A μ4‐oxide‐containing a dimeric variant of a sodium dialkyl(amido)zincate reagent

Post‐metallation derivatives of the sodium dialkyl(amido)zincate reagent (TMEDA)Na(μ‐TMP)Zn(^tBu)₂ (TMEDA is N,N,N′,N′‐tetramethylethylenediamine and TMP is 2,2,6,6‐tetramethylpiperidide) have been of structural interest due to the insight they give into aromatic metallation mechanisms. Here, the aromatic substrate is formally replaced with [ZnO]₂ to give tetra‐tert‐butyldi‐μ₄‐oxido‐bis(tetramethylethylenediamine‐κ²N,N′)bis(μ₂‐2,2,6,6‐tetramethylpiperidin‐1‐ido‐κ²N:N)disodiumtetrazinc hexane 0.59‐solvate, [Na₂Zn₄(C₄H₉)₄(C₉H₁₈N)₂O₂(C₆H₁₆N₂)₂]·0.59C₆H₁₄. The crystallographically centrosymmetric complex retains many of the structural features of its parent monomer but has an unusual dimeric structure, with a central planar Zn–O–Zn–O ring joined to two orthogonal near‐planar Zn–O–Na–N rings through the distorted tetrahedral geometries of the oxide ions.     

Synthesis of (2-aminoethyl)ferrocenes from the reaction of lithium amides with vinylferrocene

Lithium amides react with vinylferrocene in the presence of TMEDA to provide the corresponding (2-aminoethyl)ferrocenes in good to excellent yields. A range of secondary amines can be employed in this amidolithiation reaction, with cyclic derivatives affording particularly good yields of the 2-aminoethyl-substituted ferrocene product. This operationally simple procedure provides one of the most straightforward routes to this class of mono-substituted ferrocene.     

ENDOR studies of the ligation and structure of the non-heme iron site in ACC oxidase

Ethylene is a plant hormone involved in all stages of growth and development, including regulation of germination, responses to environmental stress, and fruit ripening. The final step in ethylene biosynthesis, oxidation of 1-aminocyclopropane-1-carboxylic acid (ACC) to yield ethylene, is catalyzed by ACC oxidase (ACCO). In a previous EPR and ENDOR study of the EPR-active Fe(II)-nitrosyl, [FeNO],(7) complex of ACCO, we demonstrated that both the amino and the carboxyl moieties of the inhibitor d,l-alanine, and the substrate ACC by analogy, coordinate to the Fe(II) ion in the Fe(II)-NO-ACC ternary complex. In this report, we use 35 GHz pulsed and CW ENDOR spectroscopy to examine the coordination of Fe by ACCO in more detail. ENDOR data for selectively (15)N-labeled derivatives of substrate-free ACCO-NO (E-NO) and substrate/inhibitor-bound ACCO-NO (E-NO-S) have identified two histidines as protein-derived ligands to Fe; (1,2)H and (17)O ENDOR of samples in D(2)O and H(2)(17)O solvent have confirmed the presence of water in the substrate-free Fe(II) coordination sphere (E-NO). Analysis of orientation-selective (14,15)N and (17)O ENDOR data is interpreted in terms of a structural model of the ACCO active site, both in the presence (E-NO-S) and in the absence (E-NO) of substrate. Evidence is also given that substrate binding dictates the orientation of bound O(2).     

Experimental evidence of guided-resonances in photonic crystals with aperiodically ordered supercells

We report on the first experimental evidence of guided resonances (GRs) in photonic crystal slabs based on aperiodically ordered supercells. Using Ammann-Beenker (quasiperiodic, eightfold symmetric) tiling geometry, we present our study on the fabrication, experimental characterization, and full-wave numerical simulation of two representative structures (with different filling parameters) operating at near-IR wavelengths (1300-1600 nm). Our results show a fairly good agreement between measurements and numerical predictions and pave the way for the development of new strategies (based on, e.g., the lattice symmetry breaking) for GR engineering.     

Lyot filter based multiwavelength fiber ring laser actively mode-locked at 10 GHz using an electroabsorption modulator

A multiwavelength fiber ring laser comprising of a Lyot filter and hybrid gain medium is presented. A wavelength channel spacing of 100 GHz is achieved by appropriate tuning of the Lyot filter length. Four wavelength channels are simultaneously mode-locked at 10 GHz using an electroabsorption modulator. We highlight how the intra-cavity modulator can affect the stability of the mode-locked laser spectrum when used in conjunction with a Lyot filter. We show that, due its reduced polarization sensitivity, an electroabsorption modulator significantly improves the stability of the mode-locked laser spectrum when compared to using a Mach-Zehnder modulator.     

Synthesis and reactivity of bis(imido) uranium(VI) cyclopentadienyl complexes

The bis(imido) uranium(VI)-C(5)H(5) and -C(5)Me(5) complexes (C(5)H(5))(2)U(N(t)Bu)(2), (C(5)Me(5))(2)U(N(t)Bu)(2), (C(5)H(5))U(N(t)Bu)(2)(I)(dmpe), and (C(5)H(5))(2)U(N(t)Bu)(2)(dmpe) can be synthesized from reactions between U(N(t)Bu)(2)(I)(2)(L)(x) (L=THF, x=2; L=dmpe, x=1) and Na(C(5)R(5)) (R=H, Me); these complexes represent the first structurally characterized C(5)H(5)-compounds of uranium(VI) and they further highlight the differences between UO(2)(2+) and the bis(imido) fragment.     

Photochemical Mechanisms of Fluorophores Employed in Single-Molecule Localization Microscopy

Decoding cellular processes requires visualization of the spatial distribution and dynamic interactions of biomolecules. It is therefore not surprising that innovations in imaging technologies have facilitated advances in biomedical research. The advent of super-resolution imaging technologies has empowered biomedical researchers with the ability to answer long-standing questions about cellular processes at an entirely new level. Fluorescent probes greatly enhance the specificity and resolution of super-resolution imaging experiments. Here, we introduce key super-resolution imaging technologies, with a brief discussion on single-molecule localization microscopy (SMLM). We evaluate the chemistry and photochemical mechanisms of fluorescent probes employed in SMLM. This Review provides guidance on the identification and adoption of fluorescent probes in single molecule localization microscopy to inspire the design of next-generation fluorescent probes amenable to single-molecule imaging.     

Expanding the Range of Bioorthogonal Tags for Multiplex Stimulated Raman Scattering Microscopy

Multiplex optical detection in live cells is challenging due to overlapping signals and poor signal-to-noise associated with some chemical reporters. To address this, the application of spectral phasor analysis to stimulated Raman scattering (SRS) microscopy for unmixing three bioorthogonal Raman probes within cells is reported. Triplex detection of a metallacarborane using the B−H stretch at 2480–2650 cm⁻¹, together with a bis-alkyne and deuterated fatty acid can be achieved within the cell-silent region of the Raman spectrum. When coupled to imaging in the high-wavenumber region of the cellular Raman spectrum, nine discrete regions of interest can be spectrally unmixed from the hyperspectral SRS dataset, demonstrating a new capability in the toolkit of multiplexed Raman imaging of live cells.     

Simple Ion–Gas Mixtures as a Source of Key Molecules Relevant to Prebiotic Chemistry

Very simple chemistry can result in the rapid and high-yield production of key prebiotic inorganic molecules. The two reactions investigated here involve such simple systems, (a) carbon disulfide (CS₂) and acetate (CH₃COO¯) and (b) sulfur dioxide (SO₂) and formate (HCOO¯). They have been carried out under non-aqueous conditions, either in an organic solvent or with a powdered salt exposed to the requisite gas. Under such dry conditions the first reaction generated the thioacetate anion [CH₃COS]¯ while the second produced the radical [SO₂^·]¯anion. Anhydrous conditions are not rare and may have arisen on the early earth at sites where an interface between different phases (liquid/gas or solid/gas) could be generated. This is one way to rationalize the formation of molecules and ions (such as we have produced) necessary in the prebiotic world. Interpretation of our results provides insight into scenarios consistent with the more prominent theories of abiogenesis.