Modular synthesis of cyclic ß-difluoroamines.

Fluorine-containing saturated nitrogen heterocycles are very attractive structures in medicinal and biological chemistry because fluorine can be used to tune conformation as well as key properties such as basicity and bioavailability. At present cyclic fluorinated amines are accessed using hazardous reagents such as DAST or by lengthy synthesis routes. Here we report a modular two-step synthesis of cyclic ß-fluoroalkyl amines using a photoredox-catalysed cyclisation/hydrogen atom transfer reaction of bromodifluoroethylamines.

Borylated cyclobutanes via thermal [2 + 2]-cycloaddition.

A one-step approach to borylated cyclobutanes from amides of carboxylic acids and vinyl boronates is elaborated. The reaction proceeds via the thermal [2 + 2]-cycloaddition of in situ-generated keteniminium salts.

Photosensitization enables Pauson-Khand-type reactions with nitrenes.

The Pauson-Khand reaction has in the past 50 years become one of the most common cycloaddition reactions in chemistry. Coupling two unsaturated bonds with carbon monoxide, the transformation remains limited to CO as a C1 building block. Herein we report analogous cycloaddition reactions with nitrenes as an N1 unit. The reaction of a nonconjugated diene with a nitrene precursor produces bicyclic bioisosteres of common saturated heterocycles such as piperidine, morpholine, and piperazine. Experimental and computational mechanistic studies support relaying of the diradical nature of triplet nitrene into the π-system. We showcase the reaction's utility in late-stage functionalization of drug compounds and discovery of soluble epoxide hydrolase inhibitors.

Spiro[3.3]heptane as a Saturated Benzene Bioisostere.

The spiro[3.3]heptane core, with the non-coplanar exit vectors, was shown to be a saturated benzene bioisostere. This scaffold was incorporated into the anticancer drug sonidegib (instead of the meta-benzene), the anticancer drug vorinostat (instead of the phenyl ring), and the anesthetic drug benzocaine (instead of the para-benzene). The patent-free saturated analogs obtained showed a high potency in the corresponding biological assays.

1-Azaspiro[3.3]heptane as a Bioisostere of Piperidine.

1-Azaspiro[3.3]heptanes were synthesized, characterized, and validated biologically as bioisosteres of piperidine. The key synthesis step was thermal [2+2] cycloaddition between endocyclic alkenes and the Graf isocyanate, ClO2 S-NCO, to give spirocyclic ß-lactams. Reduction of the ß-lactam ring with alane produced 1-azaspiro[3.3]heptanes. Incorporation of this core into the anesthetic drug bupivacaine instead of the piperidine fragment resulted in a new patent-free analogue with high activity.

Enhanced photoconductivity of hybrid 2D-QD MoS2-AgInS2 structures.

This study describes the fabrication of hybrid two-dimensional (2D)-quantum dot (QD) MoS2-AgInS2 photoconductive devices through the mechanical pressing of a MoS2 flake onto an AgInS2 QD film. The devices exhibit an enhanced photoresponse at both continuous and modulated optical excitations, compared with the bare MoS2 or AgInS2 layer, due to the formation of a built-in electric field near the MoS2/AgInS2 interface. The continuous wave photoresponse is significantly higher due to the effective photoconductive gain when electrons flow freely through the MoS2 flake, whereas holes are effectively trapped in AgInS2 QDs. The study highlights the potential of hybrid 2D-QD MoS2-AgInS2 devices for photovoltaic and optoelectronic applications.

Arylboration of Enecarbamates for the Synthesis of Borylated Saturated N-Heterocycles.

Two catalytic systems have been developed for the arylboration of endocyclic enecarbamates to deliver synthetically versatile borylated saturated N-heterocycles in good regio- and diastereoselectivities. A Cu/Pd dual catalytic reaction enables the synthesis of borylated, α-arylated azetidines, while a Ni-catalysed arylboration reaction efficiently functionalizes 5-, 6-, and 7-membered enecarbamates. In the case of the Cu/Pd-system, a remarkable additive effect was identified that allowed for broader scope. The products are synthetically useful, as demonstrated by manipulations of the boronic ester to access biologically active compounds.

Defect influence on in-plane photocurrent of InAs/InGaAs quantum dot array: long-term electron trapping and Coulomb screening.

Metamorphic InAs/In0.15Ga0.85As and InAs/In0.31Ga0.69As quantum dot (QD) arrays are known to be photosensitive in the telecommunication ranges at 1.3 and 1.55 µm, respectively; however, for photonic applications of these nanostructures, the effect of levels related to defects still needs in-depth investigation. We have focused on the influence of electron traps of defects on photocurrent (PC) in the plane of the QD array, studying by PC and deep level thermally stimulated current spectroscopy together with HRTEM and theoretical modeling. In the structures, a rich spectrum of electron trap levels of point defects EL6 (E c - 0.37 eV), EL7 (0.29-0.30 eV), EL8 (0.27 eV), EL9/M2 (0.22-0.23 eV), EL10/M1 (0.16 eV), M0 (∼0.11 eV) and three extended defects ED1/EL3 (0.52-0.54), ED2/EL4 (0.47-0.48 eV), ED3/EL5 (0.42-0.43 eV) has been identified. Among them, new defect levels undiscovered earlier in InAs/InGaAs nanostructures has been detected, in particular, EL8 and M0. The found electron traps are shown to affect a time-dependent PC at low temperatures. Besides a long-term kinetics due to trap charging, a prolonged PC decrement versus time is measured under constant illumination. The decrement is interpreted to be related to a Coulomb screening of the conductivity channel by the electrons captured in the QD interface traps. The decrement is well fitted by allometric exponents, which means many types of traps involved in electron capturing. This study provides new findings into the mechanism of in-plane PC of QD arrays, showing a crucial importance of growth-related defects on photoresponsivity at low temperatures.

Optical windows for head tissues in near-infrared and short-wave infrared regions: Approaching transcranial light applications.

Optical properties of the rat head tissues (brain cortex, cranial bone and scalp skin) are assessed, aiming at transcranial light applications such as optical imaging and phototherapy. The spectral measurements are carried out over the wide spectral range of 350 to 2800 nm, involving visible, near-infrared (NIR) and short-wave infrared (SWIR) regions. Four tissue transparency windows are considered: ~700 to 1000 nm (NIR-I), ~1000 to 1350 nm (NIR-II), ~1550 to 1870 nm (NIR-III or SWIR) and ~2100 to 2300 nm (SWIR-II). The values of attenuation coefficient and total attenuation length are determined for all windows and tissue types. The spectra indicate transmittance peaks in NIR, NIR-II and SWIR-II, with maximum tissue permeability for SWIR light. The use of SWIR-II window for the transcranial light applications is substantiated. Furthermore, absorbance of the head tissues is investigated in details, by defining and describing the characteristic absorption peaks in NIR-SWIR.

Interband Photoconductivity of Metamorphic InAs/InGaAs Quantum Dots in the 1.3-1.55-µm Window.

Photoelectric properties of the metamorphic InAs/In x Ga1 - xAs quantum dot (QD) nanostructures were studied at room temperature, employing photoconductivity (PC) and photoluminescence spectroscopies, electrical measurements, and theoretical modeling. Four samples with different stoichiometry of In x Ga1 - xAs cladding layer have been grown: indium content x was 0.15, 0.24, 0.28, and 0.31. InAs/In0.15Ga0.85As QD structure was found to be photosensitive in the telecom range at 1.3 µm. As x increases, a redshift was observed for all the samples, the structure with x = 0.31 was found to be sensitive near 1.55 µm, i.e., at the third telecommunication window. Simultaneously, only a slight decrease in the QD PC was recorded for increasing x, thus confirming a good photoresponse comparable with the one of In0.15Ga0.75As structures and of GaAs-based QD nanostructures. Also, the PC reduction correlate with the similar reduction of photoluminescence intensity. By simulating theoretically the quantum energy system and carrier localization in QDs, we gained insight into the PC mechanism and were able to suggest reasons for the photocurrent reduction, by associating them with peculiar behavior of defects in such a type of structures. All this implies that metamorphic QDs with a high x are valid structures for optoelectronic infrared light-sensitive devices.

Bipolar Effects in Photovoltage of Metamorphic InAs/InGaAs/GaAs Quantum Dot Heterostructures: Characterization and Design Solutions for Light-Sensitive Devices.

The bipolar effect of GaAs substrate and nearby layers on photovoltage of vertical metamorphic InAs/InGaAs in comparison with pseudomorphic (conventional) InAs/GaAs quantum dot (QD) structures were studied. Both metamorphic and pseudomorphic structures were grown by molecular beam epitaxy, using bottom contacts at either the grown n +-buffers or the GaAs substrate. The features related to QDs, wetting layers, and buffers have been identified in the photoelectric spectra of both the buffer-contacted structures, whereas the spectra of substrate-contacted samples showed the additional onset attributed to EL2 defect centers. The substrate-contacted samples demonstrated bipolar photovoltage; this was suggested to take place as a result of the competition between components related to QDs and their cladding layers with the substrate-related defects and deepest grown layer. No direct substrate effects were found in the spectra of the buffer-contacted structures. However, a notable negative influence of the n +-GaAs buffer layer on the photovoltage and photoconductivity signal was observed in the InAs/InGaAs structure. Analyzing the obtained results and the performed calculations, we have been able to provide insights on the design of metamorphic QD structures, which can be useful for the development of novel efficient photonic devices.

Comparative Study of Photoelectric Properties of Metamorphic InAs/InGaAs and InAs/GaAs Quantum Dot Structures.

Optical and photoelectric properties of metamorphic InAs/InGaAs and conventional pseudomorphic InAs/GaAs quantum dot (QD) structures were studied. We used two different electrical contact configurations that allowed us to have the current flow (i) only through QDs and embedding layers and (ii) through all the structure, including the GaAs substrate (wafer). Different optical transitions between states of QDs, wetting layers, GaAs or InGaAs buffers, and defect-related centers were studied by means of photovoltage (PV), photoconductivity (PC), photoluminescence (PL), and absorption spectroscopies. It was shown that the use of the InGaAs buffer spectrally shifted the maximum of the QD PL band to 1.3 µm (telecommunication range) without a decrease in the yield. Photosensitivity for the metamorphic QDs was found to be higher than that in GaAs buffer while the photoresponses for both metamorphic and pseudomorphic buffer layers were similar. The mechanisms of PV and PC were discussed for both structures. The dissimilarities in properties of the studied structures are explained in terms of the different design. A critical influence of the defects on the photoelectrical properties of both structures was observed in the spectral range from 0.68 to 1.0 eV for contact configuration (ii), i.e., in the case of electrically active GaAs wafer. No effect of such defects on the photoelectric spectra was found for configuration (i), when the structures were contacted to the top and bottom buffers; only a 0.83 eV feature was observed in the photocurrent spectrum of pseudomorphic structure and interpreted to be related to defects close to InAs/GaAs QDs.