Synthetic chemistry in a water world. New rules ripe for discovery

Several examples are discussed where reactions in aqueous micellar media are clearly governed by new rules, in contrast to those that prevail in traditional organic synthesis performed in organic solvents.     

Supramolecular chemistry in water

Supramolecular chemistry in water is a constantly growing research area because noncovalent interactions in aqueous media are important for obtaining a better understanding and control of the major processes in nature. This Review offers an overview of recent advances in the area of water-soluble synthetic receptors as well as self-assembly and molecular recognition in water, through consideration of the functionalities that are used to increase the water solubility, as well as the supramolecular interactions and approaches used for effective recognition of a guest and self-assembly in water. The special features and applications of supramolecular entities in aqueous media are also described.     

Organic chemistry in water

Water has emerged as a versatile solvent for organic chemistry in recent years. Water as a solvent is not only inexpensive and environmentally benign, but also gives completely new reactivity. The types of organic reactions in water are broad including pericyclic reactions, reactions of carbanion equivalent, reactions of carbocation equivalent, reactions of radicals and carbenes, transition-metal catalysis, oxidations-reductions, which we discuss in this tutorial review. Aqueous organic reactions have broad applications such as synthesis of biological compounds from carbohydrates and chemical modification of biomolecules.     

Modification of ilmenite surface chemistry for enhancing surfactants adsorption and bubble attachment

In this study, microwave irradiation is used to modify ilmenite surface chemistry to enhance the adsorption of surfactants and the air bubble attachment. The results indicate that microwave irradiation can increase ilmenite flotation recovery by 20%. A positron emission particle tracking technique is used to study the dynamic behaviour of ilmenite particles in a Denver cell. The data shows that the poor flotation recovery of ilmenite is not only due to the reduce probability of ilmenite being captured by air bubbles, but also the short residence time of the particles remaining in the froth phase. The ilmenite particles can be frequently captured by air bubbles, but dropped to the bulk liquid from the froth phase, normally over 15 s. Microwave irradiation changes the ilmenite flow pattern in the Denver cell. The average time of ilmenite remaining in froth phase is increased from 11.5 to 29.1 s.     

Sorption-photometric determination of anionic surfactants in water

The adsorption of Crystal Violet, anionic surfactants, and their ion associates on nonionic hydrophobic polymer adsorbent Amberlite XAD-16 was studied. A procedure for the sorption-photometric determination of anionic surfactants in water was developed with a detection limit of 0.001–0.003 mg/L at a sample volume of 50 mL.     

Micro-pumping flow system for spectrophotometric determination of anionic surfactants in water

A novel procedure has been developed for spectrophotometric determination of anionic surfactants in water using a solenoid micro-pump as fluid-propulsion device. The proposed method is based on substitution of methyl orange (MO) by anionic surfactants in the formation of an ion-pair with the cetyl pyridine ion (CPC⁺) at pH 5.0. The flow network comprised four solenoid micro-pumps which, under microcomputer control, enabled sample and reagent introduction, and homogenisation in the reaction zone. The system is flexible and simple to operate and control, and sensitive and precise. The analytical plot for the anionic surfactant was linear between 1.43×10^–6 and 1.43×10^–5 mol L^–1 (0.5 to 5.0 mg L^–1; R=0.997, n=5). The relative standard deviation was 0.8% (n=11) for a sample containing 5.74×10^–6 mol L^–1 (2 mg L^–1) surfactant. The limit of detection was 9.76×10^–8 mol L^–1 (0.034 mg L^–1) and the sampling throughput was 60 determinations per hour. The results obtained for washing-water samples were comparable with those obtained by use of the reference method, and no significant differences at the 95% confidence level were observed.     

New trends in polyoxometalate photoredox chemistry: from photosensitisation to water oxidation catalysis

Molecular metal oxide clusters, so-called polyoxometalates (POM) have been extensively used as homogeneous photocatalysts in various photoredox reactions such as the oxidation of alkanes, alkenes and alcohols as well as the light-induced mineralisation of various organic and inorganic pollutants. The more general application of POMs as photoactive compounds, in particular in solar energy harnessing, has been hampered as the clusters typically absorb light in the UV-region only. Over the past decade, concepts have been put forward on how the reactivity of this class of compounds can be optimised to improve their overall photoactivity, and a particular focus has been on the design of photocatalytic processes which allow the conversion of solar light into useful chemical reactivity. This perspective gives a brief overview of general aspects of POM photochemistry and critically discusses the advantages and challenges of a range of POM-based systems for photooxidations and photoreductions with a focus on the development of sustainable solar light conversion systems.     

Thermal diffusion behavior of nonionic surfactants in water

We studied the thermal diffusion behavior of hexaethylene glycol monododecyl ether (C12E6) in water by means of thermal diffusion forced Rayleigh scattering (TDFRS) and determined Soret coefficients, thermal diffusion coefficients, and diffusion constants at different temperatures and concentrations. At low surfactant concentrations, the measured Soret coefficient is positive, which implies that surfactant micelles move toward the cold region in a temperature gradient. For C12E6/water at a high surfactant concentration of w1 = 90 wt % and a temperature of T = 25 degrees C, however, a negative Soret coefficient S(T) was observed. Because the concentration part of the TDFRS diffraction signal for binary systems is expected to consist of a single mode, we were surprised to find a second, slow mode for C12E6/water system in a certain temperature and concentration range. To clarify the origin of this second mode, we investigated also, tetraethylene glycol monohexyl ether (C6E4), tetraethylene glycol monooctyl ether (C8E4), pentaethylene glycol monododecyl ether (C12E5), and octaethylene glycol monohexadecyl ether (C16E8) and compared the results with the previous results for octaethylene glycol monodecyl ether (C10E8). Except for C6E4 and C10E8, a second slow mode was observed in all systems usually for state points close to the phase boundary. The diffusion coefficient and Soret coefficient derived from the fast mode can be identified as the typical mutual diffusion and Soret coefficients of the micellar solutions and compare well with the independently determined diffusion coefficients in a dynamic light scattering experiment. Experiments with added salt show that the slow mode is suppressed by the addition of w(NaCl) = 0.02 mol/L sodium chloride. This suggests that the slow mode is related to the small amount of absorbing ionic dye, less than 10(-5) by weight, which is added in TDFRS experiments to create a temperature grating. The origin of the slow mode of the TDFRS signal will be tentatively interpreted in terms of a ternary mixture of neutral micelles, dye-charged micelles, and water.     

Extractive spectrophotometric determination of non-ionic surfactants in water

The solvent extraction of non-ionic surfactants with potassium chloride and tetrabromophenolphthalein ethyl ester potassium salt has been studied, and a method developed for determining trace amounts of non-ionic surfactants in water spectrophotometrically. Various non-ionic surfactants of general type RO(CH(2)CH(2)O)(n)H (where R is an alkyl or alkylphenyl group and n is the number-average degree of polymerization) are extracted quantitatively into o-dichlorobenzene from the water sample, and reacted in the organic phase with tetrabromophenolphthalein ethyl ester potassium salt to give a coloured product, the absorbance of which is measured at 620 nm.     

A simple salt-enhanced surface-tension technique for detection of trace surfactants in water

A simple, relatively inexpensive DuNoy tensiometer can be used to detect small amounts of surfactants in water (at the μg l^-1 level in many cases). The surfactant must be salted-out to produce the desired effect. Addition of salt to pure water produces a reproducible increase in surface tension, whereas addition of salt to a water sample containing traces of surfactant produces a distinct, reproducible decrease. For pure surfactant solutions, calibration curves can be constructed for quantitative work.     

Synthesis of thiophosphoramidates in water: click chemistry for phosphates

An aqueous method for the preparation of N,S-dialkyl thiophosphoramidates is reported. Thiophosphorylation of alkylamines was performed using SPCl(3) in aqueous reaction media, and the resulting thiophosphoramidate-S-anions were S-alkylated with soft electrophiles. Ranges of amines and electrophiles were explored.     

Interaction between water soluble polymers and surfactants

Based on literature data and some own results a short review of regularities, driving forces and mechanisms of interaction for different classes of polymers and surfactants is given. The main investigation methods of polymer‐surfactant systems are described.     

New phosphaneborane chemistry

Following a short account of pertinent literature, recent work on two classes of phosphaneboranes is summarized.H₃B(CH₃)₂PCl (1) was found to be an excellent precursor for an extended new chemistry of the H₃B(CH₃)₂P-group, which is isoelectronic with the (CH₃)₃Si-group. Boranatodimethylphosphinic acid H₃B(CH₃)₂POH, its anhydride H₃B(CH₃)₂POP(CH₃)₂BH₃, salts, complexes, esters and carboxylates have been prepared and identified through analytical and spectroscopic studies. The corresponding sulphur analogues are also available. The amide H₃B(CH₃)₂PNH₂ is formed from 1 and NH₃ as a stable crystalline product. It is easily converted into its imide H₃B(CH₃)₂PNHP(CH₃)₂BH₃ and a variety of organic derivatives. H₃B(CH₃)₂PCH₂P(CH₃)₂BH₃ has protic hydrogen atoms in the CH₂ bridge and affords a crystalline ylidic Li salt, the crystal structure of which was determined. CH₃ metallation of (CH₃)₃PBH₃ leads to similar product useful for derivatisation.The (CH₃)₃PBH₂P(CH₃)₃⁺X^? salts are starting materials for the preparation of the novel ^?CH₂(CH₃)₂PBH₂P(CH₃)₂CH₂^? ligand system. Its coordination chemistry, with examples from most groups of the Periodic Table, is reviewed, including both diamagnetic and paramagnetic species. Representative structures were determined by X-ray diffraction, and multi-nuclei NMR and magnetic data were used for further characterisation.     

Analysis of ethoxylated alcohol surfactants in water by HPLC

Summary An HPLC procedure for the determination of linear alcohol polyethoxylates in surface water, waste water, and detergents is described. After extraction of the alcohol ethoxylates into an organic phase the alcohol ethoxylates are derivatized with phenyl isocyanate to apply an UV detection. A reversed-phase HPLC procedure is used to separate different ethoxylate species by their different alkyl chain length. A normal phase procedure is employed to separate alcohol polyethoxylates by their different number of ethoxylate groups in the molecule.     

Optosensing of cationic surfactants based on host–guest chemistry

An optode membrane for cationic surfactants is presented. Plasticized poly(vinyl chloride) (PVC) membranes incorporating the hexaester of calix[6]arene and the neutral H⁺-selective chromo-ionophore (ETH5294) have proved to be excellent reversible sensing devices for cationic surfactants as exemplified by cetyltrimethylammonium bromide (CTMAB). Based on host–guest chemistry, the guest molecule CTMAB was extracted into the PVC membrane, forming a host–guest adduct with the host molecule calix[6]arene ionophore and causing a concomitant release of a proton from the protonated ETH5294 into the solution. Upon deprotonation, ETH5294 undergoes a color change which can be used as a means for the quantitation of CTMAB. Unlike small inorganic cations, such as K⁺ and Na⁺, the experimental results show that the membrane response depends to a great extent on the migration process of CTMAB from the bulk of the solution to the membrane interface. A modified theoretical equation describing the membrane response on the CTMAB concentrations has been derived and shown to be in conformity with the experimental results.     

New challenges in fullerene chemistry

The aim of this focus article is to emphasize those aspects of fullerene chemistry which currently represent important challenges for the development and future applications of these new carbon allotropes, as well as to celebrate the tenth anniversary of the fullerenes Nobel Prize.     

Mixed micelles of homologous perfluoropolyether anionic surfactants in water

The mixtures of sodium and ammonium salts of three homologous perfluoropolyether carboxylic acids having Cl-terminated perfluoroalkyl group (Cl-PFPE) and differing in the average molecular weight (MW) were examined. The surfactants, namely n2, n3 and n4, have two, three and four PFPE units, respectively. Each surfactant was studied alone and in mixture with the other surfactants with the same counterion. NMR chemical shifts were measured for each surfactant and for the mixtures in different concentrations. For a given mixture the micelle composition, X_i, can be determined from the observation of the chemical shifts of the micellar components. It was found that Cl-PFPE surfactant mixtures form in water mixed micelles which contain the surfactants in equilibrium with monomeric species. The analysis of NMR chemical shift variations allowed evaluating the partition of the various surfactants in the mixed aggregates as a function of the total concentration. Composition of mixed micelles resembles ideal mixing predictions particularly at high surfactant concentrations.