From Glucose to Polymers: A Continuous Chemoenzymatic Process

Efforts to synthesize degradable polymers from renewable resources are deterred by technical and economic challenges; especially, the conversion of natural building blocks into polymerizable monomers is inefficient, requiring multistep synthesis and chromatographic purification. Herein we report a chemoenzymatic process to address these challenges. An enzymatic reaction system was designed that allows for regioselective functional group transformation, efficiently converting glucose into a polymerizable monomer in quantitative yield, thus removing the need for chromatographic purification. With this key success, we further designed a continuous, three-step process, which enabled the synthesis of a sugar polymer, sugar poly(orthoester), directly from glucose in high yield (73 % from glucose). This work may provide a proof-of-concept in developing technically and economically viable approaches to address the many issues associated with current petroleum-based polymers.     

Visible-Light Photoswitching by Azobenzazoles

Three visible-light responsive photoswitches are reported, azobis(1-methyl-benzimidazole) ( 1 ), azobis(benzoxazole) ( 2 ) and azobis(benzothiazole) ( 3 ). Photostationary distributions are obtained upon irradiation with visible light comprising approximately 80 % of the thermally unstable isomer, with thermal half-lives up to 8 min and are mostly invariant to solvent. On protonation, compound 1 H⁺ has absorption extending beyond 600 nm, allowing switching with yellow light, and a thermal half-life just under 5 minutes. The two isomers have significantly different pK_a values, offering potential as a pH switch. The absorption spectra of 2 and 3 are insensitive to acid, although changes in the thermal half-life of 3 indicate more basic intermediates that significantly influence the thermal barrier to isomerization. These findings are supported by high-level ab initio calculations, which validate that protonation occurs on the ring nitrogen and that the Z isomer is more basic in all cases.     

Boundaries of weak peak points in noncommutative algebras of Lipschitz functions

It has been shown that any Banach algebra satisfying ‖f ²‖ = ‖f‖² has a representation as an algebra of quaternion-valued continuous functions. Whereas some of the classical theory of algebras of continuous complex-valued functions extends immediately to algebras of quaternion-valued functions, similar work has not been done to analyze how the theory of algebras of complex-valued Lipschitz functions extends to algebras of quaternion-valued Lipschitz functions. Denote by Lip(X, \mathbbF\mathbb{F}) the algebra over R of F-valued Lipschitz functions on a compact metric space (X, d), where \mathbbF\mathbb{F} = ℝ, ℂ, or ℍ, the non-commutative division ring of quaternions. In this work, we analyze a class of subalgebras of Lip(X, \mathbbF\mathbb{F}) in which the closure of the weak peak points is the Shilov boundary, and we show that algebras of functions taking values in the quaternions are the most general objects to which the theory of weak peak points extends naturally. This is done by generalizing a classical result for uniform algebras, due to Bishop, which ensures the existence of the Shilov boundary. While the result of Bishop need not hold in general algebras of quaternion-valued Lipschitz functions, we give sufficient conditions on such an algebra for it to hold and to guarantee the existence of the Shilov boundary.     

Structural stability and optical properties of nanomaterials with reconstructed surfaces

We present density functional and quantum Monte Carlo calculations of the stability and optical properties of semiconductor nanomaterials with reconstructed surfaces. We predict the relative stability of silicon nanostructures with reconstructed and unreconstructed surfaces, and we show that surface step geometries unique to highly curved surfaces dramatically reduce the optical gaps and decrease excitonic lifetimes. These predictions provide an explanation of both the variations in the photoluminescence spectra of colloidally synthesized nanoparticles and observed deep gap levels in porous silicon.     

Beliefs,Practical Knowledge,and Context: A Longitudinal Study of a Beginning Biology Teacher's 5E Unit

The purpose of this three‐year case study was to understand how a beginning biology teacher (Alice) designed and taught a 5E unit on natural selection, how the unit changed when she took a position in a different school district, and why the changes occurred. We examined Alice's developing beliefs about science teaching and learning, practical knowledge, and perceptions of school context in relation to the 5E unit. Data sources consisted of interviews, classroom observations, and lesson materials. We found that Alice placed more emphasis on the explore phase, less emphasis on the engage and explain phases, and removed the elaborate phase over time. Alice's beliefs about science teaching and learning acted as a filter for making sense of practical knowledge and perceptions of context. Although her beliefs were student centered, they aligned with discovery learning in which little intervention from the teacher is required. We discuss how her beliefs, practical knowledge, and perceptions of context explained the changes in her practice. This study sheds insight into the nature of beliefs and how they relate to the 5E lesson phases, as well as the different lenses for viewing the 5E instructional model. Implications for science teacher preparation and induction programs are discussed.     

Not All Fluorescent Nanodiamonds Are Created Equal: A Comparative Study

Fluorescent nanodiamonds (FNDs) are vital to many emerging nanotechnological applications, from bioimaging and sensing to quantum nanophotonics. Yet, understanding and engineering the properties of fluorescent defects in nanodiamonds remain challenging. The most comprehensive study to date is presented, of the optical and physical properties of five different nanodiamond samples, in which fluorescent nitrogen‐vacancy (NV) centers are created using different fabrication techniques. The FNDs' fluorescence spectra, lifetime, and spin relaxation time (T₁) are investigated via single‐particle confocal fluorescence microscopy and in ensemble measurements in solution (T₁ excepted). Particle sizes and shapes are determined using scanning electron microscopy and correlated with the optical results. Statistical tests are used to explore correlations between the properties of individual particles and also analyze average results to directly compare different fabrication techniques. Spectral unmixing is used to quantify the relative NV charge‐state (NV^? and NV⁰) contributions to the overall fluorescence. A strong variation is found and quantified in the properties of individual particles within all analyzed samples and significant differences between the different particle types. This study is an important contribution toward understanding the properties of NV centers in nanodiamonds. It motivates new approaches to the improved engineering of NV‐containing nanodiamonds for future applications.     

Long-term trend in CHF2Cl (HCFC-22) from high spectral resolution infrared solar absorption measurements and comparison with in situ measurements

The average tropospheric volume mixing ratio of CHF₂Cl (HCFC-22) has been retrieved from a time series of high spectral resolution ground-based infrared solar absorption spectra recorded with the McMath Fourier transform spectrometer located at the U.S. National Solar Observatory facility on Kitt Peak in southern Arizona (31.9°N, 111.6°W, 2.09 km altitude) for the time period October 1987–November 2002. The retrievals are based on fits to the well-isolated, unresolved 2ν₆ Q branch at 829.05 cm⁻¹ and the SFIT2 retrieval algorithm. The measured daily averages show a near linear rise per year in the mean tropospheric volume mixing ratio as a function of time with a best fit yielding an average increase rate of (5.66±0.15) parts per trillion (10⁻¹²) by volume per year, corresponding to (6.47±0.17)%yr⁻¹, 1 sigma, at the beginning of the time series. The tropospheric mixing ratios retrieved from the solar spectra have been compared with monthly average surface flask sampling measurements from the Climate Monitoring and Diagnostic Laboratory (CMDL) station at Niwot Ridge, Colorado (40.0°N, 105.5°W, 3013 m altitude), archived measurement from the same location, and early CMDL northern hemisphere Pacific cruise measurements. The average ratio of the retrieved tropospheric mixing ratio relative to the CMDL surface mixing ratio is 1.053 for the overlapping 1987 to 2002 time period. The retrieved mean tropospheric mixing ratio is consistent with the surface measurements within the errors estimated for the remote sensing observations.