Desorption and crystallisation of binary 2-propanol and water ices adsorbed on graphite

Alcohols, including 2-propanol, are important in a range of industrial applications, and are also found in cold astrophysical environments such as comets and interstellar space, where they are often frozen out on carbonaceous grain surfaces. In these regions, the interaction between alcohols and water ice plays a crucial role in the surface chemistry. We have therefore undertaken a detailed temperature programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS) investigation to elucidate the physical chemistry of the adsorption, desorption and crystallisation of 2-propanol and water ices adsorbed on graphite at 26 K. Hydrogen bonding plays a critical role in the physical chemistry of both pure 2-propanol and of binary ices containing 2-propanol and water ice. Monolayer 2-propanol physisorbs strongly on the graphite surface, and with increasing coverage, annealing leads to the desorption of first amorphous, and then crystalline, 2-propanol multilayers. Crystallisation is also evident in RAIR spectra, which show marked changes on annealing of the adsorbed 2-propanol layer. In binary ice systems containing amorphous solid water and 2-propanol, the desorption and crystallisation of the alcohol is modified. The water ice inhibits the 2-propanol crystallisation and gives rise to co-desorption in TPD. In addition, the 2-propanol also strongly influences the behaviour of the water, with even small amounts of the alcohol changing the crystallisation kinetics of water ice, leading to the desorption of water solely in its amorphous form

Coordination networks incorporating halogen-bond donor sites and azobenzene groups

Two Zn coordination networks, [Zn(1)(Py)2]2(2-propanol)n (3) and [Zn(1)2(Bipy)2](DMF)2n (4), incorporating halogen-bond (XB) donor sites and azobenzene groups have been synthesized and fully characterized. Obtaining 3 and 4 confirms that it is possible to use a ligand wherein its coordination bond acceptor sites and XB donor sites are on the same molecular scaffold (i.e., an aromatic ring) without interfering with each other. We demonstrate that XBs play a fundamental role in the architectures and properties of the obtained coordination networks. In 3, XBs promote the formation of 2D supramolecular layers, which, by overlapping each other, allow the incorporation of 2-propanol as a guest molecule. In 4, XBs support the connection of the layers and are essential to firmly pin DMF solvent molecules through I⋯O contacts, thus increasing the stability of the solvated systems

Purification of Curcumin from Ternary Extract-Similar Mixtures of Curcuminoids in a Single Crystallization Step

Crystallization-based separation of curcumin from ternary mixtures of curcuminoids having compositions comparable to commercial extracts was studied experimentally. Based on solubility and supersolubility data of both, pure curcumin and curcumin in presence of the two major impurities demethoxycurcumin (DMC) and bis(demethoxy)curcumin (BDMC), seeded cooling crystallization procedures were derived using acetone, acetonitrile and 50/50 (wt/wt) mixtures of acetone/2-propanol and acetone/acetonitrile as solvents. Starting from initial curcumin contents of 67–75% in the curcuminoid mixtures single step crystallization processes provided crystalline curcumin free of BDMC at residual DMC contents of 0.6–9.9%. Curcumin at highest purity of 99.4% was obtained from a 50/50 (wt/wt) acetone/2-propanol solution in a single crystallization step. It is demonstrated that the total product yield can be significantly enhanced via addition of water, 2-propanol and acetonitrile as anti-solvents at the end of a cooling crystallization process

Structure and dynamics of aqueous 2-propanol: a THz-TDS, NMR and neutron diffraction study.

Aqueous liquid mixtures, in particular, those involving amphiphilic species, play an important role in many physical, chemical and biological processes. Of particular interest are alcohol/water mixtures; however, the structural dynamics of such systems are still not fully understood. Herein, a combination of terahertz time-domain spectroscopy (THz-TDS) and NMR relaxation time analysis has been applied to investigate 2-propanol/water mixtures across the entire composition range; while neutron diffraction studies have been carried out at two specific concentrations. Excellent agreement is seen between the techniques with a maximum in both the relative absorption coefficient and the activation energy to molecular motion occurring at ∼90 mol% H2O. Furthermore, this is the same value at which well-established excess thermodynamic functions exhibit a maximum/minimum. Additionally, both neutron diffraction and THz-TDS have been used to provide estimates of the size of the hydration shell around 2-propanol in solution. Both methods determine that between 4 and 5 H2O molecules per 2-propanol are found in the 2-propanol/water clusters at 90 mol% H2O. Based on the acquired data, a description of the structure of 2-propanol/water across the composition range is presented.The authors would like to acknowledge CASTech (EPSRC grant EP/G011397/1), RCUK Basic Technology Grant (EP/E048811/1), STFC for beamtime allocation (RB910286) and Jon Mitchell (Cambridge) for valuable discussions.This is the final version of the article. It was first available from RSC via http://dx.doi.org/10.1039/C5CP01132

Analysis of Mesoscopic Structured 2-Propanol/Water Mixtures Using Pressure Perturbation Calorimetry and Molecular Dynamic Simulation

In this paper we demonstrate the application of pressure perturbation calorimetry (PPC) to the characterization of 2-propanol/water mixtures. PPC of different 2-propanol/water mixtures provides two useful measurements: (i) the change in heat (ΔQ); and (ii) the [δC¯p/δp]T[δC¯p/δp]T value. The results demonstrate that the ΔQ values of the mixtures deviate from that expected for a random mixture, with a maximum at ~20–25 mol% 2-propanol. This coincides with the concentration at which molecular dynamics (MD) simulations show a maximum deviation from random distribution, and also the point at which alcohol–alcohol hydrogen bonds become dominant over alcohol–water hydrogen bonds. Furthermore, the [δC¯p/δp]T[δC¯p/δp]T value showed transitions at 2.5 mol% 2-propanol and at approximately 14 mol% 2-propanol. Below 2.5 mol% 2-propanol the values of [δC¯p/δp]T[δC¯p/δp]T are negative; this is indicative of the presence of isolated 2-propanol molecules surrounded by water molecules. Above 2.5 mol% 2-propanol [δC¯p/δp]T[δC¯p/δp]T rises, reaching a maximum at ~14 mol% corresponding to a point where mixed alcohol–water networks are thought to dominate. The values and trends identified by PPC show excellent agreement not only with those obtained from MD simulations but also with results in the literature derived using viscometry, THz spectroscopy, NMR and neutron diffraction

Gradient porosity poly(dicyclopentadiene)

This article describes the preparation of gradient porosity thermoset polymers. The technique used is based on polymerizing a solution of cross-linkable dicyclopentadiene and 2-propanol. The forming polymer being insoluble in 2-propanol, phase separation occurs. Subsequent drying of the 2-propanol gives porosities up to 80%. An apparatus was built to produce a gradient in 2-propanol concentration in a flask, resulting in polymerized gradient porosity rods. The resulting materials have been characterized by scanning electron microscopy (SEM) and density measurements. A mathematical model which allows prediction of the gradient produced is also presente

Anaerobic degradation of 2-propanol: Laboratory and pilot-scale studies

The anaerobic degradation of 2-propanol, an important industrial solvent, was scaled-up from batch assays to a pilot expanded granular sludge bed (EGSB) reactor at 25 °C. Batch studies indicated that 2-propanol followed Haldane kinetics, with a maximum rate at 10 g COD L−1. Concentrations as high as 25 g COD L−1 did not inhibit the degradation of ethanol, a common co-solvent. Similar specific methanogenic activities (SMA) were obtained for water-solvent and water-brewery sludges (88 and 77 ml CH4 g-VS−1 d−1 at 5 g COD L−1). Continuous degradation showed a lag-phase of three weeks with water-brewery sludge. Increases in 2-propanol load from 0.05 to 0.18 kg COD kg-VS−1 d−1 caused a shift from the consumption of soluble matter to methane production, indicating polyhydroxybutyrates (PHB) accumulation. Conversely, smooth increases of up to 0.29 kg COD kg-VS−1 d−1 allowed 2-propanol degradation without PHB accumulation. The slowdown rate of 2-propanol-oxidizer and acetate-utilizing methanogen bacteria below 20 °C adversely impacted both removal and CH4 yield

Determination of water in organic solvents by flow-injection analysis with Karl Fischer reagent and a biamperometric detection system

A flow-injection system with a biamperometric flow-through detector provided with two platinum plate electrodes was tested for the determination of water with a two-component pyridine-free Karl Fischer reagent. The response was shown to be linear in the concentration range 0.03–0.11% water in methanol, ethanol or 2-propanol, with methanol as the carrier solvent. The maximum sampling frequency was about 150 samples per hr. It appeared to be possible to introduce a membrane separation step, thus allowing for the determination of water in fouled process streams. To avoid direct contact between the Karl Fischer solution and the pumping tubes, and thus extend the lifetime of the tubes, an indirect delivery system, based on replacement of the solution by pumped silicone oil, was also applied

Trace-gas metabolic versatility of the facultative methanotroph Methylocella silvestris

The climate-active gas methane is generated both by biological processes and by thermogenic decomposition of fossil organic material, which forms methane and short-chain alkanes, principally ethane, propane and butane1, 2. In addition to natural sources, environments are exposed to anthropogenic inputs of all these gases from oil and gas extraction and distribution. The gases provide carbon and/or energy for a diverse range of microorganisms that can metabolize them in both anoxic3 and oxic zones. Aerobic methanotrophs, which can assimilate methane, have been considered to be entirely distinct from utilizers of short-chain alkanes, and studies of environments exposed to mixtures of methane and multi-carbon alkanes have assumed that disparate groups of microorganisms are responsible for the metabolism of these gases. Here we describe the mechanism by which a single bacterial strain, Methylocella silvestris, can use methane or propane as a carbon and energy source, documenting a methanotroph that can utilize a short-chain alkane as an alternative to methane. Furthermore, during growth on a mixture of these gases, efficient consumption of both gases occurred at the same time. Two soluble di-iron centre monooxygenase (SDIMO) gene clusters were identified and were found to be differentially expressed during bacterial growth on these gases, although both were required for efficient propane utilization. This report of a methanotroph expressing an additional SDIMO that seems to be uniquely involved in short-chain alkane metabolism suggests that such metabolic flexibility may be important in many environments where methane and short-chain alkanes co-occur

Microalgae cultivation for lipids and carbohydrates production

Microalgae are photoautotrophic microorganisms that can produce energy both by using sunlight, water and CO2 (phototrophic metabolism) and by using organic sources such as glucose (heterotrophic metabolism). Heterotrophic growth is a key factor in microalgae research, due to its increased productivity and the lower capital and operative costs compared to photoautotrophic growth in photobioreactors. Carbohydrate production from microalgae is usually investigated for the production of biofuels (e.g. bioethanol) by successive fermentation, but also other applications can be envisaged in biopolymers. In this work an increment in carbohydrate purity after lipid extraction was found. Protein hydrolysis for different microalgae strains (Scenedesmus sp. and Chlorella sp.) was investigated. Microalgae were cultivated under photoautotrophic or heterotrophic conditions, collecting biomass at the end of the growth. Biomass samples were dried or freeze dried and used for carbohydrate and lipid extraction tests. Lipid extraction was achieved using different organic solvents (methanol-chloroform and hexane-2propanol). Basic protein hydrolysis has been carried out testing different temperatures and NaOH concentrations values. Lipids were spectrophotometrically quantified, while residual biomass was saccharificated and the total amount of sugars was measured. Significant differences about the purity of extracted carbohydrates were found comparing dried with freeze dried biomass. However, not a very promising purification of carbohydrates was achieved after protein hydrolysis, asking for further analysis. © Copyright 2017, AIDIC Servizi S.r.l