Four‐Membered Heterometallacyclic d0 and d1 Complexes of Group 4 Metallocenes with Amidato Ligands

A study of the coordination chemistry of different amidato ligands [(R)N?C(Ph)O] (R=Ph, 2,6‐diisopropylphenyl (Dipp)) at Group 4 metallocenes is presented. The heterometallacyclic complexes [Cp₂M(Cl){κ²‐N,O‐(R)N?C(Ph)O}] M=Zr, R=Dipp ( 1 a ), Ph ( 1 b ); M=Hf, R=Ph ( 2 )) were synthesized by reaction of [Cp₂MCl₂] with the corresponding deprotonated amides. Complex 1 a was also prepared by direct deprotonation of the amide with Schwartz reagent [Cp₂Zr(H)Cl]. Salt metathesis reaction of [Cp₂Zr(H)Cl] with deprotonated amide [(Dipp)N?C(Ph)O] gave the zirconocene hydrido complex [Cp₂M(H){κ²‐N,O‐(Dipp)N?C(Ph)O}] ( 3 ). Reaction of 1 a with Mg did not result in the desired Zr(III) complex but in formation of Mg complex [(py)₃Mg(Cl) {κ²‐N,O‐(Dipp)N?C(Ph)O}] ( 4 ; py=pyridine). The paramagnetic complexes [Cp′₂Ti{κ²‐N,O‐(R)N?C(Ph)O}] (Cp′=Cp, R=Ph ( 7 a ); Cp′=Cp, R=Dipp ( 7 b ); Cp′=Cp*, R=Ph ( 8 )) were prepared by the reaction of the known titanocene alkyne complexes [Cp₂′Ti(η²‐Me₃SiC₂SiMe₃)] (Cp′=Cp ( 5 ), Cp′=Cp* ( 6 )) with the corresponding amides. Complexes 1 a , 2 , 3 , 4 , 7 a , 7 b , and 8 were characterized by X‐ray crystallography. The structure and bonding of complexes 7 a and 8 were also characterized by EPR spectroscopy.     

Highly Crystallized Nanometer‐Sized Zeolite A with Large Cs Adsorption Capability for the Decontamination of Water

Nanometer‐sized zeolite A with a large cesium (Cs) uptake capability is prepared through a simple post‐milling recrystallization method. This method is suitable for producing nanometer‐sized zeolite in large scale, as additional organic compounds are not needed to control zeolite nucleation and crystal growth. Herein, we perform a quartz crystal microbalance (QCM) study to evaluate the uptake ability of Cs ions by zeolite, to the best of our knowledge, for the first time. In comparison to micrometer‐sized zeolite A, nanometer‐sized zeolite A can rapidly accommodate a larger amount of Cs ions into the zeolite crystal structure, owing to its high external surface area. Nanometer‐sized zeolite is a promising candidate for the removal of radioactive Cs ions from polluted water. Our QCM study on Cs adsorption uptake behavior provides the information of adsorption kinetics (e.g., adsorption amounts and rates). This technique is applicable to other zeolites, which will be highly valuable for further consideration of radioactive Cs removal in the future.     

Nanocomposite of Platinum Particles Embedded into Nanosheets of Polycarbazole for Methanol Oxidation

Nanoparticles of Pt were successfully electrodeposited onto polycarbazole (PCz) film on a stainless steel (SS‐PCz‐Pt) by chronocoulometry (0.2 C). For comparative purposes, Pt particles were deposited into stainless steel (SS‐Pt) under the same condition. Fourier transform infrared spectroscopy (FT‐IR) results confirmed PCz exists in the SS‐PCz‐Pt composite electrode. X‐ray photoelectron spectroscopy (XPS) results indicated that PCz of SS‐PCz can interact easily with Pt particles. The crystalline behavior and morphology of SS‐PCz‐Pt and SS‐Pt were determined by X‐ray diffraction (XRD) analysis, scanning electron microscopy (SEM), and Transmission Electron Microscopy (TEM). The TEM results indicated that Pt particles disperse more uniformly into the nanosheets of polycarbazole than those of SS film. Catalytic activity and stability for the oxidation of methanol were studied by using cyclic voltammetry and chronoamperometry. A high catalytic current for methanol oxidation (8.04 mA cm^?2 mg^?1) was found for the SS‐PCz‐Pt electrode in comparison to SS‐Pt electrode (5.01 mA cm^?2 mg^?1) at about 0.6 V (vs. Ag/AgCl).     

Synthesis of polyhydroxyalkanoate (PHA) from excess activated sludge under various oxidation-reduction potentials (ORP) by using acetate and propionate as carbon sources

Accumulation of poly hydroxyalkanoate (PHA) from excess activated sludge (EAS) was monitored and controlled via the oxidation-reduction potential (ORP) adjusting process. The ORP was adjusted and controlled by only regulating the gas-flow rate pumped into the cultural broth in which sodium acetate (C2) and propionate (C3) were used as carbon sources. Productivity of PHA and the PHA compositions at various C2 to C3 ratios were also investigated. When ORP was maintained at +30 mV, 35% (w/w) of PHA of cell dry weight obtained when C2 was used as sole carbon source. The PHA copolymer, poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), accumulated by EAS with different 3-hydroxyvalarate (3HV) molar fractions ranged from 8% to 78.0% when C2 and C3 was used as sole carbon source, By using ORP to monitor and control the fermentation process instead DO meter, the ORP system provided more precise control to the PHA accumulation process from EAS under low dissolved oxygen (DO) concentrations. Adjusting the C2 to C3 ratios in the media could control the composition such as the 3HV/3HB ratios of the PHBV. Furthermore, it might be an effective way to adjust the 3HV molar fractions in PHBV by controlling the DO concentration via the ORP monitoring system. The 3HV molar fractions in the PHBV declined with increasing ORP from −30 mV to +100 mV by adjusting the gas-flow rate (i.e. the DO concentration). It is concluded that the DO plays a very important role in the synthesis of 3HV subunits in PHBV co-polymer from the EAS. Therefore, a hypothetic metabolic model for PHA synthesis from EAS was proposed to try to explain the results in this study.     

SURFACE REARRANGEMENTS OF OXYGEN PLASMA TREATED POLYSTYRENE： SURFACE DYNAMICS AND HUMIDITY EFFECT

The time evolution of oxygen plasma treated polystyrene(PS)surfaces was investigated upon storing them in theair under controlled humidity conditions.The methods of water contact angle,X-ray photoelectron spectroscopy(XPS),sumfrequency generation(SFG)vibrational spectroscopy,and atomic force microscopy(AFM)were used to infer the surfaceproperties and structure.Chemical groups containing oxygen were formed on the PS surface with the plasma treatment,demonstrated by water contact angle and XPS.The surface polarity decayed markedly on time,as assessed by steady increasein the water contact angle as a function of storage time,from zero to around 60°.The observed decay is interpreted as arisingfrom surface rearrangement processes to burying polar groups away from the uppermost layer of the surfaces,which is incontact with air.On the other hand,XPS results show that the chemical composition in the first 3 nm surface layer isunaffected by the surface aging,and the depth profile of oxygen is essentially the same with time.A possible change of PSsurface roughness was examined by AFM,and it showed that the increase of water contact angle during surface aging couldnot be attributed to surface roughness.Thus,it is concluded that surface aging is attributable to surface reorganization andthe motion of oxygen containing groups is confined within the XPS probing depth.SFG spectroscopy,which is intrinsicallyinterface-specific,was used to detect the chemical structure of PS surface at the molecular level after various aging times.The results are interpreted as follows.During the aging of the plasma treated PS surfaces,the oxygen containing groupsundergo reorientation processes toward the polymer bulk and/or parallel to the surface,while the CH_2 moiety stands up onthe PS surface.Our results indicate that the surface configuration changes do not require large length scale segmentalmotions or migration of macromolecules.Motions that are responsible for surface configuration changes could be relativelysmall rotational motions.The aging behaviors under different relative humidity conditions were shown to be similar from18% to 91%,whereas the kinetics of surface polarity decays were faster in higher relative humidity.Here,the surfacerearrangement of polystyrene films that were previously treated by oxygen plasma and aged,and was investigated in terms ofcontact angle after the water immersion.The contact angles of the water-immersed samples were found to change andapproach the initial values before the immersion asymptotically.     

Effect of PANI–AC Composite on Electrochemical Synthesis of Hydrogen Peroxide by Alkaline H2–O2 Fuel Cell Reactor

Russian Journal of Electrochemistry - Effect of polyaniline on the oxygen reduction reaction during the electrochemical synthesis of H2O2 by an alkaline H2–O2 fuel cell reactor was...     

A Lyapunov-type condition for robust feedback stability of delay control systems

^** Email: spyung{at}hku.hk In this paper, we show that a delay control system can be robustlystabilized by certain closed-loop feedback if a Lyapunov-typecondition is fulfilled.     

Receptor-mediated endocytosis modeling of antibody-drug conjugates to the released payload within the intracellular space considering target antigen expression levels

An antibody-drug conjugate (ADC) is one of the effective treatment modalities designed as a targeted therapy for treating tumors. Certain ADCs such as brentuximab vedotin are known to kill negative tumor cells indirectly via membrane permeability and bystander-killing effect and to kill positive tumor cells directly. In this study, we propose a mathematical model to describe the ADC-receptor endocytosis mechanism and to predict payloads over a time profile more accurately, while considering target antigen-positive (Ag+)/negative (Ag--) cells. We discuss how the target-antigen expression levels derived using a ratio of Ag+ to Ag-- cells determine the payload release in the intracellular space. The model is aimed at capturing the amount of the payloads based on the target expression levels with the total number of cells fixed. The results indicate that (i) the profile of the total payloads over a time within the intracellular space is less influenced by the target expression levels after a time period, but the slope at the growth phase in which the payload increases is determined by the target expression levels, (ii) the change in the area under the curve of the total intracellularly released payload with a change in the ratio of Ag+ to Ag-- cells is more significant due to the initial ADC injection, (iii) the fluctuations in the released payloads within the Ag+ cells increase as the target expression levels decrease, unlike in the case of Ag-- cells or extracellular space. In addition, the time $t_{max}$ that corresponds to the maximum payload concentration $C_{max}$ is shifted towards the right as the target-antigen levels decrease, and it is strengthened by an increase in the initial free ADCs. The proposed model may reduce the discrepancy between the experiment and the model in the prediction of payloads over time profile.     

The reducible Specht modules for the Hecke algebra \mathcal{H}_{\mathbb{C},{-}1}(\mathfrak{S}_{n})

The reducible Specht modules for the Hecke algebra $\mathcal {H}_{\mathbb{F},q}(\mathfrak{S}_{n})$ have been classified except when q=?1. We prove one half of a conjecture which we believe classifies the reducible Specht modules when q=?1.     

Equivalent conditions for the general Stone-Weierstrass problem

We generalize the setting of the Stone-Weierstrass problem to the cone CP(A, H) of all completely positive linear maps of a C^*-algebra A into the C^*-algebra B(H) of all bounded linear operators on a Hilbert space H, and give some equivalent conditions for the problem. As a consequence, a new generalized spectrum, containing pure states and irreducible representations, will be introduced.