Copper-Catalyzed C4-selective Carboxylation of Pyridines with CO2 via Pyridylphosphonium Salts.

Pyridine motifs are widespread pharmacophores in many drugs. Installing various substituents through pyridine C-H bond functionalization is significant for new drug design and discovery. Developments of late-stage functionalization reactions enrich the strategies for selective functionalization of pyridines. However, late-stage C-H carboxylation of pyridines is a long-standing challenge, especially selectively carboxylation with CO2 on pyridine motifs. Herein, we describe a practical method for C4-H carboxylation of pyridines via one-pot C-H phosphination and copper-catalyzed carboxylation of the resulted phosphonium salts with CO2 . The reaction is conducted under mild conditions and compatible with multiple active groups and several pyridine drugs, providing diverse valuable isonicotinic acid compounds, demonstrating the application potential of this strategy.

Diethylzinc-promoted carboxylation of aryl/alkenyl boronic acids with CO2.

The carboxylation of aryl and alkenyl boronic acids with CO2 is rarely studied and only achieved using copper salts as the catalyst in the presence of a strong base. Herein, we report a diethylzinc-promoted carboxylation of aryl or alkenyl boronic acids with carbon dioxide. The reaction does not require a transition-metal catalyst, and has simple and mild conditions and a broad substrate scope.

Coexistence of 1 Tbps classical optical communication and quantum key distribution over a 100.96 km few-mode fiber.

The integration of quantum key distribution (QKD) and classical optical communication has attracted widespread attention. In this Letter, we experimentally demonstrate a real-time co-propagation of 1 Tbps for 10 classical channels with one discrete-variable QKD channel in the weakly coupled few-mode fiber (FMF). Based on the selection of optimal device parameters and wavelength assignment of classical channels, as well as the optimization of equipment performance, a secure key rate of as high as 2.7 kbps of coexistence transmission of QKD and classical optical communication can be achieved using a 100.96 km weakly coupled FMF. Therefore, this study is a step toward realizing long-distance quantum-classical coexistence transmission.

Field test of quantum key distribution over aerial fiber based on simple and stable modulation.

We have developed a simple time-bin phase encoding quantum key distribution system, using the optical injection locking technique. This setup incorporates both the merits of simplicity and stability in encoding, and immunity to channel disturbance. We have demonstrated the field implementation of quantum key distribution over long-distance deployed aerial fiber automatically. During the 70-day field test, we achieved approximately a 1.0 kbps secure key rate with stable performance. Our work takes an important step toward widespread implementation of QKD systems in diverse and complex real-life scenarios.

Time-bin phase-encoding quantum key distribution using Sagnac-based optics and compatible electronics.

In this work, we present a new time-bin phase-encoding quantum key distribution (QKD), where the transmitter utilizes an inherently stable Sagnac-type interferometer, and has comparable electrical requirements to existing polarization or phase encoding schemes. This approach does not require intensity calibration and is insensitive to environmental disturbances, making it both flexible and high-performing. We conducted experiments with a compact QKD system to demonstrate the stability and secure key rate performance of the presented scheme. The results show a typical secure key rate of 6.2 kbps@20 dB and 0.4 kbps@30 dB with channel loss emulated by variable optical attenuators. A continuous test of 120-km fiber spool shows a stable quantum bit error rate of the time-bin basis within 0.4%∼0.6% over a consecutive 9-day period without any adjustment. This intrinsically stable and compatible scheme of time-bin phase encoding is extensively applicable in various QKD experiments, including BB84 and measurement-device-independent QKD.

Experimental Mode-Pairing Measurement-Device-Independent Quantum Key Distribution without Global Phase Locking.

In the past two decades, quantum key distribution networks based on telecom fibers have been implemented on metropolitan and intercity scales. One of the bottlenecks lies in the exponential decay of the key rate with respect to the transmission distance. Recently proposed schemes mainly focus on achieving longer distances by creating a long-arm single-photon interferometer over two communication parties. Despite their advantageous performance over long communication distances, the requirement of phase locking between two remote lasers is technically challenging. By adopting the recently proposed mode-pairing idea, we realize high-performance quantum key distribution without global phase locking. Using two independent off-the-shelf lasers, we show a quadratic key-rate improvement over the conventional measurement-device-independent schemes in the regime of metropolitan and intercity distances. For longer distances, we also boost the key rate performance by 3 orders of magnitude via 304 km commercial fiber and 407 km ultralow-loss fiber. We expect this ready-to-implement high-performance scheme to be widely used in future intercity quantum communication networks.

Ruthenium(II)-Catalyzed Grignard-Type Nucleophilic Addition of C(sp2)-H Bonds to Unactivated Aldehydes.

The Grignard-type nucleophilic addition of C(sp2)-H bonds to aldehydes catalyzed by high-oxidation-state transition metal complexes is limited to activated aldehydes. Herein, we report the first example of Grignard-type nucleophilic addition of C(sp2)-H bonds to unactivated aldehydes catalyzed by high-oxidation-state ruthenium(II). The reaction has mild reaction conditions and good functional group tolerance. The corresponding alcohol products are obtained in good to excellent yields.

Copper-Catalyzed Carboxylation of Aryl Thianthrenium Salts with CO2.

Carboxyl group is one of the most widely used groups in organic synthesis. Herein, an efficient copper-catalyzed carboxylation of aryl thianthrenium salts with carbon dioxide (CO2 ) at room temperature has been developed. The reaction employs low loading of cuprous chloride catalyst under 1 atm CO2 and exhibits good functional group tolerance. In combination with C-H thianthrenation of aromatic hydrocarbons, this work provides an efficient method for the site-selective C-H carboxylation of aromatic hydrocarbons. It may serve as a significant late-stage carboxylation tool for the modification of drug molecules in the future.

Practical quantum access network over a 10 Gbit/s Ethernet passive optical network.

Quantum key distribution (QKD) provides an information-theoretically secure method to share keys between legitimate users. To achieve large-scale deployment of QKD, it should be easily scalable and cost-effective. The infrastructure construction of quantum access network (QAN) expands network capacity and the integration between QKD and classical optical communications reduces the cost of channel. Here, we present a practical downstream QAN over a 10 Gbit/s Ethernet passive optical network (10G-EPON), which can support up to 64 users. In the full coexistence scheme using the single feeder fiber structure, the co-propagation of QAN and 10G-EPON signals with 9 dB attenuation is achieved over 21 km fiber, and the secure key rate for each of 16 users reaches 1.5 kbps. In the partial coexistence scheme using the dual feeder fiber structure, the combination of QAN and full-power 10G-EPON signals is achieved over 11 km with a network capacity of 64-user. The practical QAN over the 10G-EPON in our work implements an important step towards the achievement of large-scale QKD infrastructure.

All optical metropolitan quantum key distribution network with post-quantum cryptography authentication.

Quantum key distribution (QKD) provides information theoretically secure key exchange requiring authentication of the classic data processing channel via pre-sharing of symmetric private keys to kick-start the process. In previous studies, the lattice-based post-quantum digital signature algorithm Aigis-Sig, combined with public-key infrastructure (PKI), was used to achieve high-efficiency quantum security authentication of QKD, and we have demonstrated its advantages in simplifying the MAN network structure and new user entry. This experiment further integrates the PQC algorithm into the commercial QKD system, the Jinan field metropolitan QKD network comprised of 14 user nodes and 5 optical switching nodes, and verifies the feasibility, effectiveness and stability of the post-quantum cryptography (PQC) algorithm and advantages of replacing trusted relays with optical switching brought by PQC authentication large-scale metropolitan area QKD network. QKD with PQC authentication has potential in quantum-secure communications, specifically in metropolitan QKD networks.

Sending or Not-Sending Twin-Field Quantum Key Distribution with Flawed and Leaky Sources.

Twin-field quantum key distribution (TF-QKD) has attracted considerable attention and developed rapidly due to its ability to surpass the fundamental rate-distance limit of QKD. However, the device imperfections may compromise its practical implementations. The goal of this paper is to make it robust against the state preparation flaws (SPFs) and side channels at the light source. We adopt the sending or not-sending (SNS) TF-QKD protocol to accommodate the SPFs and multiple optical modes in the emitted states. We analyze that the flaws of the phase modulation can be overcome by regarding the deviation of the phase as phase noise and eliminating it with the post-selection of phase. To overcome the side channels, we extend the generalized loss-tolerant (GLT) method to the four-intensity decoy-state SNS protocol. Remarkably, by decomposing of the two-mode single-photon states, the phase error rate can be estimated with only four parameters. The practical security of the SNS protocol with flawed and leaky source can be guaranteed. Our results might constitute a crucial step towards guaranteeing the practical implementation of the SNS protocol.

Field Test of Twin-Field Quantum Key Distribution through Sending-or-Not-Sending over 428 km.

Quantum key distribution endows people with information-theoretical security in communications. Twin-field quantum key distribution (TF-QKD) has attracted considerable attention because of its outstanding key rates over long distances. Recently, several demonstrations of TF-QKD have been realized. Nevertheless, those experiments are implemented in the laboratory, and therefore a critical question remains about whether the TF-QKD is feasible in real-world circumstances. Here, by adopting the sending-or-not-sending twin-field QKD (SNS-TF-QKD) with the method of actively odd parity pairing (AOPP), we demonstrate a field-test QKD over 428 km of deployed commercial fiber and two users are physically separated by about 300 km in a straight line. To this end, we explicitly measure the relevant properties of the deployed fiber and develop a carefully designed system with high stability. The secure key rate we achieved breaks the absolute key rate limit of repeaterless QKD. The result provides a new distance record for the field test of both TF-QKD and all types of fiber-based QKD systems. Our work bridges the gap of QKD between laboratory demonstrations and practical applications and paves the way for an intercity QKD network with measurement-device-independent security.

Rhodium(III)-catalyzed C4-amidation of indole-oximes with dioxazolones via C-H activation.

A novel method for the Rh(iii)-catalyzed oxime-directed C-H amidation of indoles with dioxazolones has been developed. This strategy provides an exclusive site selectivity and the directing group can be easily removed. This transformation features a wide substrate scope, good functional group tolerance and excellent yields, and may serve as a significant tool to construct structurally diverse indole derivatives for the screening of potential pharmaceuticals in the future.

Ruthenium(II)-Catalyzed α-Fluoroalkenylation of Oxime Ethers with gem-Difluorostyrenes via C-H Activation and C-F Cleavage.

A novel route for ruthenium(II)-catalyzed α-fluoroalkenylation of oxime ethers with gem-difluorostyrenes via C-H activation and C-F cleavage has been developed for the first time. Notably, the alkenyl units of products exhibit exclusive Z-configuration. This reaction features a broad substrate scope and good functional group tolerance. A plausible reaction mechanism is confirmed by an available cycloruthenated intermediate. Besides, the O-methyl oximyl-directing group can be readily removed to access the α-fluoroalkenylated acetophenones.

Photocatalytic degradation of microcystin-LR by modified TiO2 photocatalysis: A review.

Microcystin-LR (MC-LR), the most toxic and commonly encountered cyanotoxin, is produced by harmful cyanobacterial blooms and potentially threatens human and ecosystems health. Titanium dioxide (TiO2) photocatalysis is attracting growing attention and has been considered as an efficient, environmentally friendly and promising solution to eliminate MC-LR in the aquatic ecosystems. Over recent decades, scientific efforts have been directed towards the understanding of fundamentals, modification strategies, and application potentials of TiO2 photocatalysis in degrading MC-LR. In this article, recent reports have been reviewed and progress has been summarized in the development of heterogeneous TiO2-based photocatalysts for MC-LR photodegradation under visible, UV, or solar light. The proposed photocatalytic principles of TiO2 and destruction of MC-LR have been thoroughly discussed. Specifically, some main modification methods for improving the drawbacks and performance of TiO2 nanoparticle were highlighted, including element doping, semiconductor coupling, immobilization, floatability amelioration and magnetic separation. Moreover, the performance evaluation metrics quantum yield (QY) and figure of merit (FOM) were used to compare different photocatalysts in MC-LR degradation. The best performance was seen in N-TiO2 with QY and FOM values of 2.20E-07 molecules/photon and 1.00E-11 mol·L/(g·J·h). N-TiO2 or N-TiO2-based materials may be excellent options for photocatalyst design in terms of MC-LR degradation. Finally, a summary of the remaining challenges and perspectives on new tendencies in this exciting frontier and still an emerging area of research were addressed accordingly. Overall, the present review will offer a deep insight for understanding the photodegradation of MC-LR with modified TiO2 to further inspire researchers that work in associated fields.

Long-distance transmission of quantum key distribution coexisting with classical optical communication over a weakly-coupled few-mode fiber.

Quantum key distribution (QKD) is one of the most practical applications in quantum information processing, which can generate information-theoretical secure keys between remote parties. With the help of the wavelength-division multiplexing technique, QKD has been integrated with the classical optical communication networks. The wavelength-division multiplexing can be further improved by the mode-wavelength dual multiplexing technique with few-mode fiber (FMF), which has additional modal isolation and large effective core area of mode, and particularly is practical in fabrication and splicing technology compared with the multi-core fiber. Here, we present for the first time a QKD implementation coexisting with classical optical communication over weakly-coupled FMF using all-fiber mode-selective couplers. The co-propagation of QKD with one 100 Gbps classical data channel at -2.60 dBm launched power is achieved over 86 km FMF with 1.3 kbps real-time secure key generation. Compared with single-mode fiber using wavelength-division multiplexing, given the same fiber-input power, the Raman noise in FMF using the mode-wavelength dual multiplexing is reduced by 86% in average. Our work implements an important approach to the integration between QKD and classical optical communication and previews the compatibility of quantum communications with the next-generation mode division multiplexing networks.

Biodegradation of microcystin-RR and nutrient pollutants using Sphingopyxis sp. YF1 immobilized activated carbon fibers-sodium alginate.

A novel biological material named activated carbon fibers-sodium alginate@Sphingopyxis sp. YF1 (ACF-SA@YF1) was synthesized for microcystin-RR (MC-RR) and nutrient pollutant degradation in eutrophic water. The synthesized biomaterial was characterized by scanning electron microscopy (SEM). Box-Behnken design and response surface methodology (RSM) were utilized for the optimization of conditions during the MC-RR degradation. The degradation of MC-RR and nutrient pollutants was dynamically detected. The results revealed that the optimal conditions were temperature 32.51 °C, pH 6.860, and inoculum 14.97%. The removal efficiency of MC-RR, nitrogen, phosphorus, and chemical oxygen demand were 0.76 µg/mL/h, 32.45%, 94.57%, and 64.07%, respectively. In addition, ACF-SA@YF1 also performed satisfactory cyclic stability, while the MC-RR removal efficiency was 70.38% after seven cycles and 78.54% of initial activity after 20 days of storage. Therefore, it is reasonable to believe that ACF-SA@YF1 is an effective material which has a great prospect in removing MC-RR and nutrients from freshwater ecosystems.

2-Amino-5,6-difluorophenyl-1H-pyrazole-Directed PdII Catalysis: Arylation of Unactivated ß-C(sp3)-H Bonds.

Palladium-catalyzed arylation of unactivated ß-C(sp3)-H bonds in carboxylic acid derivatives with aryl iodides is described for the first time using 2-amino-5,6-difluorophenyl-1H-pyrazole as an efficient and readily removable directing group. Two fluoro groups are installed at the 5- and 6-position of the anilino moiety in 2-aminophenyl-1H-pyrazole, clearly enhancing the directing ability of the auxiliary. In addition, the protocol employs Cu(OAc)2/Ag3PO4 (1.2/0.3) as additives, evidently reducing the stoichiometric amount of expensive silver salts. Furthermore, this process exhibits high ß-site selectivity, compatibility with diverse substrates containing α-hydrogen atoms, and excellent functional group tolerance.

Experimental demonstration of counterfactual quantum communication.

Quantum effects, besides offering substantial superiority in many tasks over classical methods, are also expected to provide interesting ways to establish secret keys between remote parties. A striking scheme called "counterfactual quantum cryptography" proposed by Noh [Phys. Rev. Lett. 103, 230501 (2009).] allows one to maintain secure key distributions, in which particles carrying secret information are seemingly not being transmitted through quantum channels. We have experimentally demonstrated, for the first time, a faithful implementation for such a scheme with an on-table realization operating at telecom wavelengths. To verify its feasibility for extension over a long distance, we have furthermore reported an illustration on a 1 km fiber. In both cases, high visibilities of more than 98% are achieved through active stabilization of interferometers. Our demonstration is crucial as a direct verification of such a remarkable application, and this procedure can become a key communication module for revealing fundamental physics through counterfactuals.

A novel compact real time radiation detector.

A novel compact real time radiation detector with cost-effective, ultralow power and high sensitivity based on Geiger counter is presented. The power consumption of this detector which employs CMOS electro circuit and ultralow-power microcontroller is down to only 12.8 mW. It can identify the presences of 0.22 µCi (60)Co at a distance of 1.29 m. Furthermore, the detector supports both USB bus and serial interface. It can be used for personal radiation monitoring and also fits the distributed sensor network for radiation detection.