Selective removal of chromium (VI) from sulphates and other metal anions using an ion-imprinted polymer

A linear copolymer was prepared from 4-vinylpyridine and styrene. An ion-imprinted polymer (IIP) specific for Cr (VI) adsorption was prepared by copolymerisation of the quaternised linear copolymer (quaternised with 1,4-chlorobutane), 2-vinylpyridine functional monomer and ethylene glycol dimethacrylate (EGDMA), as the cross-linking monomer, in the presence of 1,1’-azobis(cyclohexanecarbonitrile) as initiator. Ammonium dichromate and aqueous methanol were used as a template and porogenic solvent, respectively. Leaching of the chromate template from the polymer particles was achieved with successive stirring of the ion-imprinted polymer (IIP) particles in 4 M HNO3 solutions to obtain leached materials, which were then used for selective rebinding of Cr (VI) ions from aqueous solutions. Similarly, the non-imprinted polymer/ control polymer (NIP/CP) material was also prepared under exactly the same conditions as the IIP but without the chromate anion template. Various parameters, such as solution pH, initial concentration, aqueous phase volume, sorbent dosage, contact time and leaching solution volumes, were investigated. Scanning electron microscopy (SEM), Fourier Transform Infrared (FTIR) spectroscopy, BET surface area and pore size analysis were used for the characterisation of IIP (both unleached and leached) and CP materials. Optimal parameters were as follows: solution pH, 3; contact time, 120 min; eluent, 20 mℓ of 0.1 M NaOH; and sorbent amount, 125 mg. Maximum retention capacity of IIP and CP was 37.58 and 25.44 mg∙g-1, respectively. The extraction efficiencies of the IIP and CP were compared using a batch and SPE mode of extraction. In the absence of high concentrations of ions, especially sulphate ions, both CP and IIP demonstrated no differences in binding of Cr (VI), which was almost 100%. However, in the presence of high concentrations of sulphate ions, the selectivity on the CP completely collapsed. The study clearly demonstrates the suitably of the developed IIP for selective extraction of Cr (VI) in complex samples such as those from acid mine drainage. The selectivity was also compared by direct injection of the real-world sample, both spiked and non-spiked, into that obtained after IIP selective extraction. Despite the method’s very low detection limits for direct injection (below 1 μg∙ℓ-1), no Cr (VI) was obtained. However, after IIP selective extraction, spiked Cr (VI) was detected in the spiked sample

Neue Aspekte in der Chemie von Übergangsmetallpolysulfidkomplexen: Synthese und Kristallstrukturen von Cp′3Nb3S12 und Cp′3Nb3S10O (Cp′ = t-BuC5H4)

Thermolysis of a mixture of Cp′4Nb2Sn (Cp′ = t-BuC5H4; n = 8, 9) results in the formation of the new niobium polysulfide complexes: Cp′3Nb3S12 (2), Cp′3Nb3S10O (3), Cp′3Nb3S10O (4) and Cp′4Nb4S13 (5). The structures of 2 and 3 have been established by X-ray diffraction studies. The complexes are characterized by an unusual variety of different sulfur ligands (up to five in 2), which is responsible for the absence of any metal-metal interaction

Processing and Characterization of Activated Carbon from Coconut Shell and Palm Kernel Shell Waste by H3PO4 Activation

Palm kernel shell and coconut shell are used as a precursor for the production of activated carbon, a way of mitigating the tons of waste produced in Ghana. The raw Palm kernel shell and coconut shell were activated chemically using H3PO4. A maximum activated carbon yield of 26.3 g was obtained for Palm kernel shell and 22.9 g for coconut shell at 400oC, an impregnation ratio of 1.2 and 1-hour carbonization time. Scanning electron microscopy reveals well-developed cavities of the H3PO4 activated coconut shell and Palm kernel shell compared to the non-activated carbon. Iodine number of 743.02 mg/g and 682.11 mg/g, a porosity of 0.31 and 0.49 and the electrical conductivity of 2010 μS/cm and 778 μS /cm were obtained for the AC prepared from the coconut shell and Palm kernel shell respectively. The results of this work show that high-quality activated carbon can be manufactured locally from coconut shell and Palm kernel shell waste, and a scale-up of this production will go a long way to reduce the tons of coconut shell and Palm kernel shell waste generated in the country

ICON 9-an international phase III randomized study to evaluate the efficacy of maintenance therapy with olaparib and cediranib or olaparib alone in patients with relapsed platinum-sensitive ovarian cancer following a response to platinum-based chemotherapy

BACKGROUND: Two novel biological agents-cediranib targeting angiogenesis, and olaparib targeting DNA repair processes-have individually led to an improvement in ovarian cancer control. The aim of ICON9 is to investigate the combination of cediranib and olaparib maintenance in recurrent ovarian cancer following platinum-based therapy. PRIMARY OBJECTIVE: To assess the efficacy of maintenance treatment with olaparib in combination with cediranib compared with olaparib alone following a response to platinum-based chemotherapy in women with platinum-sensitive ovarian, fallopian tube or peritoneal cancer during first relapse. STUDY HYPOTHESIS: Maintenance therapy with cediranib and olaparib in combination is associated with improved patient outcomes compared with olaparib alone. TRIAL DESIGN: International phase III randomized controlled trial. Following a response to platinum-based chemotherapy patients are randomized 1:1 to either oral olaparib and cediranib (intervention arm) or oral olaparib alone (control arm). MAJOR INCLUSION CRITERIA: Patients with a known diagnosis of high grade serous or endometrioid carcinoma of the ovary, fallopian tube or peritoneum, progressing more than 6 months after first-line platinum-based chemotherapy, who have responded to second-line platinum-based chemotherapy. PRIMARY ENDPOINTS: Progression-free and overall survival. Co-primary endpoints to be assessed using a fixed-sequence gatekeeping approach: (1) progression-free survival, all patients; (2) progression-free survival, BRCA wild type; (3) overall survival, all patients; (4) overall survival, BRCA wild type. SAMPLE SIZE: 618 patients will be recruited. ESTIMATED DATES FOR COMPLETING ACCRUAL AND PRESENTING RESULTS: Accrual is expected to be completed in 2024 with presentation of results in 2025. TRIAL REGISTRATION: ClinicalTrials.gov: NCT03278717

(Ferrocenylpyrazolyl) zinc (II) benzoates as catalysts for the ring opening polymerization of ε-caprolactone

The reaction of Zn(OAc)2 and C6H5COOH or 3,5-NO2-C6H3COOH with 3-ferrocenylpyrazolyl-methylenepyridine (L1), 3-ferrocenyl-5-methylpyrazolyl-methylenepyridine (L2), 3-ferrocenylpyrazolyl-ethylamine (L3) and 3-ferrocenyl-5-pyrazolyl-ethylamine (L4) afford the corresponding complexes [Zn(C6H5COO)2(L1)] (1), [Zn(C6H5COO)2(L2)] (2), [Zn(3,5-NO2-C6H3COO)2(L1)] (3), [Zn(3,5-NO2-C6H3 COO)2(L2)] (4), [Zn(C6H5COO)2(L3)] (5), [Zn(C6H5COO)2(L4)] (6), [Zn(3,5-NO2-C6H3COO)2(L3)] (7) and [Zn(3,5-NO2-C6H3COO)2(L4)] (8). These complexes behave as catalysts for the ring opening polymerization of e-caprolactone to produce polymers with molecular weight that range from 1480 to 7080 g mol1 and exhibited moderate to broad PDIs. Evidence of these complexes acting as catalysts was obtained from both the polymerization data and kinetic studies. The polymerization data show that variation of the [CL]/[C] from 100 to 800 produced PCL with relatively the same molecular weight indicative of a catalyst behavior. The appearance of induction period in kinetic plots strengthens the fact that these complexes are catalysts rather than initiators. MALDI-TOF MS and 1 H NMR data show di-hydroxy end groups, which support the coordination mechanism rather than insertion mechanism. To understand the broad PDIs obtained for some of the polymer, the electronic properties of the zinc complexes were investigated using cyclic voltammetry. The results show that the zinc complexes containing amine based ligands are highly electrophilic therefore making them unstable, hence the broad PDIs observed for zinc complexes containing amine based ligands. Among the eight complexes investigated, complex 7 is the most active catalyst with kp value of 1.18 107 h1 mol1 at 110 C

Interpenetrated Magnesium–Tricalcium Phosphate Composite: Manufacture, Characterization and In Vitro Degradation Test

Magnesium and calcium phosphates composites are promising biomaterials to create biodegradable load-bearing implants for bone regeneration. The present investigation is focused on the design of an interpenetrated magnesium–tricalcium phosphate (Mg–TCP) composite and its evaluation under immersion test. In the study, TCP porous preforms were fabricated by robocasting to have a prefect control of porosity and pore size and later infiltrated with pure commercial Mg through current-assisted metal infiltration (CAMI) technique. The microstructure, composition, distribution of phases and degradation of the composite under physiological simulated conditions were analysed by scanning electron microscopy, elemental chemical analysis and X-ray diffraction. The results revealed that robocast TCP preforms were full infiltrated by magnesium through CAMI, even small pores below 2 lm have been filled with Mg, giving to the composite a good interpenetration. The degradation rate of the Mg–TCP composite displays lower value compared to the one of pure Mg during the first 24 h of immersion test.Magnesium and calcium phosphates composites are promising biomaterials to create biodegradable load-bearing implants for bone regeneration. The present investigation is focused on the design of an interpenetrated magnesium–tricalcium phosphate (Mg–TCP) composite and its evaluation under immersion test. In the study, TCP porous preforms were fabricated by robocasting to have a prefect control of porosity and pore size and later infiltrated with pure commercial Mg through current-assisted metal infiltration (CAMI) technique. The microstructure, composition, distribution of phases and degradation of the composite under physiological simulated conditions were analysed by scanning electron microscopy, elemental chemical analysis and X-ray diffraction. The results revealed that robocast TCP preforms were full infiltrated by magnesium through CAMI, even small pores below 2 lm have been filled with Mg, giving to the composite a good interpenetration. The degradation rate of the Mg–TCP composite displays lower value compared to the one of pure Mg during the first 24 h of immersion test

Pyrazole Supported Zinc(II) Benzoates as Catalysts for the Ring Opening Copolymerization of Cyclohexene Oxide and Carbon Dioxide

The bis(pyrazole)zinc(II) benzoate complexes bis(3,5-diphenylpyrazole)zinc(II) benzoate (1), bis(3,5-diphenylpyrazole)zinc(II) 3,5-dinitrobenzoate (2), bis(3,5-diphenylpyrazole)zinc(II) 4-hydroxybenzoate (3), and bis(3,5-di-tert-butylpyrazole)zinc(II) 2-chlorobenzoate (4) were synthesized from the reaction of 3,5-diphenylpyrazole (L1) or 3,5-di-tert-butylpyrazole (L2), zinc(II) acetate and the appropriate benzene carboxylic acid. The molecular structure of complex 2 confirmed that these zinc(II) benzoate complexes adopt a 4-coordinate tetrahedral geometry. All four complexes were screened as catalysts for the copolymerization of carbon dioxide (CO2) and cyclohexene oxide (CHO) and were found to be active for the formation of poly(cyclohexene carbonate) (PCHC) at CO2 pressures as low as 1.0 MPa under solvent-free conditions and without the use of a co-catalyst. At some reaction condition, most of the catalysts produced PCHC with high carbonate content of up to 98% and a good amount of cyclic cyclohexene carbonate (CCHC). The copolymers produced have low to moderate molecular weights (5200–12300 g/mol) and with polydispersity indices that vary from 1.19 to 2.50. Matrix Assisted Laser Desorption/Ionization-Time of Flight Mass Spectra (MALDI-TOF MS) of these copolymers showed they have benzoate and hydroxyl end groups

Addressing the challenge of interpreting microclimatic weather data collected from urban sites

This paper presents some installation and data analysis issues from an ongoing urban air temperature and humidity measurement campaign in Hangzhou and Ningbo, China. The location of the measurement sites, the positioning of the sensors and the harsh conditions in an urban environment can result in missing values and observations that are unre-presentative of the local urban microclimate. Missing data and erroneous values in micro-scale weather time series can produce bias in the data analysis, false correlations and wrong conclusions when deriving the specific local weather patterns. A methodology is presented for the identification of values that could be false and for determining whether these are “noise”. Seven statistical methods were evaluated in their performance for replacing missing and erroneous values in urban weather time series. The two methods that proposed replacement with the mean values from sensors in locations with a Sky View Factor similar to that of the target sensor and the sensors closest to the target’s location per-formed well for all Day-Night and Cold-Warm days scenarios. However, during night time in warm weather the re-placement with the mean values for air temperature of the nearest locations outperformed all other methods. The results give some initial evidence of the distinctive urban microclimate development in time and space under different regional weather forcings