Tear-film instability is widely believed to be a signature of eye health. When an interblink is prolonged, randomly distributed ruptures occur in the tear film. "Black spots" and/or "black streaks" appear in 15 to 40 s for normal individuals. For people who suffer from dry eye, tear-film breakup time (BUT) is typically less than a few seconds. To date, however, there is no satisfactory quantitative explanation for the origin of tear rupture. Recently, it was proposed that tear-film breakup is related to locally high evaporative thinning. A spatial variation in the thickness of the tear-film lipid layer (TFLL) may lead to locally elevated evaporation and subsequent tear-film breakup. We examine the local-evaporation-driven tear-film-rupture hypothesis in a one-dimensional (1-D) model for the evolution of a thin aqueous tear film overriding the cornea subject to locally elevated evaporation at its anterior surface and osmotic water influx at its posterior surface. Evaporation rate depends on mass transfer both through the coating lipid layer and through ambient air. We establish that evaporation-driven tear-film breakup can occur under normal conditions but only for higher aqueous evaporation rates. Predicted roles of environmental conditions, such as wind speed and relative humidity, on tear-film stability agree with clinical observations. More importantly, locally elevated evaporation leads to hyperosmolar spots in the tear film and, hence, vulnerability to epithelial irritation. In addition to evaporation rate, tear-film instability depends on the strength of healing flow from the neighboring region outside the breakup region, which is determined by the surface tension at the tear-film surface and by the repulsive thin-film disjoining pressure. This study provides a physically consistent and quantitative explanation for the formation of black streaks and spots in the human tear film during an interblink.

We studied meibum architecture and its relation to bulk and interfacial rheology. Bovine and human meibomian lipids exhibit similar physical properties. From all structural probes utilized, we find a melt transition near eye temperature at which lamellar crystals liquefy. Our proposed structure for the tear-film lipid layer at physiologic temperature is a highly viscoelastic, shear-thinning liquid suspension consisting of lipid lamellar-crystallite particulates immersed in a continuous liquid phase with no long-range order. When spread over on-eye tear, the TFLL is a duplex film that exhibits bulk liquid properties and two separate interfaces, air/lipid and water/lipid, with aqueous protein and surfactantlike lipids adsorbed at the water/lipid surface.

Water-evaporation reduction by duplex-oil films is especially important to understand the physiology of the human tear film. Secreted lipids, called meibum, form a duplex film that coats the aqueous tear film and purportedly reduces tear evaporation. Lipid-layer deficiency is correlated with the occurrence of dry-eye disease; however, in-vitro experiments fail to show water-evaporation reduction by tear-lipid duplex films. We review the available literature on water-evaporation reduction by duplex-oil films and outline the theoretical underpinnings of spreading and evaporation kinetics that govern behavior of these systems. A dissolution-diffusion model unifies the data reported in the literature and identifies dewetting of duplex films into lenses as a key challenge to obtaining significant evaporation reduction. We develop an improved apparatus for measuring evaporation reduction by duplex-oil films including simultaneous assessment of film coverage, stability, and temperature, all under controlled external mass transfer. New data reported in this study fit into the larger body of work conducted on water-evaporation reduction by duplex-oil films. Duplex-oil films of oxidized mineral oil/mucin (MOx/BSM), human meibum (HM), and bovine meibum (BM) reduce water evaporation by a dissolution-diffusion mechanism, as confirmed by agreement between measurement and theory. The water permeability of oxidized-mineral-oil duplex films agrees with those reported in the literature, after correction for the presence of mucin. We find that duplex-oil films of bovine and human meibum at physiologic temperature reduce water evaporation only 6-8% for a 100-nm film thickness pertinent to the human tear film. Comparison to in-vivo human tear-evaporation measurements is inconclusive because evaporation from a clean-water surface is not measured and because the mass-transfer resistance is not characterized.

Meibum is the primary component of the tear film lipid layer. Thought to play a role in tear film stabilization, understanding the physical properties of meibum and how they change with disease will be valuable in identifying dry eye treatment targets. Grazing incidence X-ray diffraction and X-ray reflectivity were applied to meibum films at an air-water interface to identify molecular organization. At room temperature, interfacial meibum films formed two coexisting scattering phases with rectangular lattices and next-nearest neighbor tilts, similar to the Ov phase previously identified in fatty acids. The intensity of the diffraction peaks increased with compression, although the lattice spacing and molecular tilt angle remained constant. Reflectivity measurements at surface pressures of 18 mN/m and above revealed multilayers with d-spacings of 50 Å, suggesting that vertical organization rather than lateral was predominantly affected by meibum-film compression.

The compartmental periodic-steady tear-dynamics model accurately predicts tear behavior in normal and dry eyes. Inclusion of osmotic water flow is crucial to match measured tear osmolarity. Tear-dynamics predictions corroborate the use of TTR as a clinical discriminator between ADDE and EDE. The proposed model is readily extended to predict the dynamics of aqueous solutes such as drugs or fluorescent tags.

A novel in vivo flow evaporimeter is developed to measure human tear-evaporation rates. The flow evaporimeter relies on a well-defined flow field to the eye with known and adjustable flow rates and relative humidities, and quantitatively reproduces evaporation rates for pure water. Mass-transfer analysis of the evaporimeter data elucidates, for the first time, the resistance of the human tear-film lipid layer (TFLL) toward minimizing tear loss to the environment. A pilot study on human subjects validates the feasibility of the flow evaporimeter to obtain the tear-film evaporation rates in vivo. Resistance of the TFLL against tear evaporation is found subject specific. Our flow evaporimeter offers an accurate, safe, and convenient diagnostic tool for clinical evaluation of dry-eye-related maladies.

Removal of dilute bioproducts from fermenter broths is a major challenge both to avoid microbe inhibition and to recover solutes economically without water loss. We analyze a proposed new process, membrane vapor extraction (MVE), where semi‐volatile dilute aqueous solutes vaporize at the upstream side of an omniphobic, microporous membrane and dissolve into a nonpolar solvent highly favorable to the solutes but not to water. A new membrane‐process analysis is outlined and applied to the countercurrent recovery of 2 wt % aqueous butanol by a prototype solvent (dodecane) at 40°C. Thermodynamic phase equilibria, pioneered by the Prausnitz school, are crucial to MVE process design. Over 90% of the feed butanol is recovered with essentially no water loss giving a separation factor of over 1000. Energy requirements in MVE are low. Our design calculations demonstrate that MVE is a viable separation process to remove and recover dilute aqueous biosolutes. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2795–2809, 2015

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