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Single-walled zeolite nanotubes (ZNT) were recently synthesized in a narrow compositional window. ZNT structural features-thin zeolitic walls and large mesopores-can allow for easy access of small molecules to zeolite micropores, but they also impart processing limitations for these materials, such as challenges with conventional aqueous ion-exchange conditions. Conventional solid- and liquid-phase ion exchange of calcined NaOH-derived ZNT (NaH-ZNT) results in structural degradation to either 2D sheet-like phases, 3D nanocrystals, or amorphous phases, motivating different direct synthesis routes and unconventional ion-exchange procedures of uncalcined ZNT precursors. Here, a modified synthesis route for ZNT synthesis is introduced that facilitates facile ion exchange as well as incorporation of additional non-Al heteroatoms in the zeolite framework. Tetrabutylammonium hydroxide (TBAOH) is used as a hydroxide source and co-OSDA, enabling synthesis of new compositions of ZNT, otherwise unachievable by post-modification of previously reported NaH-ZNT. By varying the gel composition, synthesis temperature, crystallization time, hydroxide source, silicon source, and aluminum source, productive conditions for the new TBAOH synthesis are developed, leading to increased strong acid site density in the ZNT. The collected results demonstrate the sensitivity of the ZNT synthesis to many key parameters and show that the ZNT forms only when Si/(Al + T) ∼ 30 in these synthesis gels and with specific Si and Al sources, and always in the presence of trace Na + . Catalytic testing, via the tandem CO 2 hydrogenation to methanol and methanol to aromatics reaction, shows that ZNTs provide adequate catalytic activity (acidity), relative to their conventional 3D counterparts in converting methanol to aromatic compounds., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The challenges in reliably removing the sacrificial material from fully enclosed microfluidic channels hinder the use of three-dimensional (3D) printing to create microfluidic devices with intricate geometries. With advances in printer resolution, the etching of sacrificial materials from increasingly smaller channels is poised to be a bottleneck using the existing techniques. In this study, we introduce a microfabrication approach that utilizes centrifugation to effortlessly and efficiently remove the sacrificial materials from 3D-printed microfluidic devices with densely packed microfeatures. We characterize the process by measuring the etch rate under different centrifugal forces and developed a theoretical model to estimate process parameters for a given geometry. The effect of the device layout on the centrifugal etching process is also investigated. We demonstrate the applicability of our approach on devices fabricated using inkjet 3D printing and stereolithography. Finally, the advantages of the introduced approach over commonly used injection-based etching of sacrificial material are experimentally demonstrated in direct comparisons. A robust method to postprocess additively manufactured geometries composed of intricate microfluidic channels can help utilize both the large printing volume and high spatial resolution afforded by 3D printing in creating a variety of devices ranging from scaffolds to large-scale microfluidic assays., Competing Interests: There are no conflicts of interest to declare., (Copyright 2023, Mary Ann Liebert, Inc., publishers.)

Previous research has demonstrated that amine polymers rich in primary and secondary amines supported on mesoporous substrates are effective, selective sorbent materials for removal of CO 2 from simulated flue gas and air. Common substrates used include mesoporous alumina and silica (such as SBA-15 and MCM-41). Conventional microporous materials are generally less effective, since the pores are too small to support low volatility amines. Here, we deploy our newly discovered zeolite nanotubes, a first-of-their-kind quasi-1D hierarchical zeolite, as a substrate for poly(ethylenimine) (PEI) for CO 2 capture from dilute feeds. PEI is impregnated into the zeolite at specific organic loadings. Thermogravimetric analysis and porosity measurements are obtained to determine organic loading, pore filling, and surface area of the supported PEI prior to CO 2 capture studies. MCM-41 with comparable pore size and surface area is also impregnated with PEI to provide a benchmark material that allows for insight into the role of the zeolite nanotube intrawall micropores on CO 2 uptake rates and capacities. Over a range of PEI loadings, from 20 to 70 w/w%, the zeolite allows for increased CO 2 capture capacity over the mesoporous silica by ∼25%. Additionally, uptake kinetics for nanotube-supported PEI are roughly 4 times faster than that of a comparable PEI impregnated in SBA-15. It is anticipated that this new zeolite will offer numerous opportunities for engineering additional advantaged reaction and separation processes., Competing Interests: The authors declare the following competing financial interest(s): C.W.J. has a financial interest in Global Thermostat Operations, LLC. Georgia Tech has a conflict of interest management plan in place for C.W.J., (© 2023 The Authors. Published by American Chemical Society.)

Isolation and analysis of circulating tumor cells (CTCs) from blood samples present exciting opportunities for basic cancer research and personalized treatment of the disease. While microchip-based negative CTC enrichment offers both sensitive microfluidic cell screening and unbiased selection, conventional microchips are inherently limited by their capacity to deplete a large number of normal blood cells. In this paper, we use 3D printing to create a monolithic device that combines immunoaffinity-based microfluidic cell capture and a commercial membrane filter for negative enrichment of CTCs directly from whole blood. In our device, stacked layers of chemically-functionalized microfluidic channels capture millions of white blood cells (WBCs) in parallel without getting saturated and the leuko-depleted blood is post-filtered with a 3 μm-pore size membrane filter to eliminate anucleated blood cells. This hybrid negative enrichment approach facilitated direct extraction of viable CTCs off the chip on a membrane filter for downstream analysis. Immunofluorescence imaging of enriched cells showed ∼90% tumor cell recovery rate from simulated samples spiked with prostate, breast or ovarian cancer cells. We also demonstrated the feasibility of our approach for processing clinical samples by isolating prostate cancer CTCs directly from a 10 mL whole blood sample.