Formaldehyde-Mediated Hydride Liberation of Alkylamines for Intermolecular Reactions in Hexafluoroisopropanol.

The ability of alkylamines to spontaneously liberate hydride ions is typically restrained, except under specific intramolecular reaction settings. Herein, we demonstrate that this reactivity can be unlocked through simple treatment with formaldehyde in hexafluoroisopropanol (HFIP) solvent, thereby enabling various intermolecular hydride transfer reactions of alkylamines under mild conditions. Besides transformations of small molecules, these reactions enable unique late-stage modification of complex peptides. Mechanistic investigations uncover that the key to these intermolecular hydride transfer processes lies in the accommodating conformation of solvent-mediated macrocyclic transition states, where the aggregates of HFIP molecules act as dexterous proton shuttles. Importantly, negative hyperconjugation between the lone electron pair of nitrogen and the antibonding orbital of amine's α C-H bond plays a critical role in the C-H activation, promoting its hydride liberation.

Construction of Complex Macromulticyclic Peptides via Stitching with Formaldehyde and Guanidine.

There is a growing interest in constructing multicyclic peptide structures to expand the chemical space of peptides. Conventional strategies for constructing large peptide structures are limited by the typical reliance on the inflexible coupling between premade templates equipped with fixed reactive handles and peptide substrates via cysteine anchors. Herein, we report the development of a facile three-component condensation reaction of primary alkyl amine, formaldehyde, and guanidine for construction of complex macromulticyclic peptides with novel topologies via lysine anchors. Moreover, the reaction sequences can be orchestrated in different anchor combinations and spatial arrangements to generate various macrocyclic structures crosslinked by distinct fused tetrahydrotriazine linkages. The macrocyclization reactions are selective, efficient, versatile, and workable in both organic and aqueous media. Thus, the condensation reaction provides a smart tool for stitching native peptides in situ using simple methylene threads and guanidine joints in a flexible and programmable manner.

Ruthenium-Catalyzed Pyridine-Directed Aryl C-H Glycosylation with Glycosyl Chlorides.

Metal-catalyzed C-H glycosylation reactions with glycosyl chloride donors have emerged as a useful strategy for the synthesis of C-glycosides. Previously, palladium and nickel complexes were reported to catalyze C-H glycosylation reactions using amide-linked bidentate auxiliaries. Herein, a ruthenium-catalyzed ortho C-H glycosylation reaction of arenes with various glycosyl chloride donors using a monodentate pyridine directing group is developed. Preliminary mechanistic studies indicated that two-electron oxidative addition and reductive elimination of ruthenocycle intermediate led to the glycosylation products.

Improving the Strapdown Airborne Vector Gravimetry by a Backward Inertial Navigation Algorithm.

Strapdown airborne gravimetry is an efficient way to obtain gravity field data. A new method has been developed to improve the accuracy of airborne vector gravimetry. The method introduces a backward strapdown navigation algorithm into the strapdown gravimetry, which is the reverse process of forward algorithm. Compared with the forward algorithm, the backward algorithm has the same performance in the condition of no sensor error, but has different error characteristics in actual conditions. The differences of the two algorithms in the strapdown gravimetry data processing are presented by simulations, which show that the two algorithms have different performance in the horizontal attitude measurement and convergence of integrated navigation filter. On the basis of detailed analysis, the procedures of accuracy improvement method are presented. The result of this method is very promising when applying to an actual flight test carried out by a SGA-WZ02 strapdown gravimeter. After applying the proposed method, the repeatability of two gravity disturbance horizontal components were 1.83 mGal and 1.80 mGal under the resolution of 6 km, which validate the effectiveness of the method. Furthermore, the wavenumber correlation filter is also discussed as an alternative data fusion method.

Compensation of Horizontal Gravity Disturbances for High Precision Inertial Navigation.

Horizontal gravity disturbances are an important factor that affects the accuracy of inertial navigation systems in long-duration ship navigation. In this paper, from the perspective of the coordinate system and vector calculation, the effects of horizontal gravity disturbance on the initial alignment and navigation calculation are simultaneously analyzed. Horizontal gravity disturbances cause the navigation coordinate frame built in initial alignment to not be consistent with the navigation coordinate frame in which the navigation calculation is implemented. The mismatching of coordinate frame violates the vector calculation law, which will have an adverse effect on the precision of the inertial navigation system. To address this issue, two compensation methods suitable for two different navigation coordinate frames are proposed, one of the methods implements the compensation in velocity calculation, and the other does the compensation in attitude calculation. Finally, simulations and ship navigation experiments confirm the effectiveness of the proposed methods.

A Model of Gravity Vector Measurement Noise for Estimating Accelerometer Bias in Gravity Disturbance Compensation.

Compensation of gravity disturbance can improve the precision of inertial navigation, but the effect of compensation will decrease due to the accelerometer bias, and estimation of the accelerometer bias is a crucial issue in gravity disturbance compensation. This paper first investigates the effect of accelerometer bias on gravity disturbance compensation, and the situation in which the accelerometer bias should be estimated is established. The accelerometer bias is estimated from the gravity vector measurement, and a model of measurement noise in gravity vector measurement is built. Based on this model, accelerometer bias is separated from the gravity vector measurement error by the method of least squares. Horizontal gravity disturbances are calculated through EGM2008 spherical harmonic model to build the simulation scene, and the simulation results indicate that precise estimations of the accelerometer bias can be obtained with the proposed method.

Strapdown Airborne Gravimetry Quality Assessment Method Based on Single Survey Line Data: A Study by SGA-WZ02 Gravimeter.

Quality assessment is an important part in the strapdown airborne gravimetry. Root mean square error (RMSE) evaluation method is a classical way to evaluate the gravimetry quality, but classical evaluation methods are preconditioned by extra flight or reference data. Thus, a method, which is able to largely conquer the premises of classical quality assessment methods and can be used in single survey line, has been developed in this paper. According to theoretical analysis, the method chooses the stability of two horizontal attitude angles, horizontal specific force and vertical specific force as the determinants of quality assessment method. The actual data, collected by SGA-WZ02 from 13 flights 21 lines in certain survey, was used to build the model and elaborate the method. To substantiate the performance of the quality assessment model, the model is applied in extra repeat line flights from two surveys. Compared with internal RMSE, standard deviation of assessment residuals are 0.23 mGal and 0.16 mGal in two surveys, which shows that the quality assessment method is reliable and stricter. The extra flights are not necessary by specially arranging the route of flights. The method, summarized from SGA-WZ02, is a feasible approach to assess gravimetry quality using single line data and is also suitable for other strapdown gravimeters.

A New Method for Land Vehicle Gravimetry Using SINS/VEL.

n/a.

An SINS/GNSS Ground Vehicle Gravimetry Test Based on SGA-WZ02.

In March 2015, a ground vehicle gravimetry test was implemented in eastern Changsha to assess the repeatability and accuracy of ground vehicle SINS/GNSS gravimeter-SGA-WZ02. The gravity system developed by NUDT consisted of a Strapdown Inertial Navigation System (SINS), a Global Navigation Satellite System (GNSS) remote station on test vehicle, a GNSS static master station on the ground, and a data logging subsystem. A south-north profile of 35 km along the highway in eastern Changsha was chosen and four repeated available measure lines were obtained. The average speed of a vehicle is 40 km/h. To assess the external ground gravity disturbances, precise ground gravity data was built by CG-5 precise gravimeter as the reference. Under relative smooth conditions, internal accuracy among repeated lines shows an average agreement at the level of 1.86 mGal for half wavelengths about 1.1 km, and 1.22 mGal for 1.7 km. The root-mean-square (RMS) of difference between calculated gravity data and reference data is about 2.27 mGal/1.1 km, and 1.74 mGal/1.7 km. Not all of the noises caused by vehicle itself and experiments environments were eliminated in the primary results. By means of selecting reasonable filters and improving the GNSS observation conditions, further developments in ground vehicle gravimetry are promising.

Optimized Design of the SGA-WZ Strapdown Airborne Gravimeter Temperature Control System.

The temperature control system is one of the most important subsystems of the strapdown airborne gravimeter. Because the quartz flexible accelerometer based on springy support technology is the core sensor in the strapdown airborne gravimeter and the magnet steel in the electromagnetic force equilibrium circuits of the quartz flexible accelerometer is greatly affected by temperature, in order to guarantee the temperature control precision and minimize the effect of temperature on the gravimeter, the SGA-WZ temperature control system adopts a three-level control method. Based on the design experience of the SGA-WZ-01, the SGA-WZ-02 temperature control system came out with a further optimized design. In 1st level temperature control, thermoelectric cooler is used to conquer temperature change caused by hot weather. The experiments show that the optimized stability of 1st level temperature control is about 0.1 °C and the max cool down capability is about 10 °C. The temperature field is analyzed in the 2nd and 3rd level temperature control using the finite element analysis software ANSYS. The 2nd and 3rd level temperature control optimization scheme is based on the foundation of heat analysis. The experimental results show that static accuracy of SGA-WZ-02 reaches 0.21 mGal/24 h, with internal accuracy being 0.743 mGal/4.8 km and external accuracy being 0.37 mGal/4.8 km compared with the result of the GT-2A, whose internal precision is superior to 1 mGal/4.8 km and all of them are better than those in SGA-WZ-01.

Experimental investigations on airborne gravimetry based on compressed sensing.

Gravity surveys are an important research topic in geophysics and geodynamics. This paper investigates a method for high accuracy large scale gravity anomaly data reconstruction. Based on the airborne gravimetry technology, a flight test was carried out in China with the strap-down airborne gravimeter (SGA-WZ) developed by the Laboratory of Inertial Technology of the National University of Defense Technology. Taking into account the sparsity of airborne gravimetry by the discrete Fourier transform (DFT), this paper proposes a method for gravity anomaly data reconstruction using the theory of compressed sensing (CS). The gravity anomaly data reconstruction is an ill-posed inverse problem, which can be transformed into a sparse optimization problem. This paper uses the zero-norm as the objective function and presents a greedy algorithm called Orthogonal Matching Pursuit (OMP) to solve the corresponding minimization problem. The test results have revealed that the compressed sampling rate is approximately 14%, the standard deviation of the reconstruction error by OMP is 0.03 mGal and the signal-to-noise ratio (SNR) is 56.48 dB. In contrast, the standard deviation of the reconstruction error by the existing nearest-interpolation method (NIPM) is 0.15 mGal and the SNR is 42.29 dB. These results have shown that the OMP algorithm can reconstruct the gravity anomaly data with higher accuracy and fewer measurements.

Long-term stability of the SGA-WZ strapdown airborne gravimeter.

Accelerometers are one of the most important sensors in a strapdown airborne gravimeter. The accelerometer's drift determines the long-term accuracy of the strapdown inertial navigation system (SINS), which is the primary and most critical component of the strapdown airborne gravimeter. A long-term stability test lasting 104 days was conducted to determine the characteristics of the strapdown airborne gravimeter's long-term drift. This stability test was based on the first set of strapdown airborne gravimeters built in China, the SGA-WZ. The test results reveal a quadratic drift in the strapdown airborne gravimeter data. A drift model was developed using the static data in the two end sections, and then this model was used to correct the test data. After compensating for the drift, the drift effect improved from 70 mGal to 3.46 mGal with a standard deviation of 0.63 mGal. The quadratic curve better reflects the drift's real characteristics. In comparison with other methodologies, modelling the drift as a quadratic curve was shown to be more appropriate. Furthermore, this method allows the drift to be adjusted throughout the course of the entire campaign.

Silver-Catalyzed Activation of Pyridotriazoles for Formal Intramolecular Carbene Insertion into Vinylic C(sp2)-H Bonds.

A silver-catalyzed intramolecular denitrogenative annulation of pyridotriazole with alkene was reported to achieve the challenging carbene insertion into the vinylic C(sp2)-H bond. This protocol has enabled the construction of functionalized 1H-indenes with high efficiency and excellent functional group tolerance. Experimental and computational studies suggest a stepwise mechanism involving a water-promoted hydrogen atom transfer with the aid of a silver catalyst.