Biocompatible Microfabrication of 3D Isolation Chambers for Targeted Confinement of Individual Cells and Their Progeny

We describe a technique to physically isolate single/individual cells from their surrounding environment by fabricating three-dimensional microchambers around selected cells under biocompatible conditions. Isolation of targeted cells is achieved via rapid fabrication of protein hydrogels from a biocompatible precursor solution using multiphoton lithography, an intrinsically 3D laser direct write microfabrication technique. Cells remain chemically accessible to environmental cues enabling their propagation into well-defined, high density populations. We demonstrate this methodology on gram negative (<i>E. coli</i>), gram positive (<i>S. aureus</i>), and eukaryotic (<i>S. cerevisiae</i>) cells. The opportunities to confine viable, single/individual-cells and small populations within user-defined microenvironments afforded by this approach should facilitate the study of cell behaviors across multiple generations

Biocompatible Microfabrication of 3D Isolation Chambers for Targeted Confinement of Individual Cells and Their Progeny

We describe a technique to physically isolate single/individual cells from their surrounding environment by fabricating three-dimensional microchambers around selected cells under biocompatible conditions. Isolation of targeted cells is achieved via rapid fabrication of protein hydrogels from a biocompatible precursor solution using multiphoton lithography, an intrinsically 3D laser direct write microfabrication technique. Cells remain chemically accessible to environmental cues enabling their propagation into well-defined, high density populations. We demonstrate this methodology on gram negative (<i>E. coli</i>), gram positive (<i>S. aureus</i>), and eukaryotic (<i>S. cerevisiae</i>) cells. The opportunities to confine viable, single/individual-cells and small populations within user-defined microenvironments afforded by this approach should facilitate the study of cell behaviors across multiple generations

Mechanically Encoded Cellular Shapes for Synthesis of Anisotropic Mesoporous Particles

The asymmetry that pervades molecular mechanisms of living systems increasingly informs the aims of synthetic chemistry, particularly in the development of catalysts, particles, nanomaterials, and their assemblies. For particle synthesis, overcoming viscous forces to produce complex, nonspherical shapes is particularly challenging; a problem that is continuously solved in nature when observing dynamic biological entities such as cells. Here we bridge these dynamics to synthetic chemistry and show that the intrinsic asymmetric shapes of erythrocytes can be directed, captured, and translated into composites and inorganic particles using a process of nanoscale silica-bioreplication. We show that crucial aspects in particle design such as particle–particle interactions, pore size, and macromolecular accessibility can be tuned using cellular responses. The durability of resultant particles provides opportunities for shape-preserving transformations into metallic, semiconductive, and ferromagnetic particles and assemblies. The ability to use cellular responses as “structure directing agents” offers an unprecedented toolset to design colloidal-scale materials

Using Laser-Induced Thermal Voxels to Pattern Diverse Materials at the Solid–Liquid Interface

We describe a high-resolution patterning approach that combines the spatial control inherent to laser direct writing with the versatility of benchtop chemical synthesis. By taking advantage of the steep thermal gradient that occurs while laser heating a metal edge in contact with solution, diverse materials comprising transition metals are patterned with feature size resolution nearing 1 μm. We demonstrate fabrication of reduced metallic nickel in one step and examine electrical properties and air stability through direct-write integration onto a device platform. This strategy expands the chemistries and materials that can be used in combination with laser direct writing

Molecular Tuning of the Vibrational Thermal Transport Mechanisms in Fullerene Derivative Solutions

Control over the thermal conductance from excited molecules into an external environment is essential for the development of customized photothermal therapies and chemical processes. This control could be achieved through molecule tuning of the chemical moieties in fullerene derivatives. For example, the thermal transport properties in the fullerene derivatives indene-C₆₀ monoadduct (ICMA), indene-C₆₀ bisadduct (ICBA), [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM), [6,6]-phenyl C₆₁ butyric acid butyl ester (PCBB), and [6,6]-phenyl C₆₁ butyric acid octyl ester (PCBO) could be tuned by choosing a functional group such that its intrinsic vibrational density of states bridge that of the parent molecule and a liquid. However, this effect has never been experimentally realized for molecular interfaces in liquid suspensions. Using the pump–probe technique time domain thermotransmittance, we measure the vibrational relaxation times of photoexcited fullerene derivatives in solutions and calculate an effective thermal boundary conductance from the opto-thermally excited molecule into the liquid. We relate the thermal boundary conductance to the vibrational modes of the functional groups using density of states calculations from molecular dynamics. Our findings indicate that the attachment of an ester group to a C₆₀ molecule, such as in PCBM, PCBB, and PCBO, provides low-frequency modes which facilitate thermal coupling with the liquid. This offers a channel for heat flow in addition to direct coupling between the buckyball and the liquid. In contrast, the attachment of indene rings to C₆₀ does not supply the same low-frequency modes and, thus, does not generate the same enhancement in thermal boundary conductance. Understanding how chemical functionalization of C₆₀ affects the vibrational thermal transport in molecule/liquid systems allows the thermal boundary conductance to be manipulated and adapted for medical and chemical applications

Laser Direct Write Synthesis of Lead Halide Perovskites

Lead halide perovskites are increasingly considered for applications beyond photovoltaics, for example, light emission and detection, where an ability to pattern and prototype microscale geometries can facilitate the incorporation of this class of materials into devices. Here we demonstrate laser direct write of lead halide perovskites, a remarkably simple procedure that takes advantage of the inverse dependence between perovskite solubility and temperature by using a laser to induce localized heating of an absorbing substrate. We demonstrate arbitrary pattern formation of crystalline CH₃NH₃PbBr₃ on a range of substrates and fabricate and characterize a microscale photodetector using this approach. This direct write methodology provides a path forward for the prototyping and production of perovskite-based devices

Controlling the Metal to Semiconductor Transition of MoS₂ and WS₂ in Solution

Lithiation-exfoliation produces single to few-layered MoS₂ and WS₂ sheets dispersible in water. However, the process transforms them from the pristine semiconducting 2H phase to a distorted metallic phase. Recovery of the semiconducting properties typically involves heating of the chemically exfoliated sheets at elevated temperatures. Therefore, it has been largely limited to sheets deposited on solid substrates. Here, we report the dispersion of chemically exfoliated MoS₂ sheets in high boiling point organic solvents enabled by surface functionalization and the controllable recovery of their semiconducting properties directly in solution. This process connects the scalability of chemical exfoliation with the simplicity of solution processing, ultimately enabling a facile method for tuning the metal to semiconductor transitions of MoS₂ and WS₂ within a liquid medium