Iron oxide nanoparticles are formidable multifunctional systems capable of contrast enhancement in magnetic resonance imaging; guidance under remote fields; heat generation; and biodegradation. Yet, this potential is underutilized in that each function manifests at different nanoparticle sizes. Here, sub-micrometer discoidal magnetic nanoconstructs are realized by confining 5 nm ultra-small super-paramagnetic iron oxide nanoparticles (USPIOs) within two different mesoporous structures, made out of silicon and polymers. These nanoconstructs exhibit transversal relaxivities up to ~10 times (r2 ~ 835 (mM·s)−1) higher than conventional USPIOs and, under external magnetic fields, collectively cooperate to amplify tumor accumulation. The boost in r2 relaxivity arises from the formation of mesoscopic USPIO clusters within the porous matrix, inducing a local reduction in water molecule mobility as demonstrated via molecular dynamics simulations. The cooperative accumulation under static magnetic field derives from the large amount of iron that can be loaded per nanoconstuct (up to ~ 65 fg) and the consequent generation of significant inter-particle magnetic dipole interactions. In tumor bearing mice, the silicon-based nanoconstructs provide MRI contrast enhancement at much smaller doses of iron (~ 0.5 mg of Fe/kg animal) as compared to current practice.

We introduce a novel and simple method to fabricate calcium carbonate (CaCO) micromodels by in situ growing a thin layer of CaCO nanocrystals with a thickness of 1-2 μm in microfluidic channels. This approach enables us to fabricate synthetic CaCO reservoir micromodels having surfaces fully covered with calcite, while the dimensions and geometries of the micromodels are controllable on the basis of the original microfluidic channels. We have tuned the wettability of the CaCO-coated microchannels at simulated oil reservoir conditions without introducing any chemical additives to the system; thus the resulting oil-wet surface makes the micromodel more faithfully resemble a natural carbonate reservoir rock. With the advantage of its excellent optical transparency, the micromodel allows us to directly visualize the complex multiphase flows and geochemical fluid-calcite interactions by spectroscopic and microscopic imaging techniques. The CaCO-coated microfluidic channels provide new capabilities as a micromodel system to mimic real carbonate reservoir properties, which would allow us to perform a water-oil displacement experiment in small-volume samples for the rapid screening of candidate fluids for enhanced oil recovery (EOR). The immiscible fluid displacement process within carbonate micromodels has been demonstrated showing the water-oil-carbonate interactions at pore-scale in real time by fluorescence microscopic imaging.

Enhanced oil recovery (EOR) plays a significant role in improving oil production. Tertiary EOR, including surfactant flooding, can potentially mobilize residual oil after water flooding. Prior to the field deployment, the surfactant performance must be evaluated using site-specific crude oil at reservoir conditions. Core flood experiments are common practice to evaluate surfactants for oil displacement efficiency using core samples. Core flood experiments, however, are expensive and time-consuming and do not allow for pore scale observations of fluid-fluid interactions. This work introduces the framework to evaluate the performance of EOR surfactants via a Reservoir-on-a-Chip approach, which uses microfluidic devices to mimic the oil reservoir. A unique feature of this study is the use of chemically modified micromodels such that the pore surfaces are representative of carbonate reservoir rock. To represent calcium carbonate reservoir pores, the inner channels of glass microfluidic devices were coated with thin layers of calcium carbonate nanocrystals and the surface was modified to exhibit oil-wet conditions through a crude oil aging process. During surfactant screening, oil and water phases were imaged by fluorescence microscopy to reveal the micro to macro scale mechanisms controlling surfactant-assisted oil recovery. The role of the interfacial tension (IFT) and wettability in the microfluidic device was simulated using a phase-field model and compared to laboratory results. We demonstrated the effect of low IFT at the oil-water interface and wettability alteration on surfactant-enhanced oil displacement efficiency; thus providing a time-efficient and low-cost strategy for quantitative and qualitative assessment. In addition, this framework is an effective method for prescreening EOR surfactants for use in carbonate reservoirs prior to further core and field scale testing. Crude oil is used to produce gasoline and petrochemicals that are later used to manufacture a variety of consumer goods. Therefore, oil production significantly affects the global economy and as such, improving oil recovery is a high priority 1. Oil recovery is initiated by a geological investigation to identify oil and gas reservoirs. Once reservoirs are identified, injector and producer wells are drilled in strategic locations. During primary hydrocarbon recovery (depletion), reservoir pressure drives hydrocarbons from the reservoir to the surface through the complex pore network of the reservoir rock. In many cases, primary recovery is followed by secondary recovery where water is injected to push hydrocarbons to the producer wells. Rock properties, including wettability, capillarity, and permeability, vary and affect hydrocarbon recovery efficiency. Typically, only 30-50% of original oil

Porous silicon has been used for the delivery of therapeutic and imaging agents in several biomedical applications. Here, mesoporous silicon nanoconstructs (SiMPs) with a discoidal shape and a sub-micrometer size (1,000 × 400 nm) have been conjugated with gadolinium-tetraazacyclododecane tetraacetic acid Gd(DOTA) molecules and proposed as contrast agents for Magnetic Resonance Imaging. The surface of the SiMPs with different porosities – small pore (SP: ~ 5 nm) and huge pore (HP: ~ 40 nm) – and of bulk, non-porous silica beads (1,000 nm in diameter) have been modified with covalently attached (3-aminopropyl)triethoxysilane (APTES) groups, conjugated with DOTA molecules, and reacted with an aqueous solution of GdCl3. The resulting Gd(DOTA) molecules confined within the small pores of the Gd-SiMPs achieve longitudinal relaxivities r1 of ~ 17 (mM·s)−1, which is 4 times greater than for free Gd(DOTA). This enhancement is ascribed to the confinement and stable chelation of Gd(DOTA) molecules within the SiMP mesoporous matrix. The resulting nanoconstructs possess no cytotoxicity and accumulate in ovarian tumors up to 2% of the injected dose per gram tissue, upon tail vein injection. All together this data suggests that Gd-SiMPs could be efficiently used for MR vascular imaging in cancer and other diseases.