Efficient catalyst-free N2 fixation by water radical cations under ambient conditions.

The growth and sustainable development of humanity is heavily dependent upon molecular nitrogen (N2) fixation. Herein we discover ambient catalyst-free disproportionation of N2 by water plasma which occurs via the distinctive HONH-HNOH+• intermediate to yield economically valuable nitroxyl (HNO) and hydroxylamine (NH2OH) products. Calculations suggest that the reaction is prompted by the coordination of electronically excited N2 with water dimer radical cation, (H2O)2+•, in its two-center-three-electron configuration. The reaction products are collected in a 76-needle array discharge reactor with product yields of 1.14 µg cm-2 h-1 for NH2OH and 0.37 µg cm-2 h-1 for HNO. Potential applications of these compounds are demonstrated to make ammonia (for NH2OH), as well as to chemically react and convert cysteine, and serve as a neuroprotective agent (for HNO). The conversion of N2 into HNO and NH2OH by water plasma could offer great profitability and reduction of polluting emissions, thus giving an entirely look and perspectives to the problem of green N2 fixation.

Hydroxyl transfer versus cyclization reaction in the gas phase: Sequential loss of NH3 and CH2CO from protonated phenylalanine derivatives.

Collisional activation of protonated phenylalanine derivatives deamination products leads to hydroxyl skeletal rearrangement versus cyclization reaction, and to form hydroxylbenzyl cation via elimination of CH2CO. To better clarify this unusual fragmentation reaction, accurate mass measurements experiments, native isotope experiments, multiple-stage mass spectrometry experiments, different substituents experiments, and density functional theory (DFT) calculations were carried out to investigate the dissociation mechanistic pathways of protonated phenylalanine derivatives deamination products. In route 1, a three-membered ring-opening reaction and a 1,3-hydroxyl transfer (from the carbonyl carbon atom to the interposition carbon atom of carbonyl) occurs to form 3-hydroxy-1-oxo-3-phenylpropan-1-ylium, followed by dissociation to lose CH2CO to give hydroxy (phenyl)methylium. In route 2, a successive cyclization rearrangement reaction and proton transfer occur to form a 2-hydroxylphenylpropionyl cation or protonated 2-hydroxy-4H-benzopyran, followed by dissociation to lose CH2CO or CH≡COH to give 2-hydroxylbenzyl cation. In route 3, a successive hydroxyl transfer (from the carbonyl carbon atom to the ortho carbon atom on benzene) and two stepwise proton transfer (1,2-proton transfer to the ipso-carbon atom of the phenyl ring followed by 1,3-proton transfer to the ortho carbon atom of carbonyl) occurs to form a 2-hydroxylphenylpropionyl cation, which subsequently dissociates to form 2-hydroxylbenzyl cation by elimination of CH2CO. DFT calculations suggested that route 1 was more favorable than route 2 and route 3 from a thermodynamic point of view.

An Improved Weighted Gradient Projection Method for Inverse Kinematics of Redundant Surgical Manipulators.

Different from traditional redundant manipulators, the redundant manipulators used in the surgical environment require the end effector (EE) to have high pose (position and orientation) accuracy to ensure the smooth progress of the operation. When analyzing the inverse kinematics (IK) of traditional redundant manipulators, gradient-projection method (GPM) and weighted least-norm (WLN) method are commonly used methods to avoid joint position limits. However, for the traditional GPM and WLN method, when joints are close to their limits, they stop moving, which greatly reduces the accuracy of the IK solution. When robotic manipulators enter a singular region, although traditional damped least-squares (DLS) algorithms are used to handle singularities effectively, motion errors of the EE will be introduced. Furthermore, selecting singular region through trial and error may cause some joint velocities exceed their corresponding limits. More importantly, traditional DLS algorithms cannot guide robotic manipulators away from singular regions. Inspired by the merits of GPM, WLN, and DLS methods, an improved weighted gradient projection method (IWGPM) is proposed to solve the IK problem of redundant manipulators used in the surgical environment with avoiding joint position limits and singularities. The weighted matrix of the WLN method and the damping factor of the DLS algorithm have been improved, and a joint limit repulsive potential field function and singular repulsive potential field function belong to the null space are introduced to completely keep joints away from the damping interval and redundant manipulators away from the unsafe region. To verify the validity of the proposed IWGPM, simulations on a 7 degree of freedom (DOF) redundant manipulator used in laparoscopic surgery indicate that the proposed method can not only achieve higher accuracy IK solution but also avoid joint position limits and singularities effectively by comparing them with the results of the traditional GPM and WLN method, respectively. Furthermore, based on the proposed IWGPM, simulation tests in two cases show that joint position limits have a great impact on the orientation accuracy, and singular potential energy function has a great impact on the position accuracy.