 10 nm, with magnetic saturation at 300 K varying between 20 to 80 emu/g, depending on the used material. Different magnetic fillers allowed for exploring their impact on the conducting properties of the materials, and most importantly, allowed for studying the influence of the shell on the final electromagnetic properties of the nanocomposite. The conduction mechanism was well defined with the help of the variable range hopping model, and a possible mechanism of electrical conduction was proposed. Finally, the observed negative magnetoresistance of up to 5.5% at 180 K, and up to 1.6% at room temperature, was measured and discussed. Thoroughly described results show the role of the interface in the complex materials, as well as clarify room for improvement of the well-known magnetoelectric materials.

The Memristive Properties and Spike Timing-Dependent Plasticity in Electrodeposited Copper Tungstates and Molybdates.

Memristors possess non-volatile memory, adjusting their electrical resistance to the current that flows through them and allowing switching between high and low conducting states. This technology could find applications in fields such as IT, consumer electronics, computing, sensors, and medicine. In this paper, we report successful electrodeposition of thin-film materials consisting of copper tungstate and copper molybdate (CuWO4 and Cu3Mo2O9), which showed notable memristive properties. Material characterisation was performed with techniques such as XRD, XPS, and SEM. The electrodeposited materials exhibited the ability to switch between low and high resistive states during varied cyclic scans and short-term impulses. The retention time of these switched states was also explored. Using these materials, the effects seen in biological systems, specifically spike timing-dependent plasticity, were simulated, being based on analogue operation of the memristors to achieve multiple conductivity states. Bio-inspired simulations performed directly on the material could possibly offer energy and time savings for classical computations. Memristors could be crucial for the advancement of high-efficiency, low-energy neuromorphic electronic devices and technologies in the future.

Surface engineering of mixed conjugated/polyelectrolyte brushes - Tailoring interface structure and electrical properties.

HYPOTHESIS: Mixed polymer brushes (MPBs) could be synthesized by surface dilution of homopolymer brushes and subsequent grafting of other type of chains in the formed voids. Nanophase separation and dynamics of surface-grafted chains could be tailored by modification of their molecular architecture. Mixed polyelectrolyte and conjugated chains contribute synergistically to tailor properties of the coating. EXPERIMENTS: A new synthetic strategy that allowed spatially controlled grafting of poly(sodium 4-styrenesulfonate) chains (PSSNa) in close neighborhood of poly(3-methylthienyl methacrylate) (PMTM) brushes (precursors of the conjugated chains) using surface-initiated polymerizations was developed. The final mixed conjugated/polyelectrolyte brushes were prepared by template polymerization of pendant thiophene groups in PMTM chains. Surface dynamics and nanophase separation of MPBs were studied by nanoscale resolution IR imaging, SIMS profiling and AFM mapping in selective solvents. FINDINGS: Unconjugated MPBs were shown to undergo vertical, and horizontal nanophase separation, while the size and shape of the nanodomains were dependent on molar ratio of the mixed chains and their relative lengths. Generation of the conjugated chains led to diminishing of nanophase separation thanks to stronger mutual interactions of conjugated PMTM and PSSNa (macromolecular mixing). The obtained systems demonstrated tunable interfacial structure and resistance switching phenomenon desired in construction of smart surfaces or memristive devices.

Dendrite Formation on the Poly(methyl methacrylate) Surface Reactively Sputtered with a Cesium Ion Beam.

The development of topography plays an important role when low-energy projectiles are used to modify the surface or analyze the properties of various materials. It can be a feature that allows one to create complex structures on the sputtered surface. It can also be a factor that limits depth resolution in ion-based depth profiling methods. In this work, we have studied the evolution of microdendrites on poly(methyl methacrylate) sputtered with a Cs 1 keV ion beam. Detailed analysis of the topography of the sputtered surface shows a sea of pillars with islands of densely packed pillars, which eventually evolve to fully formed dendrites. The development of the dendrites depends on the Cs fluence and temperature. Analysis of the sputtered surface by physicochemical methods shows that the mechanism responsible for the formation of the observed microstructures is reactive ion sputtering. It originates from the chemical reaction between the target material and primary projectile and is combined with mass transport induced by ion sputtering. The importance of chemical reaction for the formation of the described structures is shown directly by comparing the change in the surface morphology under the same dose of a nonreactive 1 keV xenon ion beam.

Hydrogen Bubble Size Distribution on Nanostructured Ni Surfaces: Electrochemically Active Surface Area Versus Wettability.

Emerging manufacturing technologies make it possible to design the morphology of electrocatalysts on the nanoscale in order to improve their efficiency in electrolysis processes. The current work investigates the effects of electrode-attached hydrogen bubbles on the performance of electrodes depending on their surface morphology and wettability. Ni-based electrocatalysts with hydrophilic and hydrophobic nanostructures are manufactured by electrodeposition, and their surface properties are characterized. Despite a considerably larger electrochemically active surface area, electrochemical analysis reveals that the samples with more pronounced hydrophobic properties perform worse at industrially relevant current densities. High-speed imaging shows significantly larger bubble detachment radii with higher hydrophobicity, meaning that the electrode surface area that is blocked by gas is larger than the area gained by nanostructuring. Furthermore, a slight tendency toward bubble size reduction of 7.5% with an increase in the current density is observed in 1 M KOH.

Mimicking natural electrical environment with cellulose acetate scaffolds enhances collagen formation of osteoblasts.

The medical field is continuously seeking new solutions and materials, where cellulose materials due to their high biocompatibility have great potential. Here we investigate the applicability of cellulose acetate (CA) electrospun fibers for bone tissue regeneration. For the first time we show the piezoelectric properties of electrospun CA fibers via high voltage switching spectroscopy piezoresponse force microscopy (HVSS-PFM) tests, which are followed by surface potential studies using Kelvin probe force microscopy (KPFM) and zeta potential measurements. Piezoelectric coefficient for CA fibers of 6.68 ± 1.70 pmV-1 along with high surface (718 mV) and zeta (-12.2 mV) potentials allowed us to mimic natural electrical environment favoring bone cell attachment and growth. Importantly, the synergy between increased surface potential and highly developed structure of the fibrous scaffold led to the formation of a vast 3D network of collagen produced by osteoblasts only after 7 days of in vitro culture. We clearly show the advantages of CA scaffolds as a bone replacement material, when long-lasting structural support is needed.

Catalytic reductions of nitroaromatic compounds over heterogeneous catalysts with rhenium sub-nanostructures.

Nitroaromatic compounds (NACs) are key contaminants of anthropogenic origin and pose a severe threat to human and animal lives. Although the catalytic activities of Re nanostructures (NSs) are significantly higher than those of other heterogeneous catalysts containing NSs, few studies have been reported on the application of Re-based nanocatalysts for NAC hydrogenation. Accordingly, herein, catalytic reductions of nitrobenzene (NB), 4-nitrophenol (4-NP), 2-nitroaniline (2-NA), 4-nitroaniline (4-NA), and 2,4,6-trinitrophenol (2,4,6-TNP) over new Re-based heterogeneous catalysts were proposed. The catalytic materials were designed to enable effective syntheses and stabilisation of particularly small Re structures over them. Accordingly, catalytic hydrogenations of NACs under mild conditions were significantly enhanced by Re sub-nanostructures (Re-sub-NSs). The highest pseudo-first-order rate constants for NB, 4-NP, 2-NA, 4-NA, and 2,4,6-TNP reductions over the catalyst acquired by stabilising Re using bis(3-aminopropyl)amine (BAPA), which led to Re-sub-NSs with Re concentrations of 16.7 wt%, were 0.210, 0.130, 0.100, 0.180, and 0.090 min-1, respectively.