The effects of surfactant molecules involved in macro-, mini-, nano-, and microemulsions used in cosmetics and pharmaceuticals are related to their amphiphilic interactions with oil and water phases. Basic ideas on their behavior when they are put together in a system have resulted in the energy balance concept labeled the hydrophilic-lipophilic deviation (HLD) from optimum formulation. This semiempirical equation integrates in a simple linear relationship the effects of six to eight variables including surfactant head and tail, sometimes a cosurfactant, oil-phase nature, aqueous-phase salinity, temperature, and pressure. This is undoubtedly much more efficient than the hydrophilic-lipophilic balance (HLB) which has been used since 1950. The new HLD is quite important because it allows researchers to model and somehow predict the phase behavior, the interfacial tension between oil and water phases, their solubilization in single-phase microemulsion, as well as the corresponding properties for various kinds of macroemulsions. However, the HLD correlation, which has been developed and used in petroleum applications, is sometimes difficult to apply accurately in real cases involving ionic–nonionic surfactant mixtures and natural polar oils, as it is the case in cosmetics and pharmaceuticals. This review shows the confusion resulting from the multiple definitions of HLD and of the surfactant parameter, and proposes a “normalized” Hydrophilic-Lipophilic Deviation (HLD_N) equation with a surfactant contribution parameter (SCP), to handle more exactly the effects of formulation variables on the phase behavior and the micro/macroemulsion properties.

Formulation is an ancient concept, although the word has been used only recently. The first formulations made our civilization advance by inventing bronze, steel, and gunpowder; then, it was used in medieval alchemy. When chemistry became a science and with the golden age of organic synthesis, the second formulation period began. This made it possible to create new chemical species and new combinations “à la carte.” However, the research and developments were still carried out by trial and error. Finally, the third period of formulation history began after World War II, when the properties of a system were associated with its ingredients and the way they were assembled or combined. Therefore, the formulation and the systems’ phenomenology were related to the generation of some synergy to obtain a commercial product. Winsor’s formulation studies in the 1950s were enlightening for academy and industries that were studying empirically surfactant-oil-water (SOW) systems. One of its key characteristics was how the interfacial interaction of the adsorbed surfactant with oil and water phases could be equal by varying the physicochemical formulation of the system. Then, Hansen’s solubility parameter in the 1960s helped to reach a further understanding of the affinity of some substances to make them suitable to oil and water phases. In the 1970s, researchers such as Shinoda and Kunieda, and different groups working in Enhanced Oil Recovery (EOR), among them Schechter and Wade’s group at the University of Texas, made formulation become a science by using semiempirical correlations to attain specific characteristics in a system (e.g., low oil-water interfacial tension, formulation of a stable O/W or W/O emulsion, or high-performance solubilization in a bicontinuous microemulsion system at the so-called optimum formulation). Nowadays, over 40 years of studies with the hydrophilic-lipophilic deviation equation (HLD) have made it feasible for formulators to improve products in many different applications using surfactants to attain a target system using HLD in its original or its normalized form, i.e., HLD_N. Thus, it can be said that there is still current progress being made towards an interdisciplinary applied science with numerical guidelines. In the present work, the state-of-the-art of formulation in multiphase systems containing two immiscible phases like oil and water, and therefore systems with heterogeneous or micro-heterogeneous interfaces, is discussed. Surfactants, from simple to complex or polymeric, are generally present in such systems to solve a wide variety of problems in many areas. Some significant cases are presented here as examples dealing with petroleum, foods, pharmaceutics, cosmetics, detergency, and other products occurring as dispersions, emulsions, or foams that we find in our everyday lives.

The oscillatory spinning drop method has been proven recently to be an accurate technique to measure dilational interfacial rheological properties. It is the only available equipment for measuring dilational moduli in low interfacial tension systems, as it is the case in applications dealing with surfactant-oil-water three-phase behavior like enhanced oil recovery, crude oil dehydration, or extreme microemulsion solubilization. Different systems can be studied, bubble-in-liquid, oil-in-water, microemulsion-in-water, oil-in-microemulsion, and systems with the presence of complex natural surfactants like asphaltene aggregates or particles. The technique allows studying the characteristics and properties of water/oil interfaces, particularly when the oil contains asphaltenes and when surfactants are present. In this work, we present a review of the measurements of crude oil-brine interfaces with the oscillating spinning drop technique. The review is divided into four sections. First, an introduction on the oscillating spinning drop technique, fundamental and applied concepts are presented. The three sections that follow are divided according to the complexity of the systems measured with the oscillating spinning drop, starting with simple surfactant-oil-water systems. Then the complexity increases, presenting interfacial rheology properties of crude oil-brine systems, and finally, more complex surfactant-crude oil-brine systems are reviewed. We have found that using the oscillating spinning drop method to measure interfacial rheology properties can help make precise measurements in a reasonable amount of time. This is of significance when systems with long equilibration times, e.g., asphaltene or high molecular weight surfactant-containing systems are measured, or with systems formulated with a demulsifier which is generally associated with low interfacial tension.

Leishmania parasites are the etiological agents of Leishmaniasis, a tropical disease that affects around 15 million people in about 90 countries. The chosen therapy for this disease is based on antimony V compounds, such as meglumine antimoniate. It can be administered as a parenteral, subcutaneous or perilesional form as successive infiltrations with pre-established doses localized in the border of the granuloma that characterizes the wound of Cutaneous Leishmaniasis (CL). Herein, a topical pharmaceutical recipe, such as an emulsion, is proposed to eliminate the trauma caused by administering the medicine in parenteral form to the face or other difficult access zones. The evaluation of this vehicle was performed by analyzing parameters such as pH, viscosity, homogeneity and droplet size distribution. Furthermore, the effectiveness of the emulsion was proved by in vitro experiments using Strat-M synthetic membranes, showing that the transdermal passage of the antimonial complex is guaranteed. Moreover, complete healing of the wound has been attained in patients with CL, as shown with two clinical cases in this article.