Template-Directed Synthesis of Strained meso-meso-Linked Porphyrin Nanorings.

Strained macrocycles display interesting properties, such as conformational rigidity, often resulting in enhanced π-conjugation or enhanced affinity for non-covalent guest binding, yet they can be difficult to synthesize. Here we use computational modeling to design a template to direct the formation of an 18-porphyrin nanoring with direct meso-meso bonds between the porphyrin units. Coupling of a linear 18-porphyrin oligomer in the presence of this template gives the target nanoring, together with an unexpected 36-porphyrin ring by-product. Scanning tunneling microscopy (STM) revealed the elliptical conformations and flexibility of these nanorings on a Au(111) surface.

Covalent Template-Directed Synthesis of a Spoked 18-Porphyrin Nanoring.

Rings of porphyrins mimic natural light-harvesting chlorophyll arrays and offer insights into electronic delocalization, providing a motivation for creating larger nanorings with closely spaced porphyrin units. Here, we demonstrate the first synthesis of a macrocycle consisting entirely of 5,15-linked porphyrins. This porphyrin octadecamer was constructed using a covalent six-armed template, made by cobalt-catalyzed cyclotrimerization of an H-shaped tolan with porphyrin trimer ends. The porphyrins around the circumference of the nanoring were linked together by intramolecular oxidative meso-meso coupling and partial ß-ß fusion, to give a nanoring consisting of six edge-fused zinc(II) porphyrin dimer units and six un-fused nickel(II) porphyrins. STM imaging on a gold surface confirms the size and shape of the spoked 18-porphyrin nanoring (calculated diameter: 4.7 nm).

A soft x-ray probe of a titania photoelectrode sensitized with a triphenylamine dye.

We present a thorough soft x-ray photoelectron spectroscopy (XPS) study of a mesoporous titanium dioxide electrode sensitized with the dye 4-(diphenylamino)phenylcyanoacrylic acid, referred to as "L0." Supported by calculations, the suite of XPS, x-ray absorption spectroscopy, and resonant photoelectron spectroscopy allows us to examine bonding interactions between the dye and the surface and the frontier electronic structure at the molecule-oxide interface. While placing these measurements in the context of existing literature, this paper is intended as a useful reference for further studies of more complex triphenylamine based sensitizers.

Porphyrin-fused graphene nanoribbons.

Graphene nanoribbons (GNRs), nanometre-wide strips of graphene, are promising materials for fabricating electronic devices. Many GNRs have been reported, yet no scalable strategies are known for synthesizing GNRs with metal atoms and heteroaromatic units at precisely defined positions in the conjugated backbone, which would be valuable for tuning their optical, electronic and magnetic properties. Here we report the solution-phase synthesis of a porphyrin-fused graphene nanoribbon (PGNR). This PGNR has metalloporphyrins fused into a twisted fjord-edged GNR backbone; it consists of long chains (>100 nm), with a narrow optical bandgap (~1.0 eV) and high local charge mobility (>400 cm2 V-1 s-1 by terahertz spectroscopy). We use this PGNR to fabricate ambipolar field-effect transistors with appealing switching behaviour, and single-electron transistors displaying multiple Coulomb diamonds. These results open an avenue to π-extended nanostructures with engineerable electrical and magnetic properties by transposing the coordination chemistry of porphyrins into graphene nanoribbons.

Simultaneous Nanorheometry and Nanothermometry Using Intracellular Diamond Quantum Sensors.

The viscoelasticity of the cytoplasm plays a critical role in cell morphology, cell division, and intracellular transport. Viscoelasticity is also interconnected with other biophysical properties, such as temperature, which is known to influence cellular bioenergetics. Probing the connections between intracellular temperature and cytoplasmic viscoelasticity provides an exciting opportunity for the study of biological phenomena, such as metabolism and disease progression. The small length scales and transient nature of changes in these parameters combined with their complex interdependencies pose a challenge for biosensing tools, which are often limited to a single readout modality. Here, we present a dual-mode quantum sensor capable of performing simultaneous nanoscale thermometry and rheometry in dynamic cellular environments. We use nitrogen-vacancy centers in diamond nanocrystals as biocompatible sensors for in vitro measurements. We combine subdiffraction resolution single-particle tracking in a fluidic environment with optically detected magnetic resonance spectroscopy to perform simultaneous sensing of viscoelasticity and temperature. We use our sensor to demonstrate probing of the temperature-dependent viscoelasticity in complex media at the nanoscale. We then investigate the interplay between intracellular forces and the cytoplasmic rheology in live cells. Finally, we identify different rheological regimes and reveal evidence of active trafficking and details of the nanoscale viscoelasticity of the cytoplasm.

Studying manganese carbonyl photochemistry in a permanently porous metal-organic framework.

Mn(diimine)(CO)3X (X = halide) complexes are critical components of chromophores, photo- and electrocatalysts, and photoactive CO-releasing molecules (photoCORMs). While these entities have been incorporated into metal-organic frameworks (MOFs), a detailed understanding of the photochemical and chemical processes that occur in a permanently porous support is lacking. Here we site-isolate and study the photochemistry of a Mn(diimine)(CO)3Br moiety anchored within a permanently porous MOF support, allowing for not only the photo-liberation of CO from the metal but also its escape from the MOF crystals. In addition, the high crystallinity and structural flexibility of the MOF allows crystallographic snapshots of the photolysis products to be obtained. We report these photo-crystallographic studies in the presence of coordinating solvents, THF and acetonitrile, showing the changing coordination environment of the Mn species as CO loss proceeds. Using time resolved experiments, we report complementary spectroscopic studies of the photolysis chemistry and characterize the final photolysis product as a possible Mn(ii) entity. These studies inform the chemistry that occurs in MOF-based photoCORMs and where these moieties are employed as catalysts.

Bending a photonic wire into a ring.

Natural light-harvesting systems absorb sunlight and transfer its energy to the reaction centre, where it is used for photosynthesis. Synthetic chromophore arrays provide useful models for understanding energy migration in these systems. Research has focused on mimicking rings of chlorophyll molecules found in purple bacteria, known as 'light-harvesting system 2'. Linear meso-meso linked porphyrin chains mediate rapid energy migration, but until now it has not been possible to bend them into rings. Here we show that oligo-pyridyl templates can be used to bend these rod-like photonic wires to create covalent nanorings that consist of 24 porphyrin units and a single butadiyne link. Their elliptical conformations have been probed by scanning tunnelling microscopy. This system exhibits two excited state energy transfer processes: one from a bound template to the peripheral porphyrins and one, in the template-free ring, from the exciton-coupled porphyrin array to the π-conjugated butadiyne-linked porphyrin dimer segment.

An institutional analysis of graduate outcomes reveals a contemporary workforce footprint for biomedical master's degrees.

There is continued growth in the number of master's degrees awarded in the life sciences to address the evolving needs of the biomedical workforce. Academic medical centers leverage the expertise of their faculty and industry partners to develop one to two year intensive and multidisciplinary master's programs that equip students with advanced scientific skills and practical training experiences. However, there is little data published on the outcomes of these graduates to evaluate the effectiveness of these programs and to inform the return on investment of students. Here, the authors show the first five-year career outlook for master of science graduates from programs housed at an academic medical center. Georgetown University Biomedical Graduate Education researchers analyzed the placement outcomes of 1,204 graduates from 2014-2018, and the two-year outcomes of 412 graduates from 2016 and 2017. From the 15 M.S. programs analyzed, they found that 69% of graduates entered the workforce, while 28% entered an advanced degree program such as a Ph.D., allopathic or osteopathic medicine (M.D. or D.O.), or health professions degree. International students who pursue advanced degrees largely pursued Ph.D. degrees, while domestic students represent the majority of students entering into medical programs. Researchers found that a majority of the alumni that entered the workforce pursue research-based work, with 59% of graduates conducting research-based job functions across industries. Forty-nine percent of employed graduates analyzed from 2016 and 2017 changed employment positions, while 15% entered advanced degree programs. Alumni that changed positions changed companies in the same job function, changed to a position of increasing responsibility in the same or different organization, or changed to a different job function in the same or different company. Overall, standalone master's programs equip graduates with research skills, analytical prowess, and content expertise, strengthening the talent pipeline of the biomedical workforce.

Three-Dimensional Printing and Electrospinning Dual-Scale Polycaprolactone Scaffolds with Low-Density and Oriented Fibers to Promote Cell Alignment.

Complex and hierarchically functionalized scaffolds composed of micro- and nanoscale structures are a key goal in tissue engineering. The combination of three-dimensional (3D) printing and electrospinning enables the fabrication of these multiscale structures. This study presents a polycaprolactone 3D-printed and electrospun scaffold with multiple mesh layers and fiber densities. The results show successful fabrication of a dual-scale scaffold with the 3D-printed scaffold acting as a gap collector with the printed microfibers as the electrodes and the pores a series of insulating gaps resulting in aligned nanofibers. The electrospun fibers are highly aligned perpendicular to the direction of the printed fiber and form aligned meshes within the pores of the scaffold. Mechanical testing showed no significant difference between the number of mesh layers whereas the hydrophobicity of the scaffold increased with increasing fiber density. Biological results indicate that increasing the number of mesh layers improves cell proliferation, migration, and adhesion. The aligned nanofibers within the microscale pores allowed enhanced cell bridging and cell alignment that was not observed in the 3D-printed only scaffold. These results demonstrate a facile method of incorporating low-density and aligned fibers within a 3D-printed scaffold that is a promising development in multiscale hierarchical scaffolds where alignment of cells can be desirable.

How do Self-Assembling Antimicrobial Lipopeptides Kill Bacteria?

Antimicrobial peptides are promising alternatives to traditional antibiotics. A group of self-assembling lipopeptides was formed by attaching an acyl chain to the N-terminus of α-helix-forming peptides with the sequence Cx-G(IIKK)yI-NH2 (CxGy, x = 4-12 and y = 2). CxGy self-assemble into nanofibers above their critical aggregation concentrations (CACs). With increasing x, the CACs decrease and the hydrophobic interactions increase, promoting secondary structure transitions within the nanofibers. Antimicrobial activity, determined by the minimum inhibition concentration (MIC), also decreases with increasing x, but the MICs are significantly smaller than the CACs, suggesting effective bacterial membrane-disrupting power. Unlike conventional antibiotics, both C8G2 and C12G2 can kill Staphylococcus aureus and Escherichia coli after only minutes of exposure under the concentrations studied. C12G2 nanofibers have considerably faster killing dynamics and lower cytotoxicity than their nonaggregated monomers. Antimicrobial activity of peptide aggregates has, to date, been underexploited, and it is found to be a very promising mechanism for peptide design. Detailed evidence for the molecular mechanisms involved is provided, based on superresolution fluorescence microscopy, solid-state nuclear magnetic resonance, atomic force microscopy, neutron scattering/reflectivity, circular dichroism, and Brewster angle microscopy.

Forefoot narrowing with external fixation for problem cleft wounds.

Healing of forefoot cleft wounds can be a difficult management problem in patients with peripheral vascular disease, diabetes or both. This is a prospective review of 15 patients with these conditions with nonhealing middle-ray cleft wounds managed with a temporary mini-external fixator to close the cleft wound. Fourteen (93%) of the 15 patients had a successful obliteration of the cleft and skin coverage. Twelve (80%) of 15 were able to resume their previous level of activity with the reconstructed, mechanically sound forefoot. Fourteen (93%) of the 15 patients received hyperbaric oxygen treatments as an adjunct to wound healing. All patients avoided a transmetatarsal or higher amputation.

Teaching for adaptive expertise in biomedical engineering ethics.

This paper considers an approach to teaching ethics in bioengineering based on the How People Learn (HPL) framework. Curricula based on this framework have been effective in mathematics and science instruction from the kindergarten to the college levels. This framework is well suited to teaching bioengineering ethics because it helps learners develop "adaptive expertise". Adaptive expertise refers to the ability to use knowledge and experience in a domain to learn in unanticipated situations. It differs from routine expertise, which requires using knowledge appropriately to solve routine problems. Adaptive expertise is an important educational objective for bioengineers because the regulations and knowledge base in the discipline are likely to change significantly over the course of their careers. This study compares the performance of undergraduate bioengineering students who learned about ethics for stem cell research using the HPL method of instruction to the performance of students who learned following a standard lecture sequence. Both groups learned the factual material equally well, but the HPL group was more prepared to act adaptively when presented with a novel situation.