Chromium is a non-essential and well-known toxic metal for microorganisms and plants. The widespread industrial use of this heavy metal has caused it to be considered as a serious environmental pollutant. Chromium exists in nature as two main species, the trivalent form, Cr(III), which is relatively innocuous, and the hexavalent form, Cr(VI), considered a more toxic species. At the intracellular level, however, Cr(III) seems to be responsible for most toxic effects of chromium. Cr(VI) is usually present as the oxyanion chromate. Inhibition of sulfate membrane transport and oxidative damage to biomolecules are associated with the toxic effects of chromate in bacteria. Several bacterial mechanisms of resistance to chromate have been reported. The best characterized mechanisms comprise efflux of chromate ions from the cell cytoplasm and reduction of Cr(VI) to Cr(III). Chromate efflux by the ChrA transporter has been established in Pseudomonas aeruginosa and Cupriavidus metallidurans (formerly Alcaligenes eutrophus) and consists of an energy-dependent process driven by the membrane potential. The CHR protein family, which includes putative ChrA orthologs, currently contains about 135 sequences from all three domains of life. Chromate reduction is carried out by chromate reductases from diverse bacterial species generating Cr(III) that may be detoxified by other mechanisms. Most characterized enzymes belong to the widespread NAD(P)H-dependent flavoprotein family of reductases. Several examples of bacterial systems protecting from the oxidative stress caused by chromate have been described. Other mechanisms of bacterial resistance to chromate involve the expression of components of the machinery for repair of DNA damage, and systems related to the homeostasis of iron and sulfur.
Flexible nanoporous chromium or iron terephtalates (BDC) MIL-53(Cr, Fe) or M(OH)[BDC] have been used as matrices for the adsorption and in vitro drug delivery of Ibuprofen (or α-p-isobutylphenylpropionic acid). Both MIL-53(Cr) and MIL-53(Fe) solids adsorb around 20 wt % of Ibuprofen (Ibuprofen/dehydrated MIL-53 molar ratio = 0.22(1)), indicating that the amount of inserted drug does not depend on the metal (Cr, Fe) constitutive of the hybrid framework. Structural and spectroscopic characterizations are provided for the solid filled with Ibuprofen. In each case, the very slow and complete delivery of Ibuprofen was achieved under physiological conditions after 3 weeks with a predictable zero-order kinetics, which highlights the unique properties of flexible hybrid solids for adapting their pore opening to optimize the drug-matrix interactions.
A series of polyethyleneimine (PEI) incorporated MIL-101 adsorbents with different PEI loadings were reported for the first time in the present work. Although the surface area and pore volume of MIL-101 decreased significantly after loading PEI, all the resulting composites exhibited dramatically enhanced CO2 adsorption capacity at low pressures. At 100 wt% PEI loading, the CO2 adsorption capacity at 0.15 bar reached a very competitive value of 4.2 mmol g(-1) at 25 degrees C, and 3.4 mmol g(-1) at 50 degrees C. More importantly, the resulting adsorbents displayed rapid adsorption kinetics and ultrahigh selectivity for CO2 over N-2 in the designed flue gas with 0.15 bar CO2 and 0.75 bar N-2. The CO2 over N-2 selectivity was up to 770 at 25 degrees C, and 1200 at 50 degrees C. We believe that the PEI based metal-organic frameworks is an attractive adsorbent for CO2 capture.
Naturally occurring Cr(VI) has recently been reported in ground and surface waters. Rock strata rich in Cr(III)-bearing minerals, in particular chromite, are universally found in these areas that occur near convergent plate margins. Here we report experiments demonstrating accelerated dissolution of chromite and subsequent oxidation of Cr(III) to aqueous Cr(VI) in the presence of birnessite, a common manganese mineral, explaining the generation of Cr(VI) by a Cr(III)-bearing mineral considered geochemically inert. Our results demonstrate that Cr(III) within ultramafic- and serpentinitederived soils/sediments can be oxidized and dissolved through natural processes, leading to hazardous levels of aqueous Cr(VI) in surface and groundwater.
By synchrotron X-ray absorption spectroscopy, chemical structures of hexavalent chromium (Cr(VI))/trivalent chromium (Cr(III)) adsorbed on humic acid (HA)-zeolite Y and extracted in an ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4])) have been studied. By combining the competitive adsorption results and reduction of Cr(VI)-HA with the carboxyl groups of HA, Cr(III)-HA (58%) was shown to be the major compound in HA-zeolite Y using synchrotron X-ray absorption near-edge structure (XANES) spectroscopy. In an ionic liquid phase, the reduction of Cr(VI)-HA to Cr(III)-HA and the desorption of Cr(III) from HA were caused by [C4mim][BF4]. The 9F nuclear magnetic resonance (NMR) spectra show that the perturbation of the [C4mim][BF4] anion was affected by the extractable chromium species. The formation of a Cr(III) ion affected the increase in the bond distance for the 1st shell CrO of the chromium species in [C4mim][BF4] using extended X-ray absorption fine structure (EXAFS) spectroscopy. The changes in the non-extractable chromium species remaining in HA-zeolite Y were also caused by [C4mim][BF4] during extraction. The desorption of the absorbed Cr(III) on HA and zeolite Y was observed to form Cr(III) ions. As the percentage of Cr(III) ions remaining in HA-zeolite Y increased, a slightly greater bond distance for CrO was found at 2.01 Å. The enhanced reduction of Cr(VI)-HA and desorption of Cr(III) adsorbed on the HA and zeolite Y to form Cr(III) ions were affected by [C4mim][BF4]. Increased mobility of Cr(III) in the simulated soil can promote the migration of Cr(III) ions into the H2O during soil washing for remediation. [Display omitted] •The reduction and desorption of Cr compounds in an ionic liquid (IL) increased the mobility of Cr(III) in simulated soil for remediation.•Interaction between IL anions and Cr compounds occurred in IL.•The remediation of contaminated soils is revealed in molecular-scale understandings.
A sweet conversion! A NHC–Cr/ionic liquid system has achieved excellent efficiency and the highest 5‐hydroxymethylfurfural (1; see scheme; NHC=N‐heterocyclic carbene) yields reported thus far for both fructose and glucose feedstocks. The catalyst and ionic liquid are tolerant of high substrate loading and can be recycled after extraction of the product.
Display omitted] ► New SPE method for Cr(III) separation/preconcentration was described. ► Silica gel modified with Schiff base was used as adsorbent. ► Conditions for quantitative preconcentration, elution and GFAAS determination were studied. ► The method can be applied to the highly saline samples. ► This method is a simple, effective, accurate and reproducible. N,N′-bis-(α-methylsalicylidene)-2,2-dimethyl-1,3-propanediimine (SBTD) modified silica gel was prepared and used as sorbent for solid phase extraction of Cr(III) ions from aqueous solution. This sorbent showed a high sorption affinity for Cr(III) while recovery of Cr(VI) was very low. The analyte ion retained on the column was eluted with 1 mol L −1 HNO 3. The chromium ion in the eluent was determined by graphite furnace atomic absorption spectrometry. The effects of different parameters such as pH, eluent type and volume, Schiff's base concentration, sample and eluent flow rate, interfering ions and adsorbent amount were investigated.
Using Lorenz microscopy and small-angle electron diffraction, we directly present that the chiral magnetic soliton lattice (CSL) continuously evolves from a chiral helimagnetic structure in small magnetic fields in Cr1/3NbS2. An incommensurate CSL undergoes a phase transition to a commensurate ferromagnetic state at the critical field strength. The period of a CSL, which exerts an effective potential for itinerant spins, is tuned by simply changing the field strength. Chiral magnetic orders observed do not exhibit any structural dislocation, indicating their high stability and robustness in Cr1/3NbS2.
A combined experimental and computational study of the ionic-liquid-mediated dehydration of glucose and fructose by CrII and CrIII chlorides has been performed. The ability of chromium to selectively dehydrate glucose to 5-hydroxymethylfurfural (HMF) in the ionic liquid 1-ethyl-3-methyl imidazolium chloride does not depend on the oxidation state of chromium. Nevertheless, CrIII exhibits higher activity and selectivity to HMF than CrII. Anhydrous CrCl2 and CrCl36¿H2O readily catalyze glucose dehydration with HMF yields of 60 and 72¿%, respectively, after 3 h. Anhydrous CrCl3 has a lower activity, because it only slowly dissolves in the reaction mixture. The transformation of glucose to HMF involves the formation of fructose as an intermediate. The exceptional catalytic performance of the chromium catalysts is explained by their unique ability to catalyze glucose to fructose isomerization and fructose to HMF dehydration with high selectivity. Side reactions leading to humins by means of condensation reactions take predominantly place during fructose dehydration. The higher HMF selectivity for CrIII is tentatively explained by the higher activity in fructose dehydration compared to CrII. This limits the concentration of intermediates that are involved in bimolecular condensation reactions. Model DFT calculations indicate a substantially lower activation barrier for glucose isomerization by CrIII compared to CrII. Qualitatively, glucose isomerization follows a similar mechanism for CrII and CrIII. The mechanism involves ring opening of D-glucopyranose coordinated to a single Cr ion, followed by a transient self-organization of catalytic chromium complexes that promotes the rate-determining hydrogen-shift step.