Arylsilanes: application to gold-catalyzed oxyarylation of alkenes

Arylsilanes are efficient reagents for the gold-catalyzed oxyarylation of alkenes (21 examples, up to 85% isolated yield). Using commercially available Ph(3)PAuCl and readily prepared, benign arylsilanes, these two- and three-component reactions proceed smoothly in air. The oxidant, Selectfluor, not only facilitates entry to the Au(I/III) manifold but also provides a fluoride anion for silane activation, thereby avoiding the need for addition of a stoichiometric base.     

Uranium(VI) bis(imido) disulfonamide and dihalide complexes: Synthesis density functional theory analysis

Novel cis- and trans-bis(imido) uranium disulfonamide derivatives have been prepared from iodide metathesis reactions between two equivalents of K[N(Me)(SO₂Ar’)] (Ar’ = 4-Me-C₆H₄) and U(N^tBu)₂(I)₂(L)_x (L = OPPh₃, x = 2; Me₂bpy, x = 1; Me₂bpy = 4,4’-dimethyl-2,2’-bipyridyl). These bis(amide) derivatives serve as useful precursors for the synthesis of the trans-diphenolate complex U(N^tBu)₂(O-2-^tBuC₆H₄)₂(OPPh₃)₂ (5), cis- and trans-dithiolate complexes U(N^tBu)₂(SPh)₂(L)_x (L = OPPh₃ (6); Me₂bpy (7)), and cis- and trans-dihalide complexes with the general formulas U(N^tBu)₂(X)₂(L)_x (X = Cl, L = OPPh₃ (8), L = Me₂bpy (10); X = Br, L = OPPh₃ (9), L = Me₂bpy (11)). DFT calculations performed on the trans-dihalide series U(N^tBu)₂(X)₂(L)₂ and the UO₂²⁺ analogues UO₂X₂(OPPh₃)₂ suggest that the uranium centers in the [U(N^tBu)₂]²⁺ ions possess more covalent character than analogous UO₂²⁺ derivatives but that the U-X bonds in the U(N^tBu)₂X₂L₂ complexes possess a more ionic nature.     

Characterization of time-resolved laser differential phase using 3D complementary cumulative distribution functions

An experimental method for characterizing the time-resolved phase noise of a fast switching tunable laser is discussed. The method experimentally determines a complementary cumulative distribution function of the laser's differential phase as a function of time after a switching event. A time resolved bit error rate of differential quadrature phase shift keying formatted data, calculated using the phase noise measurements, was fitted to an experimental time-resolved bit error rate measurement using a field programmable gate array, finding a good agreement between the time-resolved bit error rates.     

Linewidth of SG-DBR laser and its effect on DPSK transmission

In this paper the linewidth of widely tunable SG-DBR lasers has been investigated theoretically and experimentally. We demonstrate experimentally the importance of obtaining low linewidth operation for the application of SG-DBR laser with advanced modulation format transmission. This is achieved by choosing two sets of tuning currents for an SG-DBR laser that give the same wavelength channel and good SMSR, but different linewidths. When the laser is employed in a DPSK system only the operating point (the set of drive currents used to obtain specific output characteristics) that portrays low linewidth achieves error free transmission. This work shows that although calibration of tunable lasers is normally based on achieving sufficient SMSR and output power, it will be important to consider the linewidth parameter as these lasers begin to be used in more spectrally efficient WDM systems employing advanced modulation formats. The simulation results illustrate that the operating points which achieve narrow linewidth are correlated with those that exhibit low threshold current. This finding may be used for calibration of SG-DBR lasers to achieve minimum linewidth at each operating wavelength.     

Programmable Biopolymers for Advancing Biomedical Applications of Fluorescent Nanodiamonds

A versatile biopolymer platform for advancing nanodiamonds (NDs) as unique magnetooptic materials for biomedical applications is presented here. Precision biopolymer coatings are designed by chemical reprogramming the functionalities of serum albumin via a straightforward synthesis protocol. Such biopolymers offer high biocompatibility and precise modification with various functional entities due to the large number of available reactive amino acid residues. Premodification of these biopolymers provides a convenient approach to customized surface functionalization of NDs. As an example, the anticancer drug doxorubicin (DOX) is conjugated to the biopolymer with high reproducibility and full characterization. The biopolymer‐coated NDs reveal excellent colloidal stabilities in all physiological media tested, even after loading with high numbers of hydrophobic DOX. The intracellular distribution of NDs and DOX is analyzed in living cells by recording the fluorescence spectra in different cellular compartments, which proves efficient intracellular release of DOX from the carrier. Studies in vitro as well as in a chick tumor xenograft model reveal efficient antitumor effects. The facile and versatile biopolymer coating strategy reported herein will greatly accelerate the availability of customized NDs with reliable and reproducible features to exploit their great potential in single molecular bioimaging, in vivo biosensing, and high resolution quantum optics.     

Order parameters for the multistep crystallization of clathrate hydrates

Recent reports indicate that the crystallization of clathrate hydrates occurs in multiple steps that involve amorphous intermediates and metastable clathrate crystals. The elucidation of the reaction coordinate for clathrate crystallization requires the use of order parameters able to identify the reactants, products, and intermediates in the crystallization pathway. Nevertheless, existing order parameters cannot distinguish between amorphous and crystalline clathrates or between different clathrate crystals. In this work, we present the first set of order parameters that discern between the sI and sII clathrate crystals, the amorphous clathrates, the blob of solvent-separated guests and the liquid solution. These order parameters can be used to monitor the advance of the crystallization and for the efficient implementation of methods to sample the rare clathrate nucleation events in molecular simulations. We illustrate the use of these order parameters in the analysis of the growth and the dissolution of clathrate crystals and the spontaneous nucleation and growth of clathrates under conditions of high supercooling.     

Synthesis of Nitro-Aryl Functionalised 4-Amino-1,8-Naphthalimides and Their Evaluation as Fluorescent Hypoxia Sensors

Fluorescent sensors are a vital research tool, enabling the study of intricate cellular processes in a sensitive manner. The design and synthesis of responsive and targeted probes is necessary to allow such processes to be interrogated in the cellular environment. This remains a challenge, and requires methods for functionalisation of fluorophores with multiple appendages for sensing and targeting groups. Methods to synthesise more structurally complex derivatives of fluorophores will expand their potential scope. Most known 4-amino-1,8-naphthalimides are only functionalised at imide and 4-positions, and structural modifications at additional positions will increase the breadth of their utility as responsive sensors. In this work, methods for the incorporation of a hypoxia sensing group to 4-amino-1,8-naphthalimide were evaluated. An intermediate was developed that allowed us to incorporate a sensing group, targeting group, and ICT donor to the naphthalimide core in a modular fashion. Synthetic strategies for attaching the hypoxia sensing group and how they affected the fluorescence of the naphthalimide were evaluated by photophysical characterisation and time-dependent density functional theory. An extracellular hypoxia probe was then rationally designed that could selectively image the hypoxic and necrotic region of tumour spheroids. Our results demonstrate the versatility of the naphthalimide scaffold and expand its utility. This approach to probe design will enable the flexible, efficient generation of selective, targeted fluorescent sensors for various biological purposes.     

Graphene-Based Technologies for Tackling COVID-19 and Future Pandemics

The COVID-19 pandemic highlighted the need for rapid tools and technologies to combat highly infectious viruses. The excellent electrical, mechanical and other functional properties of graphene and graphene-like 2D materials (2DM) can be utilized to develop novel and innovative devices to tackle COVID-19 and future pandemics. Here, the authors outline how graphene and other 2DM-based technologies can be used for the detection, protection, and continuous monitoring of infectious diseases including COVID-19. The authors highlight the potential of 2DM-based biosensors in rapid testing and tracing of viruses to enable isolation of infected patients, and stop the spread of viruses. The possibilities of graphene-based wearable devices are discussed for continuous monitoring of COVID-19 symptoms. The authors also provide an overview of the personal protective equipment, and potential filtration mechanisms to separate, destroy or degrade highly infectious viruses, and the potential of graphene and other 2DM to increase their efficiency, and enhance functional and mechanical properties. Graphene and other 2DM could not only play a vital role for tackling the ongoing COVID-19 pandemic but also provide technology platforms and tools for the protection, detection and monitoring of future viral diseases.     

Controlled-Atmosphere Flame Fusion Single-Crystal Growth of Non-Noble fcc,hcp, and bcc Metals Using Copper,Cobalt, and Iron

The growth of noble-metal single crystals via the flame fusion method was developed in the 1980s. Since then, there have been no major advancements to the technique until the recent development of the controlled-atmosphere flame fusion (CAFF) method to grow non-noble Ni single crystals. Herein, we demonstrate the generality of this method with the first preparation of fcc Cu as well as the first hcp and bcc single crystals of Co and Fe, respectively. The high quality of the single crystals was verified using scanning electron microscopy and Laue X-ray backscattering. Based on Wulff constructions, the equilibrium shapes of the single-crystal particles were studied, confirming the symmetry of the fcc, hcp, and bcc single-crystal lattices. The low cost of the CAFF method makes all kinds of high-quality non-noble single crystals independent of their lattice accessible for use in electrocatalysis, electrochemistry, surface science, and materials science.