γ-Graphyne is the most symmetric sp 2 /sp 1 allotrope of carbon, which can be viewed as graphene uniformly expanded through the insertion of two-carbon acetylenic units between all the aromatic rings. To date, synthesis of bulk γ-graphyne has remained a challenge. We here report the synthesis of multilayer γ-graphyne through crystallization-assisted irreversible cross-coupling polymerization. A comprehensive characterization of this new carbon phase is described, including synchrotron powder X-ray diffraction, electron diffraction, lateral force microscopy, Raman spectroscopy, infrared spectroscopy, and cyclic voltammetry. Experiments indicate that γ-graphyne is a 0.48 eV band gap semiconductor, with a hexagonal a-axis spacing of 6.88 Å and an interlayer spacing of 3.48 Å, which is consistent with theoretical predictions. The observed crystal structure has an aperiodic sheet stacking. The material is thermally stable up to 240 °C but undergoes transformation at higher temperatures. While conventional 2D polymerization and reticular chemistry rely on error correction through reversibility, we demonstrate that a periodic covalent lattice can be synthesized under purely kinetic control. The reported methodology is scalable and inspires extension to other allotropes of the graphyne family.

Developing well‐defined iron‐based catalysts for olefin metathesis would be a breakthrough achievement in the field not only to replace existing catalysts by inexpensive metals but also to attain a new reactivity taking advantage of the unique electronic structure of the base metals. Here, we present a two‐coordinate homoleptic iron complex, Fe(HMTO)2 [HMTO=O‐2,6‐(2,4,6‐Me3C6H2)2C6H3], that is capable of performing ring‐opening metathesis polymerization of norbornene to produce highly stereoregular polynorbornene (99 % cis, syndiotactic). The use of heteroleptic Fe(HMTO)(RO) [RO=(CH3)2CF3CO, CH3(CF3)2CO, or Ph(CF3)2CO] prepared in situ significantly increases the polymerization rate while preserving selectivity. The resulting polymers were characterized by 1H and 13C NMR spectroscopy and gel‐permeation chromatography.

Evanescent wave cavity ring-down spectroscopy (EW-CRDS) is used to observe the adsorption isotherm for hemoglobin (Hb) from controlled urine samples to assess the potential for rapid diagnosis in hemoglobinuria. The absorbance of Hb at 425 nm is monitored using an alexandrite laser-pumped, room temperature, LiF:F2+** color-center pulsed laser. A minimum absorbance detection level of 2.57 x 10(-4) is achieved, corresponding to a minimum detectable concentration of Hb in urea of 5.8 nM. A multilayered Hb biofilm is formed, and a minimum of eight layers are required to model the adsorption isotherm, allowing for cooperative binding within the layers and extending 56 nm into the interface. A binding constant for Hb to silica 18.23+/-7.58 x 10(6) M is derived, and a binding constant for Hb to Hb in subsequent layers is determined to be 5.631+/-0.432 x 10(5) M. Stoichiometric binding coefficients of 1.530+/-0.981 for layer one and 1.792+/-0.162 for subsequent layers suggest that cooperative binding both to the silica surface and between the layers of the biofilm is important.

Tight glucose monitoring is essential for the reduction of diabetic complications. This research investigated the changes of absorption spectra observed in serum at three prominent glucose absorption peaks in the middle infrared using a demountable liquid, transmission cell. Two frequencies of light were used to determine the glucose absorption: one at 1193 cm(-1 ) to determine the background water absorption and the other at one of the characteristic peaks (1035, 1080, and 1109 cm(-1)). The peak at 1035 cm(-1) was best for quantitative determination with a standard of error of 20.6 mg/dl (1.1 mmol/L). While interference from other serum constituents could cause problems, urea and albumin-two constituents known to have close absorption peaks-were determined to have no effect on the ability to determine the glucose levels at 1035 cm( -1).

Advances in middle infrared technology are leading researchers beyond the Fourier transform infrared spectrometer and to the quantum cascade laser. While most research focuses on gas-phase detection, recent research explores its use for condensed-phase matter studies. This work investigates its use for monitoring biologically relevant samples of glucose in serum. Samples with physiological glucose concentrations were monitored with a laser at 1036 cm-1. A 0.992 R2 linearity value was observed. In addition, using another laser at 1194 cm-1 as a measure of the background spectroscopic characteristics, a linearity of 0.998 R2 was observed. The average predictive standard errors of the mean (SEM) were 32.5 and 24.7 mg/dL, respectively, for each method. Quantum cascade lasers could be used to develop middle infrared devices for uses beyond the confines of the laboratory.