Aerobic biodegradability of hydroxypropyl-β-cyclodextrins in soil

Hydroxylpropyl-β-cyclodextrins (HP-β-CDs), hydroxyalkyl derivatives of β-CD, used in a broad range of applications in food, pharmaceutical, agriculture and bioremediation of soil because of their specific chemical properties. The possibility of varying the biodegradation rate of HP-β-CDs by changing the DS and substitution pattern makes HP-β-CDs suitable for various applications. Therefore, their biodegradation fate has been of great concern. In this study, the biodegradation of various HP-β -CDs, which have different degrees and patterns of substitution in different soil ecosystems, was investigated. The degree and pattern of substitution of HP-β-CDs were determined by the reductive-cleavage method and methylation analysis. Two common soils and a contaminated soil were used in the biodegradation test. All CDs were found to be more or less biodegradable. Increasing the degree of substitution (DS) had negative effect on the biodegradation rate of HP-β-CDs. The substitution pattern affected the biodegradation, too. The biodegradation rates of CDs in the contaminated soil were higher than that obtained in the uncontaminated soils. The contamination removing ability of CDs was highly affected by their own biodegradation fate in soil.     

Environmental aspects of PAH biodegradation

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants, some of which are on the US Environmental Protection Agency priority pollutant list. Consequently, timely clean-up of contaminated sites is important. The lower-mol-wt PAHs are amenable to bioremediation; however, higher-mol-wt PAHs seem to be recalcitrant to microbial degradation. The rates of biodegradation of PAHs are highly variable and are dependent not only on PAH structure, but also on the physicochemical parameters of the site as well as the number and types of microorganisms present. PAHs sorb to organic matter in soils and sediments, and the rate of their desorption strongly influences the rate at which microorganisms can degrade the pollutants. Much of the current PAH research focuses on techniques to enhance the bioavailability and, therefore, the degradation rates of PAHs at polluted sites. Degradation products of PAHs are, however, not necessarily less toxic than the parent compounds. Therefore, toxicity assays need to be incorporated into the procedures used to monitor the effectiveness of PAH bioremediation. In addition, this article highlights areas of PAH research that require further investigation.     

Enhanced effect of RM-β-cyclodextrin on biodegradation of toluene in wastewater by activated sludge

Recently, air and ground water pollution and contamination of soil by toluene have been drawing increasing attention and became an urgently important problem in environmental pollution. Hence, the development of highly sophisticated removal techniques of toluene is required for the global environmental preservation. Since toluene is a highly volatile material, it is difficult to treat it by usual activated sludge water treatment. In this study, in order to prevent volatilization of toluene, randomly methylated β-cyclodextrin (RM-β-CD) was used to complex with toluene and by reason of that, facilitates the biodegradation of toluene by activated sludge. The enhanced effect of RM-β-CD for the biodegradation of toluene by activated sludge was studied in batch systems. The addition of RM-β-CD dominantly promoted proliferation of activated sludge. This implied that the addition of RM-β-CD prevented toluene from evaporating during treatment, and as a result, toluene was effectively decomposed by the activated sludge.     

Biodegradation of Crude Oil from the BP Oil Spill in the Marsh Sediments of Southeast Louisiana, USA

The significant challenges presented by the April 20, 2010 explosion, sinking, and subsequent oil spill of the Deepwater Horizon drilling platform in Canyon Block 252 about 52 miles southeast of Venice, LA, USA greatly impacted Louisiana??s coastal ecosystem including the sea food industry, recreational fishing, and tourism. The short-term and long-term impact of this oil spill are significant, and the Deepwater Horizon spill is potentially both an economic and an ecological disaster. Microbes present in the water column and sediments have the potential to degrade the oil. Oil degradation could be enhanced by biostimulation method. The conventional approach to bioremediation of petroleum hydrocarbon is based on aerobic processes. Anaerobic bioremediation has been tested only in a very few cases and is still considered experimental. The currently practiced conventional in situ biorestoration of petroleum-contaminated soils and ground water relies on the supply of oxygen to the subsurface to enhance natural aerobic processes to remediate the contaminants. However, anaerobic microbial processes can be significant in oxygen-depleted subsurface environments and sediments that are contaminated with petroleum-based compounds such as oil-impacted marshes in Louisiana. The goal of this work was to identify the right conditions for the indigenous anaerobic bacteria present in the contaminated sites to enhance degradation of petroleum hydrocarbons. We evaluated the ability of microorganisms under a variety of electron acceptor conditions to degrade petroleum hydrocarbons. Researched microbial systems include sulfate-, nitrate-reducing bacteria, and fermenting bacteria. The results indicated that anaerobic bacteria are viable candidates for bioremediation. Enhanced biodegradation was attained under mixed electron acceptor conditions, where various electron-accepting anaerobes coexisted and aided in degrading complex petroleum hydrocarbon components of marsh sediments in the coastal Louisiana. Significant degradation of oil also occurred under sulfate-reducing and nitrate-reducing conditions.     

Improvement of Solubility and Stability of Valsartan by Hydroxypropyl-\boldbeta-Cyclodextrin

Aim of the present work was to investigate the effect of hydroxypropyl-β-cyclodextrin (HP-β-CD) on the solubility, dissolution rate and stability of Valsartan (VAL), a drug used orally for the treatment of hypertension. Phase solubility studies demonstrated the ability of the HP-β-CD to complex VAL and to increase drug solubility. The dissolved amount of VAL increased linearly with the addition of HP-β-CD according to an A_L type plot. The apparent stability constant of the complex, calculated supposing a 1:1 stoichiometry, was 296±7 M⁻¹. VAL/HP-β-CD interactions were also studied by ¹³C-NMR spectroscopy. Equimolar VAL/HP-β-CD solid systems were prepared by physical-mixing and freeze-drying, and their properties in the solid state studied by DSC and FT-IR analysis. The results provided clear indications of the formation of a new solid phase corresponding to the inclusion complex in the freeze-dried sample. The dissolution profiles of the drug from each solid system were affected by its physico-chemical properties, the freeze-dried being the most rapidly dissolving form. The thermal stability of the complex was studied, also determining the number and identity of the decomposition products of the drug. The stability studies revealed that the VAL/HP-β-CD complex significantly decreases the rate of VAL degradation. These results suggest that CD technology would be a very useful method to overcome the solubility and the stability problems of VAL.     

Long-lived phosphorescence of arenes in complexes with cyclodextrins 2. Room-temperature phosphorescence of ternary complexes of naphthalene and phenanthrene with β-cyclodextrin and adamantane derivatives in the presence of oxygen

Long-lived room-temperature phosphorescence (RTP) of arene—β-cyclodextrin (β-CD)— cage hydrocarbon complexes in the presence of oxygen was studied. Naphthalene-d₈, phenanthrene, and fluorene were used as arenes and adamantane, 1,3-dimethyladamantane, diamantane, and diadamantyl were used as the cage hydrocarbons (according to PM3 quantum chemical calculations, the use of these compounds might cause the appearance of long-lived RTP). The RTP lifetime of the naphthalene-d8—β-CD—diadamantyl complex is 11.9 s at 20 °C. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2661–2665, December, 2005.     

Detailed analysis of petroleum hydrocarbon attenuation in biopiles by high-performance liquid chromatography followed by comprehensive two-dimensional gas chromatography

Enhanced bioremediation of petroleum hydrocarbons in two biopiles was quantified by high-performance liquid chromatography (HPLC) followed by comprehensive two-dimensional gas chromatography (GCXGC). The attenuation of 34 defined hydrocarbon classes was calculated by HPLC–GCXGC analysis of representative biopile samples at start-up and after 18 weeks of biopile operation. In general, a-cyclic alkanes were most efficiently removed from the biopiles, followed by monoaromatic hydrocarbons. Cycloalkanes and polycyclic aromatic hydrocarbons (PAHs) were more resistant to degradation. A-cyclic biomarkers farnesane, trimethyl-C13, norpristane, pristane and phytane dropped to only about 10% of their initial concentrations. On the other hand, C29–C31 hopane concentrations remained almost unaltered after 18 weeks of biopile operation, confirming their resistance to biodegradation. They are thus reliable indicators to estimate attenuation potential of petroleum hydrocarbons in biopile processed soils.     

Potential use of cyclodextrins in soil bioremediation

Bioavailability and toxic effect of contaminants are the main limitations during soil bioremediation. Cyclodextrins may influence bioavailability of the contaminants during biodegradation and also toxicity of the pollutant on soil microbes and plants since their ability to form inclusion complei with organic compounds. The effect of cyclodextrins on bioremediation and on toxic effect of hydrocarbons was investigated by testing the activity of hydrocarbon degrading microflora and of plant growth. The effect of cyclodextrins could be demonstrated in both cases: biodegradation of hydrocarbons could be enhanced and toxic effect of hydrocarbons on plants and soil microbes could be decreased by adding cyclodextrins.     

Bench Scale Studies of the Soil Aeration Process for Bioremediation of Petroleum Hydrocarbons

An alternative to traditional hydrocarbon bioremediation is to pump air through unsaturated soils to create aerobic conditions and induce biodegradation. This study examines the effects of moisture and nutrient augmentation on biodegradation of petroleum hydrocarbons in aerated soils. Findings indicate that forced aeration, coupled with additions of nutrients and moisture, stimulate hydrocarbon-degrading microorganisms and present a feasible approach to bioremediation management.     

Analysis of intermediates from polycyclic aromatic hydrocarbon biodegradation

A major difficulty in assessing bioremediation in hydrocarbon impacted field sites is the determination of the extent and products of contaminant biodegradation. Previously, various analytical techniques, including mass spectrometry and chromatography, have been used to characterize components in mixtures resulting from biodegradation. In this work, the applicability of capillary electrophoresis (CE) to this area of research is demonstrated. CE methods were optimized for analysis of compounds that are known metabolites of polycyclic aromatic hydrocarbon (PAH) biodegradation.     

Effects of Cyclodextrins on Dodecane Biodegradation

Bioremediation of non-chlorinated hydrocarbon-polluted soils is mainly affectedby low bioavailability, due to hydrophobicity of these xenobiotics. In fact, severalmicroorganisms can use hydrocarbons as energy and carbon sources, but theirdegradative activity takes place into the aqueous phase of the soil, where just tracesof hydrocarbons are found because of their low water solubility. So, natural attenuationusually occurs in hydrocarbon-polluted soils, but this process is very slow. It has alreadybeen demonstrated that cyclodextrins increase hydrocarbon solubility and bioavailabilityand accelerate their biodegradation. In this work it was investigated if their efficacy onbiodegradation of a model hydrocarbon (dodecane) is affected by the kind (,-, - and hydroxypropyl--cyclodextrin) and the concentrationof cyclodextrin and by environmental factors such as temperature and composition ofthe microbial indigenous population. The results obtained show that all the testedfactors influence the biodegradation kinetics. The best results were obtained with-cyclodextrin at a concentration near to its water solubility limit; moreover,biodegradation rate increases with temperature and different microbial strains showdifferent degradative activity and metabolic behaviour.     

Enhancement of cyclosporine aqueous solubility using α- and hydroxypropyl β-cyclodextrin mixtures

Cyclodextrins (CDs) are cyclic oligosaccharides that form inclusion complexes with lipophilic molecules through their hydrophobic central cavity. In this study, the effect of α-CD, hydroxylpropyl-β-CD (HP-β-CD) and mixtures of these two CDs on the aqueous solubility of cyclosporine A (CyA) was investigated. Infrared spectroscopy and thermal analysis were used to confirm CyA-CD complex formation. CyA aqueous solubility was increased by 10 and 80 fold in the presence of α-CD and HP β-CD, respectively. The phase-solubility profile for HP-β-CD was linear while that for α-CD had positive deviation from linearity. In the presence of constant concentration of α-CD (15% w/v), aqueous solubility of CyA was further increased upon addition of HP-β-CD up to a concentration of 20% w/v. At higher HP-β-CD concentrations, aqueous solubility of CyA was observed to decrease. Addition of sodium acetate (up to 5% w/v) to aqueous solutions containing 20% w/v HP-β-CD and increasing concentrations of α-CD resulted in a significant reduction in CyA solubility. Complex formation between CyA and both α-CD and HP-β-CD was confirmed by differential scanning calorimetry (DSC). No significant changes were observed in the IR spectra of either CyA or CD following complex formation suggesting chemical interaction between CyA and the CD was unlikely. Phase-solubility studies showed that α-CD had a much greater effect on the solubility of CyA than HP-β-CD. Addition of HP-β-CD to aqueous solutions of α-CD affected the solubility of CyA in these systems. A mixture of 15% w/v α-CD and 20% w/v HP-β-CD was optimal for increasing aqueous solubility of CyA.     

Effect of β-cyclodextrin on the aggregation of the non-ionic surfactant Igepal CO-630 in water as studied by 1D and 2D NMR spectroscopy

The micellization process of the non-ionic surfactant, Igepal CO-630, and its inclusion complexes with β-cyclodextrin (β-CD) have been investigated by NMR spectroscopy. The critical micelle concentration of Igepal was determined by measuring the chemical shifts of different resonances. The structure and binding of the inclusion complexes between the Igepal and the β-CD have been studied by 1D proton NMR and ROESY experiments. The stoichiometry of the inclusion complex is mainly 1:1, with a slight contribution of 2:1. At high concentrations of surfactant, the plots of the chemical shifts in the absence and presence of β-CD coalesce, which indicates that the complexes do not take part into the micelles. The ROESY spectrum displays strong correlations between the internal cavity protons of the CD and the aromatic and aliphatic regions of the Igepal, suggesting the formation of a 2:1 primary face-to-face inclusion complex at high concentrations of β-CD.     

Theoretical study for quercetin/β-cyclodextrin complexes: quantum chemical calculations based on the PM3 and ONIOM2 method

The inclusion interaction between quercetin and β-cyclodextrin (β-CD) binding site has been investigated, based on PM3 and ONIOM2 methods. The obtained results clearly indicate that the orientation in which the B ring of the guest molecule located near the secondary hydroxyls of the β-CD cavity is preferred in the binding energy. Moreover, Analyses regarding the complex structures suggest that one hydrogen bond between 7-hydroxy group (OH) of quercetin and 6-OH of β-CD is formed. This hydrogen bond interaction plays an important role in the bound quercetin/β-CD complex.     

Application of Biosurfactant from Sphingobacterium spiritivorum AS43 in the Biodegradation of Used Lubricating Oil

This study aimed at investigating the application of biosurfactant from Sphingobacterium spiritivorum AS43 using molasses as a substrate and fertilizer to enhance the biodegradation of used lubricating oil (ULO). The cell surface hydrophobicity of bacteria, the emulsification activity, and the biodegradation efficiency of ULO were measured. The bacterial adhesion in the hydrocarbon test was used to denote the cell surface hydrophobicity of the used bacterial species. The results indicate a strong correlation between cell surface hydrophobicity, emulsification activity, and the degree of ULO biodegradation. The maximum degradation of ULO (62 %) was observed when either 1.5 % (w/v) of biosurfactant or fertilizer was added. The results also revealed that biosurfactants alone are capable of promoting biodegradation to a large extent without added fertilizer. The data indicate the potential for biosurfactant production by using low-cost substrate for application in the bioremediation of soils contaminated with petroleum hydrocarbons or oils.     

Binary Systems of Nifedipine And Various Cyclodextrins in The Solid State. Thermal,FTIR, XRD studies

Nifedipine complexes with β-cyclodextrin (β-CD), γ-cyclodextrin (γ-CD), 2-hydroxypropyl-β-cyclodextrin (2HP-β-CD), randomly methylated-β-cyclodextrin (RM-β-CD) and heptakis(2,6-O-dimethyl)-β-cyclodextrin (DM-β-CD) have been prepared by both kneading and heating methods and their behaviour studied by differential scanning calorimetry (DSC), diffuse reflectance mid-infrared spectroscopy (FTIR) and X-ray diffractometry (XRD). DSC revealed the nifedipine melting endotherm with onset at approximately 171°C for the kneaded mixtures with β-CD, γ-CD and 2HP-β-CD, thus confirming the presence of nifedipine in the crystalline state, while some decrease in crystallinity was observed in the DM-β-CD kneaded mixture. With RM-β-CD, however, broadening and shifting of the nifedipine endotherm and reduction in its intensity suggested that the kneading could have produced an amorphous inclusion complex. These differing extents of interaction of nifedipine with the cyclodextrins were confirmed by FTIR and XRD studies. This revised version was published online in August 2006 with corrections to the Cover Date.     

Grafting of cyclodextrins onto filter paper

Grafting of cyclodextrins and cyclodextrins derivatives on cellulosic surface, such as paper or filter paper, provides hosting cavities that can include a large variety of chemicals for specific cellulose finishing. In this study grafting of monocholorotriazinyl-β-cyclodextrin (MCT-β-CD) and β-cyclodextrin (β-CD) to filter paper has been performed. β-cyclodextrin has been bonded to filter paper using 1,4-butanediol diglycidyl ether as the crosslinking agent. The untreated and treated filter papers were characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), demonstrating the covalent binding of cyclodextrins to filter paper. The quantification of β-CD and MCT-β-CD grafted to filter paper was determined by the dye extinction method with the inclusion of phenolphthalein. The final β-CD content amounted to 15.9 μmol per gram of support (1.8% by weight), and 72.8 μmol per gram of support (11.3% by weight) for MCT-β-CD.     

Biodegradation of Fluoranthene by Basidiomycetes Fungal Isolate <Emphasis Type="Italic">Pleurotus Ostreatus</Emphasis> HP-1

The biodegradation of fluoranthene, a high molecular weight polycyclic aromatic hydrocarbon (PAH), was investigated in submerged culture using the wood decaying fungus isolated from forest locality in Gujarat, India. The basidiomycete fungal isolate was found to have an ability to grow on sabaroud dextrose agar containing 50 mgl⁻¹ of each naphthalene, anthracene, acenaphthene, benzo (a) anthracene, pyrene, flouranthene, carbazole, and biphenyl. The involvement of extracellular fungal peroxidases such as manganese peroxidase (MnP) and laccase (Phenol oxidase) in the degradation of fluoranthene was studied. On the eighth day of incubation 54.09% of 70 mg l⁻¹ fluoranthene was removed. There after no PAHs removal was observed till the 20th day of the incubation period. The isolate was identified as Pleurotus ostreatus by 18S rRNA, 5.8S rRNA, and partial 28S rRNA gene sequencing. To the best of our knowledge this is the first time Pleurotus ostreatus have been reported to degrade such a high concentration of fluoranthene within much lower time period of incubation. Depletion in the residual fluoranthene in the culture medium was determined by HPLC. Attempts were made to identify the degradation product in the culture medium with the help of FT-IR, NMR, and HPTLC analysis. In the present study positive correlation between fluoranthene degradation and the ligninolytic enzyme (MnP and laccase) production is observed, thus this isolate can play an effective role for bioremediation of PAHs contaminated sites.     

Thermal Properties of Binary Mixtures of β-Cyclodextrin with Carbamazepine Polymorphs

The thermal behaviour of binary mixtures between β-cyclodextrin (β-CD) and either carbamazepine polymorphic Form I (CBZ I), Form III (CBZ III) or dihydrate was investigated in order to assess possible interactions of CBZ solid phases with β-CD. Physical mixtures and kneaded binaries of β-CD and different CBZ crystal forms were studied by differential scanning calorimetry, thermogravimetric analysis and hot stage microscopy. The pattern of transition of CBZ Form III into Form I is strongly influenced by β-CD. The liquid-solid transition is practically absent when anhydrous CBZ/β-CD mixes are tested, as a consequence of an interaction between β-CD and liquid CBZ that hinders CBZ recrystallisation as Form I occurring after CBZ Form III melting. Water loss on heating of CBZ dihydrate in the presence of β-CD leads in all cases to the formation of CBZ Form I. This revised version was published online in August 2006 with corrections to the Cover Date.     

Functionalization of polymeric membranes by impregnation and in situ cross-linking of a PDMS/β-cyclodextrin network

In this paper a new method for the functionalization of porous membranes with β-CD is reported. Porous polypropylene (PP) hollow fibres have been impregnated with a mixture composed by a partially cross-linked polydimethylsiloxane (PDMS) and β-cyclodextrin (β-CD). The prepolymerization of the PDMS components was necessary to avoid their inclusion in the β-CD cavity. The firm heterogenization of the β-CD was obtained by in situ cross-linking of the PDMS/β-CD network in the porous membranes. The presence of the PDMS/β-CD network in the membranes was confirmed by FT-IR-ATR (on the outer and inner surfaces) and EDX analyses (on the cross-section).The effect of the impregnation times on membrane morphology, loading and porosity has been investigated. The binding capacity of the heterogenized β-CDs has been tested using the phenolphthalein as guest molecule.