Photosynthetic Antenna‐Reaction Center Mimicry with a Covalently Linked Monostyryl Boron‐Dipyrromethene–Aza‐Boron‐Dipyrromethene–C60 Triad

An efficient functional mimic of the photosynthetic antenna‐reaction center has been designed and synthesized. The model contains a near‐infrared‐absorbing aza‐boron‐dipyrromethene (ADP) that is connected to a monostyryl boron‐dipyrromethene (BDP) by a click reaction and to a fullerene (C₆₀) using the Prato reaction. The intramolecular photoinduced energy and electron‐transfer processes of this triad as well as the corresponding dyads BDP‐ADP and ADP‐C₆₀ have been studied with steady‐state and time‐resolved absorption and fluorescence spectroscopic methods in benzonitrile. Upon excitation, the BDP moiety of the triad is significantly quenched due to energy transfer to the ADP core, which subsequently transfers an electron to the fullerene unit. Cyclic and differential pulse voltammetric studies have revealed the redox states of the components, which allow estimation of the energies of the charge‐separated states. Such calculations show that electron transfer from the singlet excited ADP (¹ADP*) to C₆₀ yielding ADP^.+‐C₆₀^.? is energetically favorable. By using femtosecond laser flash photolysis, concrete evidence has been obtained for the occurrence of energy transfer from ¹BDP* to ADP in the dyad BDP‐ADP and electron transfer from ¹ADP* to C₆₀ in the dyad ADP‐C₆₀. Sequential energy and electron transfer have also been clearly observed in the triad BDP‐ADP‐C₆₀. By monitoring the rise of ADP emission, it has been found that the rate of energy transfer is fast (≈10¹¹ s^?1). The dynamics of electron transfer through ¹ADP* has also been studied by monitoring the formation of C₆₀ radical anion at 1000 nm. A fast charge‐separation process from ¹ADP* to C₆₀ has been detected, which gives the relatively long‐lived BDP‐ADP^.+C₆₀^.? with a lifetime of 1.47 ns. As shown by nanosecond transient absorption measurements, the charge‐separated state decays slowly to populate mainly the triplet state of ADP before returning to the ground state. These findings show that the dyads BDP‐ADP and ADP‐C₆₀, and the triad BDP‐ADP‐C₆₀ are interesting artificial analogues that can mimic the antenna and reaction center of the natural photosynthetic systems.     

Development of novel graphene-like layered hexagonal boron nitride for adsorptive removal of antibiotic gatifloxacin from aqueous solution

Graphene-like layered hexagonal boron nitride (g-BN) was prepared and characterized. The performance of using g-BN as an adsorbent for removal of fluoroquinolone antibiotic gatifloxacin (GTF) from aqueous solution was evaluated. g-BN showed an excellent adsorption capability with notable GTF adsorption ratio of more than 90%. Data of equilibrium adsorption of GTF onto g-BN at different temperatures were represented by Langmuir, Freundlich and Tempkin isotherm models, and Langmuir exhibited the best fitting with the maximum adsorption capacity of 88.5 mg·g^?1 at 288 K. GTF adsorption was insignificantly affected by solution pH. Competitive role of Na⁺ and Ca²⁺ in the solution inhibited the adsorption of GTF and decreased the adsorption capacity a bit. The adsorption process was spontaneous and exothermic. The adsorption was probably governed by π–π interaction between GTF and g-BN, and electrostatic interaction may also exist in the adsorption process.     

Effects of post-deposition annealing on chemical composition of SiNx film in SiO2/SiNx/SiO2/Si stacked structure

To systematically evaluate the quality of SiN_x films in multi-stacked structures, we investigated the effects of post-deposition annealing (PDA) on the film properties of SiN_x within the SiO₂/SiN_x/SiO₂/Si stacked structure by performing X-ray photoelectron spectroscopy (XPS), X-ray reflectivity (XRR), Fourier transform infrared (FT-IR) spectroscopy, and scanning transmission electron microscope–electron energy loss spectroscopy (STEM-EELS) analyses. The XPS results showed that PDA induces the oxidation of the SiN_x layer. In particular, new finding is that Si-rich SiN_x in the SiN_x layer is preferentially oxidized by PDA even in multi-stacked structure. The XRR results showed that the SiN_x layer becomes thinner, whereas the interface layer between the SiN_x layer and Si becomes thicker. It is concluded by STEM-EELS and XPS that this interface layer is SiON layer. The density of N–H and Si–H bonding within the stacked structure strongly depends on the PDA temperature. Our study helps elucidate the properties of SiN_x films in stacked structures from various perspectives.     

Solution Phase Reactivity of Dibenzo[c,e][1,2]azaborinine: Activation and Insertion into Si-E Single Bonds (E=H,OSi(CH3)3, F,Cl) by a BN-Aryne

The boron-nitrogen analogue of ortho-benzyne, 1,2-azaborinine, is a reactive intermediate that features a formal boron-nitrogen triple bond. We here show by combining experimental and computational techniques that the Lewis acidity of the boron center of dibenzo[c,e][1,2]azaborinine allows interaction with the silicon containing single bonds Si−E through the silicon bonding partner E (E=F, Cl, OR, H). The binding to boron activates the Si−E bonds for subsequent insertion reaction. This shows that the BN-aryne is a ferocious species that even can activate and insert into the very strong Si−F bond.     

Bistriazoles Connected Through a B−B Bridge,Synthesized by Highly Selective Dipolar Cycloaddition Reactions of a Diazido-diborane(4)

In this work we report the first cycloaddition reactions between a diazido diborane(4) and terminal alkynes, providing unique access to bis-1,2,3-triazoles connected by a B−B bridge. The catalyst-free reactions are highly selective, yielding exclusively the thermodynamically disfavored bis-1,4-triazoles. The reactions are enabled by the high thermal stability of the diazido-diborane [B(hpp)(N₃)]₂ (hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-α]pyrimidinate). Due to the tetra-coordinate boron atoms in this reagent, the reactions are tolerant with respect to the introduction of Lewis-basic groups at the alkyne. The scope and limitations of the new reactions are discussed.     

Controlling Energy Gaps of π-Conjugated Polymers by Multi-Fluorinated Boron-Fused Azobenzene Acceptors for Highly Efficient Near-Infrared Emission

We demonstrate that multi-fluorinated boron-fused azobenzene (BAz) complexes can work as a strong electron acceptor in electron donor-acceptor (D-A) type π-conjugated polymers. Position-dependent substitution effects were revealed, and the energy level of the lowest unoccupied molecular orbital (LUMO) was critically decreased by fluorination. As a result, the obtained polymers showed near-infrared (NIR) emission (λ_PL=758–847 nm) with high absolute photoluminescence quantum yield (Φ_PL=7–23%) originating from low-lying LUMO energy levels of the BAz moieties (−3.94 to −4.25 eV). Owing to inherent solid-state emissive properties of the BAz units, deeper NIR emission (λ_PL=852980 nm) was detected in film state. Clear solvent effects prove that the NIR emission is from a charge transfer state originating from a strong D-A interaction. The effects of fluorination on the frontier orbitals are well understandable and predictable by theoretical calculation with density functional theory. This study demonstrates the effectiveness of fluorination to the BAz units for producing a strong electron-accepting unit through fine-tuning of energy gaps, which can be the promising strategy for designing NIR absorptive and emissive materials.     

A Novel Carbon Nitride Nanosheets-based Electrochemical Sensor for Determination of Hydroxychloroquine in Pharmaceutical Formulation and Synthetic Urine Samples

This study introduces modified carbon paste electrodes with carbon nitride nanosheets (CNNS) and outlines their application for the determination of hydroxychloroquine sulfate (HCQ) in tablets and synthetic urine samples. CNNS were synthesized by hydrothermal route (200 °C, 10 h) using melamine and citric acid as their precursors. The carbon nitride nanosheets-based electrode (CNNS/E) presented a linear dynamic range for HCQ (LDR), ranging from 10.0 nmol l⁻¹ to 6.92 μmol l⁻¹, and detection (LOD) and quantification limits (LOQ) of 0.16 nmol l⁻¹ and 0.52 nmol l⁻¹, respectively. LOD and LOQ were calculated by the equations: LOD=3(S_d/b), and LOQ=10(S_d/b). The modified sensor presented excellent relative standard deviations for parameters such as repeatability (2.39 % and 1.87 %) and reproducibility (3.22 % and 2.32 %) in HCQ oxidation peaks (1 and 2). The CNNS/E has not shown significant variations in its anodic signal intensity in the presence of some organic and inorganic substances. It is worth bearing in mind that CNNS/E can be easily manufactured and the sensor has the lowest HCQ detection limits reported so far. The proposed sensor was successfully applied for HCQ determination in tablets and synthetic urine, showing good recovery values and an error of 0.60 % about comparative method in tablet samples, assuring the quality of the method.     

Novel microwave plasma‐assisted CVD reactor for diamond delta doping

We report on building a novel chemical vapor deposition (CVD) reactor for diamond delta‐doping. The main features of our reactor are: a) the use of rapid gas switching system, (b) the reactor design providing the laminar gas flow. These features provide the creation of ultra‐sharp interfaces between doped and undoped material and minimize the prolonged ”tails” formation in the doping profile. It is proved by optical emission spectroscopy that gas switching time is not more than 10 seconds. Using the novel reactor we have grown the nanometer‐thin layers of boron doped diamond. The FWHM of boron concentration profile is about 2 nm which is proved by SIMS. It is shown that the both single delta‐layer and multiple delta‐layers could be grown using the novel CVD reactor. In principle, the reactor could be used for diamond delta doping with other dopants, like nitrogen, phosphorus etc. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Investigation of fill factor losses on 20.2% efficient n‐type mono‐like silicon solar cells with laser contact opening

Large area (243.36 cm²) back‐junction passivated emitter, rear totally diffused (PERT) solar cells with laser contact opening (LCO) on n‐type mono‐like crystalline Si with efficiencies of 20.2% are presented. Boron emitters with high electrical quality (implied open circuit voltage iV_OC up to 700 mV) are formed during a co‐diffusion step using SiO_x:B layers. Increasing the rear metal contact coverage, we observed a decrease in fill factor (FF) instead of the expected increase due to the decrease of the back side series resistance. We show that it can be attributed to recombination centers (RCs) in the space charge region underneath the contact spots inducing an increasing second diode contribution. The presented empirical model for the RCs implemented in Synopsys Sentaurus TCAD allows for a successful reproduction of the FF, pseudo FF and V_OC behaviour with contact coverage. According to this model, the RCs induced by laser ablation and subsequently evaporation of Al have a shallow exponential distribution with a characteristic length of L_T = 0.2 µm and an effective surface density of N *_T0 = 25 cm^–1. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)