Academic literature on the topic 'Solubility phase diagram'

During the 1990s, the chemical industry has focused on ways to reduce and prevent pollution caused by chemical synthesis and manufacturing. The goal of this approach is to modify existing reaction conditions and/or to develop new chemistries that do not require the use of toxic reagents or solvents, or that do not produce toxic by-products. The terms “environmentally benign synthesis and processing” and “green chemistry” have been coined to describe this approach where the environmental impact of a process is as important an issue as reaction yield, efficiency, or cost. Most chemical reactions require the use of a solvent that may serve several functions in a reaction: for example, ensuring homogeneity of the reactants, facilitating heat transfer, extraction of a product (or by-product), or product purification via chromatography. However, because the solvent is only indirectly involved in a reaction (i.e., it is not consumed), its disposal becomes an important issue. Thus, one obvious approach to “green chemistry” is to identify alternative solvents that are nontoxic and/or environmentally benign. Supercritical carbon dioxide (sc CO2) has been identified as a solvent that may be a viable alternative to solvents such as CCl4, benzene, and chloroflurocarbons (CFCs), which are either toxic or damaging to the environment. The critical state is achieved when a substance is taken above its critical temperature and pressure (Tc, Pc). Above this point on a phase diagram, the gas and liquid phases become indistinguishable. The physical properties of the supercritical state (e.g., density, viscosity, solubility parameter, etc.) are intermediate between those of a gas and a liquid, and vary considerably as a function of temperature and pressure. The interest in sc CO2 specifically is related to the fact that CO2 is nontoxic and naturally occurring. The critical parameters of CO2 are moderate (Tc = 31 °C, Pc = 74 bar), which means that the supercritical state can be achieved without a disproportionate expenditure of energy. For these two reasons, there is a great deal of interest in sc CO2 as a solvent for chemical reactions. This chapter reviews the literature pertaining to free-radical reactions in sc CO2 solvent.

In this chapter, we consider what happens when solids begin to form from solution. To grow solids from solution, solution conditions are changed from a condition in which all species are completely soluble to a condition in which they are insoluble. In the context of hydrolysis diagrams, the solution composition moves in pH and total dissolved metal concentration from a regime below a solubility or saturation limit (given by the bold solid line in Figs. 5.2 and 5.3) to a regime above this limit where the solution is supersaturated. Supersaturated solutions are inherently unstable and have the potential to generate hydroxide or oxide solids. Sometimes these solutions can be maintained in a metastable state in which precipitation does not occur immediately. However, Mother Nature eventually reduces the energy of the solution by forming a stable mixture of solids plus solution species. As solids form, soluble complexes are removed from solution until concentrations drop back to the solubility limit. The precipitation of a solid from an aqueous solution is a surprisingly complex process, involving nucleation and growth phenomena that occur at nanometer-length scales. Nucleation involves reactions between oligomers to form new clusters or particles that are sufficiently large that they do not redissolve spontaneously via the reversible reactions denoted in hydrolysis diagrams. Homogeneous and heterogeneous nucleation processes represent events that occur within the bulk solution or at the interface of another phase, respectively. Growth involves the addition of monomers to clusters in solution or oligomers to existing particles or surfaces. The combination of nucleation and growth phenomena can lead to oxides exhibiting a bewildering range of sizes, shapes, and crystal structures. How do metal complexes decide whether to form a new particle or add to an existing particle? What determines the size, shape, and crystal structure of evolving particles? Do the particles aggregate with one another in an organized fashion? Because nucleation typically involves extremely rapid (<1 millisecond) events involving objects that are extremely small (on the order of a nanometer), it is difficult to probe such phenomena at a molecular level.

There are many methods to crystallize biological macromolecules (for reviews see refs 1-3), all of which aim at bringing the solution of macromolecules to a supersaturation state (see Chapters 10 and 11). Although vapour phase equilibrium and dialysis techniques are the two most favoured by crystallographers and biochemists, batch and interface diffusion methods will also be described. Many chemical and physical parameters influence nucleation and crystal growth of macromolecules (see Chapter 1, Table 1). Nucleation and crystal growth will in addition be affected by the method used. Thus it may be wise to try different methods, keeping in mind that protocols should be adapted (see Chapter 4). As solubility is dependent on temperature (it could increase or decrease depending on the protein), it is strongly recommended to work at constant temperature (unless temperature variation is part of the experiment), using commercially thermoregulated incubators. Refrigerators can be used, but if the door is often open, temperature will vary, impeding reproducibility. Also, vibrations due to the refrigerating compressor can interfere with crystal growth. This drawback can be overcome by dissociating the refrigerator from the compressor. In this chapter, crystallization will be described and correlated with solubility diagrams as described in Chapter 10. Observation is an important step during a crystallization experiment. If you have a large number of samples to examine, then this will be time-consuming, and a zoom lens would be an asset. The use of a binocular generally means the presence of a lamp; use of a cold lamp avoids warming the crystals (which could dissolve them). If crystals are made at 4°C and observation is made at room temperature, observation time should be minimized. Preparation of the solutions of all chemicals used for the crystallization of biological macromolecules should follow some common rules: • when possible, use a hood (such as laminar flux hood) to avoid dust • all chemicals must be of purest chemical grade (ACS grade) • stock solutions are prepared as concentrated as possible with double distilled water. Solubility of most chemicals are given in Merck Index. Filter solutions with 0.22 μm minifilter.

Unlike the crystallization of small inorganic molecules, the problem of protein crystallization was first approached by trial and error methods without any theoretical background. A physico-chemical approach was chosen because crystallographers and biochemists needed criteria to rationally select crystallization conditions. In fact, the problem of the production of homogeneous and structurally perfect protein crystals is set the same as the production of high-quality crystals for opto-electronic applications, because, in both cases, the crystal growth mechanisms are the same. Biological macromolecules and small organic molecules follow the same rules concerning crystallization even if each material exhibits specific characteristics. This chapter introduces the fundamentals of crystallization: supersaturation, nucleation, and crystal growth mechanisms. Phase diagrams are presented in Chapter 10. Special attention will be paid to the behaviour of the macromolecules in solution and to the techniques used for their analysis: light scattering (LS), small angle X-ray scattering (SAXS), small angle neutron scattering (SANS), and osmotic pressure (OP). Before obtaining any nucleation or growth, it is necessary to dissolve the biological macromolecules under consideration in some good solvent. However, it may immediately be asked whether a good solvent is a solvent in which the material is highly soluble, or in which nucleation is easily controlled, or in which growth is fast, or solvent in which the crystals exhibit the appropriate morphology. In practice, the choice of the solvent often depends on the nature of the material to be dissolved, taking into account the well known rule which says that ‘like dissolves like’. This means that, for dissolution to occur, it is necessary that the solute and the solvent exchange bonds: between an ion and a dipole, a dipole and another dipole, hydrogen bonds, and/or Van der Waals bonds. Therefore, the nature of the bonds depends on both the nature of the solute and the solvent which can be dipolar protic, dipolar aprotic, or completely apolar. Once the material has dissolved, the solution must be supersaturated in order to observe nucleation or growth. The solution is supersaturated when the solute concentration exceeds its solubility. There are several ways to achieve supersaturation.

A protein’s atomic level three-dimensional structure is typically determined by X-ray diffraction of a high-quality protein crystal (Figure 1a). The X-ray bream is diffracted inside the crystal producing spots at various locations (Figure 1b) which can be used to back out the location of the electron cloud of the protein which is used to solve the structure (Figure 1c). The current bottleneck in these structural determination projects is in growing a diffraction quality protein crystal. Current growth methods involve testing hundreds of conditions in this multi-parametric process without knowl

Humic substances (HS) have a wide spectrum of biological activity including inhibitory activity against β-lactamases.1 The latter are capable of hydrolyzing beta-lactam antibiotics and represent one of the main pathways of bacterial antibiotic resistance. HS are characterized by low toxicity and good solubility in water. A use of HS for therapeutic purposes is hindered by extreme molecular heterogeneity and high level of isomeric complexity. Solid-phase extraction (SPE) fractionation in combination with ultra-high resolution mass spectrometry (FTICR MS) is a promising method to simplify this m

Hydrate formation is one of the major challenges faced by the Oil and Gas industry in offshore facilities due to its potential to plug wells and reduce production. Several experimental studies have been published so far in order to understand the mechanisms that govern the hydrate formation process under its thermodynamic favorable conditions; however, the results are not very accurate due to the uncertainties related to measurements and metastable behavior observed in some cases involving hydrate formation. Moreover, thermodynamic models have been proposed to overcome the latter constraints b