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Abstract Regioselective distal C−H functionalization of nitroarenes by overriding proximal C−H activation has remained an unsolved challenge. Herein, we present a palladium-catalyzed meta-C−H alkenylation of nitroarene substrate, achieved through leveraging the non-covalent hydrogen bonding interactions. Urea-based templates comprising an elongated biphenyl linker designed in such a way that it interacts with nitro group via strong hydrogen bonding interaction, while a cyano based directing group is attached along the template to coordinate with the palladium center, thereby facilitating the activation of the remote meta-C−H bond of nitrobenzene. Computational mechanistic investigation and the analysis of non-covalent interaction deciphers the crucial role of H-bonding in regulating the regioselectivity.

Abstract Dehydrogenation chemistry has long been established as a fundamental aspect of organic synthesis, commonly encountered in carbonyl compounds. Transition metal catalysis revolutionized it, with strategies like transfer-dehydrogenation, single electron transfer and C–H activation. These approaches, extended to multiple dehydrogenations, can lead to aromatization. Dehydrogenative transformations of aliphatic carboxylic acids pose challenges, yet engineered ligands and metal catalysis can initiate dehydrogenation via C–H activation, though outcomes vary based on substrate structures. Herein, we have developed a catalytic system enabling cyclohexane carboxylic acids to undergo multifold C–H activation to furnish olefinated arenes, bypassing lactone formation. This showcases unique reactivity in aliphatic carboxylic acids, involving tandem dehydrogenation-olefination-decarboxylation-aromatization sequences, validated by control experiments and key intermediate isolation. For cyclopentane carboxylic acids, reluctant to aromatization, the catalytic system facilitates controlled dehydrogenation, providing difunctionalized cyclopentenes through tandem dehydrogenation-olefination-decarboxylation-allylic acyloxylation sequences. This transformation expands carboxylic acids into diverse molecular entities with wide applications, underscoring its importance.

With the fast development of low earth orbit (LEO) enhanced global navigation satellite system (LeGNSS), there is huge demand in LEO real-time precise orbit determination. Real-time service from international GNSS service (IGS) provides the real-time precise GNSS orbit and clock products, which gives an opportunity to make use of kinematic precise point positioning (PPP) method for LEO POD. However, real-time precise GNSS products and onboard GNSS observations interrupt inevitably or even frequently (especially for real-time clock products), resulting in PPP reconvergence as well as large orbit errors in LEO orbit solutions. A new method is put forward to reduce such influence of two types of data interruptions. For interruption of clock products, the Chebyshev extrapolation is used to maintain the continuity of real-time GNSS clock products. For the onboard observation interruption, the predicted dynamic orbits are employed as constraints to overcome the PPP reconvergence. Results show that zero-reconvergence PPP can be realized with our new method, which means there is almost no reconvergence time after data interruption. Moreover, clock prediction can reduce the root–mean-square errors (RMSE) for real-time LEO orbit from 5.40, 4.70, and 7.33 cm to 5.18, 4.55, and 5.99 cm in along-track, cross-track, and radial directions, respectively, while the predicted dynamic orbit constraints reduce the orbit RMSE by 20--30% in cross-track component and 60%–80% in other two components.

The recruitment of the Low Earth Orbit (LEO) constellation is recognized as an effective way to augment Global Navigation Satellite System (GNSS) Precise Point Positioning (PPP) in the near future. Its potential to accelerate PPP convergence has been proved with simulated data. However, the mechanism of how the geometric change of LEO accelerates the convergence of GNSS PPP has not been studied from a theoretical perspective, which hampers the understanding and exploitation of the enhancement of LEO. In this article, the convergence mechanism of LEO enhanced GNSS PPP is investigated in terms of theoretical analysis and simulated verification. To show the characteristics of the ambiguities during convergence, eigenvalue decomposition is used to divide the ambiguities into orthogonal components, named geometric-related component, clock-error-related component, and independent component. The results show that the precision of geometric-related components of ambiguities, which correlates with position parameters, is low at a single epoch, while the precision can be greatly improved with the fast geometric change of LEO. On the other hand, the precision of clock-error-related components of ambiguities, which correlates with clock errors, cannot be improved by fast geometric change of LEO constellation due to its irrelevance to geometry, which causes the precision of each ambiguity to be low. Further investigations show that single-differenced ambiguities could overcome this drawback and are beneficial to ambiguity resolution.

A metal-free and Selectfluor-mediated selective oxidation reaction of benzo[d]isothiazol-3(2H)-ones in aqueous media is presented. This novel strategy provides a facile, green, and efficient approach to access important benzo[d]isothiazol-3(2H)-one-1-oxides with excellent yields and high tolerance to various functional groups. Furthermore, the purification of benzoisothiazol-3-one-1-oxides does not rely on column chromatography. Moreover, the preparation of saccharine derivatives has been achieved through sequential, double oxidation reactions in a one-pot aqueous media.

In order to solve the problems of semantic loss and inaccurate boundary detection in the process of object tracking, a visual tracking algorithm combining parallel structure with dual attention-aware mechanism is proposed in this paper. As backbone network, parallel structure is composed of Convolutional neural network and Attention Cooperative(CAC) processing module, which is used for feature extraction. Because this structure can capture the local and global information of the target at the same time, it can solve the problem of semantic information loss. Dual Attention-aware Network(DAN) is used for feature enhancement, which is composed of target-aware attention and boundary-aware attention. Template online updating strategy is used to improve template quality, and an effective score prediction module-Template Elimination Mechanism(TEM) is designed in the CAC processing module to select high quality templates. This kind of object tracking algorithm which combines local and global information is called TrackCAC. The evaluation results on different datasets show that the algorithm can maintain high tracking precision and success in different scenarios. It shows good robustness and accuracy in the performance evaluation results on VOT datasets.

Cascade reactions—chemical processes consisting of two or more reactions in one pot—offer considerable advantages in terms of time, cost, atom efficiency, and reduced waste generation, and have thus unsurprisingly attracted considerable attention amongst the chemical community in recent decades. On the other hand, transition metal-catalyzed site-selective carbon-hydrogen (C–H) bond functionalization represents one of the most significant and efficient synthetic approaches in organic chemistry, enabling the conversion of common petroleum chemicals into highly valuable products in a single step. Utilization of this approach in cascades dramatically improves its applicability by allowing for the efficient construction of complex molecules from simple starting materials in a single pot. This perspective summarizes the developments in palladium (II)-catalyzed cascade reactions initiated with directed activation of unactivated aliphatic C–H bonds and our recent efforts in synthesizing bicyclic lactones, followed by current challenges and future opportunities.

2-Pyridone ligand-facilitated palladium-catalyzed direct C–H bond functionalization via the transient directing group strategy has become an attractive topic. Here, we report a Pd-catalyzed direct β-C(sp3)–H arylation reaction of tertiary aliphatic aldehydes by using an α-amino acid as a transient directing group in combination with a 2-pyridone ligand.

Although deformations are mostly insignificant, they can be catastrophic when accumulated to certain amounts. Precise point positioning (PPP) can work with one receiver, preventing problems caused by the base station constrain upon employment of current methods such as real-time kinematics (RTK). However, current methods employing PPP focus on high-frequency monitoring such as earthquake or geological calamity monitoring, and these methods are not suitable for structures. Thus, this study proposes a new method for the deformation monitoring of structures via PPP. First, we obtained the coordinate sequence of structures via static PPP when setting the interval. Then, we transformed the coordinates to the same coordinate system with the same basis. Finally, we decomposed the sequences via empirical mode decomposition (EMD) to obtain a low-frequency part, which is the deformation of the target structure. The result of the monitoring experimentation on IGS stations shows that the monitoring index, Sd, of the sequence under different intervals using this method could be 1–2 mm on average in the directions of E, N, and U, which is much better than the original monitoring sequence. Alongside that, it prevented a fall in accuracy when the interval decreased. Therefore, all results proved the feasibility and validity of the method.

Thioether skeletons are widely present in drugs, natural products, functional materials, and life science. In the past decade, the selective C–H functionalization of thioethers has been extensively studied to construct novel thioether derivatives. This mini-review systematically introduces the recent advances in the field of the direct α-C(sp3)-H functionalization of thioethers.

Abstract Real-Time Precise Point Positioning (RT-PPP) has been one of the research hotspots in GNSS (Global Navigation Satellite System) community for decades. Real-time precise products of satellite orbits and clocks are the prerequisite for RT-PPP. Thus, it is of great importance to investigate the current multi-GNSS real-time precise products in State Space Representation (SSR) from different analysis centers. In this article, SSR products from 10 analysis centers are comprehensively evaluated by comparing them with the final products and performing the kinematic PPP. The results show that analysis centers CNES (Centre National D'Etudes Spatiales) and WHU (GNSS Research Center of Wuhan University) provide the most complete products with the best quality. Concerning the accuracy of real-time products for the GNSSs, the accuracies of orbit and clock products are better than 5 cm and 0.15 ns, respectively, for Global Positioning System (GPS), followed by Galileo navigation satellite system (Galileo), BeiDou-3 Navigation Satellite System (BDS-3), GLObal NAvigation Satellite System (GLONASS), and BeiDou-2 Navigation Satellite System (BDS-2). Meanwhile, the results of the RT-PPP with quad-system show that the positioning accuracies are 1.76, 1.12 and 2.68 cm in east, north, and up directions, respectively, and the convergence time to 0.1, 0.1, 0.2 m for corresponding directions is 15.35 min.

With the completion of Chinese BeiDou Navigation Satellite System (BDS), the world has begun to enjoy the Positioning, Navigation, and Timing (PNT) services of four Global Navigation Satellite Systems (GNSS). In order to improve the GNSS performance and expand its applications, Low Earth Orbit (LEO) Enhanced Global Navigation Satellite System (LeGNSS) is being vigorously advocated. Combined with high-, medium-, and low- earth orbit satellites, it can improve GNSS performance in terms of orbit determination, Precise Point Positioning (PPP) convergence time, etc. This paper comprehensively reviews the current status of LeGNSS, focusing on analyzing its advantages and challenges for precise orbit and clock determination, PPP convergence, earth rotation parameter estimation, and global ionosphere modeling. Thanks to the fast geometric change brought by LEO satellites, LeGNSS is expected to fundamentally solve the problem of the long convergence time of PPP without any augmentation. The convergence time can be shortened within 1 minute if appropriate LEO constellations are deployed. However, there are still some issues to overcome, such as the optimization of LEO constellation as well as the real time LEO precise orbit and clock determination.

The ubiquitous presence of sp3 C−H bonds in natural feedstock makes them inexpensive, easily accessible, and attractive synthons for the preparation of common and/or complex molecular frameworks in biologically active natural products, pharmaceutics, agrochemicals, and materials. However, the inertness of these bonds due to the high bond dissociation energies and low polarity difference between the carbon and hydrogen atoms makes them challenging reaction partners. Moreover, the desired site-selectivity is often an issue in reactions with multiple analogous sp3 C−H bonds. To overcome these problems, transition metal-catalyzed C−H functionalization has been developed with the assistance of various well-designed directing groups which can coordinate to a metal center to deliver it on a targeted C−H bond through an appropriate spatial arrangement, enabling C−H activation via the formation of a cyclometalated species. However, the frequent requirement of additional steps for the construction of the directing groups and their subsequent removal after the desired operation severely hampers the efficacy and compatibility of the reactions. A promising solution would be the utilization of a transient ligand which can bind to the substrate and coordinate to the metal center in a reversible fashion. In this way, the directing group is installed, sp3 C−H functionalization occurs, and the directing group is then removed in situ without affecting the substrate function after the catalysis is finished. Overall, the whole process occurs in a single reaction pot. Herein, we are presenting our studies on transition metal-catalyzed transient directing group-enabled C−H functionalization reaction.

N-heterocycles are ubiquitous in natural products, pharmaceuticals, organic materials, and numerous functional molecules. Among the current synthetic approaches, transition metal-catalyzed C–H functionalization has gained considerable attention in recent years due to its advantages of simplicity, high atomic economy, and the ready availability of starting materials. In the field of N-heterocycle synthesis via C–H functionalization, nickel has been recognized as one of the most important catalysts. In this review, we will introduce nickel-catalyzed intramolecular and intermolecular pathways for N-heterocycle synthesis from 2008 to 2021.

This meta-analysis was conducted to assess the consistency and strength of the relationship between polymorphism of IL-2 -330T/G and susceptibility to pulmonary tuberculosis (TB). PubMed, Web of Knowledge and CNKI were searched to find eligible studies about the relationship between IL-2 -330T/G polymorphism and susceptibility to pulmonary TB. A total of eight studies comprising 971 cases and 1519 controls were grouped together for the purpose of elucidating the relationship between polymorphism of IL-2 -330T/G and pulmonary TB susceptibility. The allele model (G vs. T: odds ratio (OR) = 1.34; 95% confidence interval (CI) 1.05–1.71, P het = 0.001) and the recessive model (GG+GT vs. TT: OR = 1.60; 95% CI 1.08–2.38, P het = 0.0001) showed an increased risk of development of pulmonary TB. However, the homozygous model (GG vs. TT: OR = 1.74; 95% CI 0.98–3.09, P het = 0.0005) and the dominant model (GG vs. TT + TG: OR = 1.30; 95% CI = 0.80-2.14, P het = 0.001) failed to show an increased incidence of pulmonary TB. When analysis was stratified by ethnicity, no obvious associations were identified in the Caucasian subgroup under all four genetic models. Additionally, heterogeneity disappeared in the analysis of Caucasian subgroup. Our combined data suggested that there was no association between IL-2 -330T/G polymorphism and pulmonary TB among Caucasians.

The precise orbit determination (POD) accuracy of the Chinese BeiDou Navigation Satellite System (BDS) is still not comparable to that of the Global Positioning System because of the unfavorable geometry of the BDS and the uneven distribution of BDS ground monitoring stations. Fortunately, low Earth orbit (LEO) satellites, serving as fast moving stations, can efficiently improve BDS geometry. Nearly all studies on Global Navigation Satellite System POD enhancement using large LEO constellations are based on simulations and their results are usually overly optimistic. The receivers mounted on a spacecraft or an LEO satellite are usually different from geodetic receivers and the observation conditions in space are more challenging than those on the ground. The noise level of spaceborne observations needs to be carefully calibrated. Moreover, spaceborne observational errors caused by space weather events, i.e., solar geomagnetic storms, are usually ignored. Accordingly, in this study, the actual spaceborne observation noises are first analyzed and then used in subsequent observation simulations. Then, the observation residuals from the actual-processed LEO POD during a solar storm on 8 September 2017 are extracted and added to the simulated spaceborne observations. The effect of the observational errors on the BDS POD augmented with different LEO constellation configurations is analyzed. The results indicate that the noise levels from the Swarm-A, GRACE-A, and Sentinel-3A satellites are different and that the carrier-phase measurement noise ranges from 2 mm to 6 mm. Such different noise levels for LEO spaceborne observations cause considerable differences in the BDS POD solutions. Experiments calculating the augmented BDS POD for different LEO constellations considering spaceborne observational errors extracted from the solar storm indicate that these errors have a significant influence on the accuracy of the BDS POD. The 3D root mean squares of the BDS GEO, IGSO, and MEO satellite orbits are 1.30 m, 1.16 m, and 1.02 m, respectively, with a Walker 2/1/0 LEO constellation, and increase to 1.57 m, 1.72 m, and 1.32 m, respectively, with a Walker 12/3/1 constellation. When the number of LEO satellites increases to 60, the precision of the BDS POD improves significantly to 0.89 m, 0.77 m, and 0.69 m for the GEO, IGSO, and MEO satellites, respectively. While 12 satellites are sufficient to enhance the BDS POD to the sub-decimeter level, up to 60 satellites can effectively reduce the influence of large spaceborne observational errors, i.e., from solar storms.

The Korean government has a plan to build a new regional satellite navigation system called the Korean Positioning System (KPS). The initial KPS constellation is designed to consist of seven satellites, which include three geostationary Earth orbit (GEO) satellites and four inclined geosynchronous orbit (IGSO) satellites. KPS will provide an independent positioning, navigation, and timing (PNT) service in the Asia-Oceania region and can also be compatible with GPS. In the simulation for KPS, we employ 24 GPS as designed initially and 7 KPS satellites. Compared to the true orbit that we simulated, the averaged root mean square (RMS) values of orbit-only signal-in-space ranging errors (SISRE) are approximately 4.3 and 3.9 cm for KPS GEO and IGSO. Two different positioning solutions are analyzed to demonstrate the KPS performance. KPS standard point positioning (SPP) errors in the service area are about 4.7, 3.9, and 7.1 m for east (E), north (N), and up (U) components, respectively. The combined KPS+GPS SPP accuracy can be improved by 25.0%, 31.8%, and 35.0% compared to GPS in E, N, and U components. The averaged position errors for KPS kinematic precise point positioning (KPPP) are less than 10 cm. In the fringe of the KPS service area, however, the position RMS errors can reach about 40 cm. Unlike KPS, GPS solutions show high positioning accuracy in the KPS service area. The combined KPS+GPS can be improved by 28.7%, 27.1%, and 30.5% compared to GPS in E, N, and U components, respectively. It is noted that KPS can provide better performance with GPS in the Asia-Oceania region.

Low Earth Orbit (LEO) satellites have been widely used in scientific fields or commercial applications in recent decades. The demands of the real time scientific research or real time applications require real time precise LEO orbits. Usually, the predicted orbit is one of the solutions for real time users, so it is of great importance to investigate LEO orbit prediction for users who need real time LEO orbits. The centimeter level precision orbit is needed for high precision applications. Aiming at obtaining the predicted LEO orbit with centimeter precision, this article demonstrates the traditional method to conduct orbit prediction and put forward an idea of LEO orbit prediction by using onboard accelerometer data for real time applications. The procedure of LEO orbit prediction is proposed after comparing three different estimation strategies of retrieving initial conditions and dynamic parameters. Three strategies are estimating empirical coefficients every one cycle per revolution, which is the traditional method, estimating calibration parameters of one bias of accelerometer hourly for each direction by using accelerometer data, and estimating calibration parameters of one bias and one scale factor of the accelerometer for each direction with one arc by using accelerometer data. The results show that the predicted LEO orbit precision by using the traditional method can reach 10 cm when the predicted time is shorter than 20 min, while the predicted LEO orbit with better than 5 cm for each orbit direction can be achieved with accelerometer data even to predict one hour.

The main challenge of precise point positioning (PPP) applications is the long convergence time of typically a half hour, or even more, to achieve centimeter accuracy. Even when the multi-constellation is involved and ambiguity resolution is implemented, it still requires about ten minutes. It is becoming a hot spot to incorporate the low Earth orbit (LEO) satellite constellation for enhancing the Global Navigation Satellite System (GNSS), named here as LEO-enhanced GNSS (LeGNSS). In this system, the LEO satellites cannot only receive GNSS signals, but also serve as GNSS satellites by transmitting similar navigation signals to the ground users, but with higher signal strength and much faster geometric change due to their low altitude. As a result, the convergence time of PPP is expected to be shortened to a few minutes, or even seconds. Simulation software is developed to simulate GNSS and LEO observations for ground stations taking into account tropospheric delay, satellite clock errors, observation noises, as well as other error sources. Then the number of visible satellites, the geometry dilution of precision (GDOP), and the convergence time of the kinematic mode of PPP are evaluated on a global scale compared to those of GNSS systems. The simulation results show that LeGNSS can decrease the PPP convergence to 5 min. If there are more LEO satellites included in the LeGNSS, it is expected that the initialization of PPP can be further shortened.