Synthesis and Properties of Surfactants derived from N‐Acetyl‐D‐Glucosamine

The synthesis of 2‐acetamido‐2‐deoxy‐6‐O‐octanoyl‐D‐glucono‐1,5‐lactone 9 and 2‐acetamido‐2‐deoxy‐6‐O‐octanoyl‐α‐D‐glucopyranose 7 from 2‐acetamido‐2‐deoxy‐α‐D‐glucopyranose is reported. For both targets, the key intermediate was allyl 2‐acetamido‐3,4‐di‐O‐benzyl‐2‐deoxy‐6‐O‐octanoyl‐α‐D‐glucopyranoside 5. Surface tension measurements (critical micellar concentration of 22.3 mM and 5 mM for 9 and 7, respectively) showed up the surface activity of both compounds, while enzyme inhibition assays indicated that 9 could inhibit bovine β‐N‐acetylglucosaminidase (K_i=6.5 µM) but not Serratia marcescens chitobiase nor hen egg‐white lysozyme. Moreover, 7 was shown to induce chitinase production of S. marcescens and to be readily metabolized by these bacteria.      

Substituent Effects on Oxidation‐Induced Formation of Quinone Methides from Arylboronic Ester Precursors

A series of arylboronic esters containing different aromatic substituents and various benzylic leaving groups (Br or N⁺Me₃Br^?) have been synthesized. The substituent effects on their reactivity with H₂O₂ and formation of quinone methide (QM) have been investigated. NMR spectroscopy and ethyl vinyl ether (EVE) trapping experiments were used to determine the reaction mechanism and QM formation, respectively. QMs were not generated during oxidative cleavage of the boronic esters but by subsequent transformation of the phenol products under physiological conditions. The oxidative deboronation is facilitated by electron‐withdrawing substituents, such as aromatic F, NO₂, or benzylic N⁺Me₃Br^?, whereas electron‐donating substituents or a better leaving group favor QM generation. Compounds containing an aromatic CH₃ or OMe group, or a good leaving group (Br), efficiently generate QMs under physiological conditions. Finally, a quantitative relationship between the structure and activity has been established for the arylboronic esters by using a Hammett plot. The reactivity of the arylboronic acids/esters and the inhibition or facilitation of QM formation can now be predictably adjusted. This adjustment is important as some applications may benefit and others may be limited by QM generation.     

Kinetic Behavior of Quaternary Ammonium Hydroxides in Mixed Methane and Carbon Dioxide Hydrates

This study evaluates the kinetic hydrate inhibition (KHI) performance of four quaternary ammonium hydroxides (QAH) on mixed CH₄ + CO₂ hydrate systems. The studied QAHs are; tetraethylammonium hydroxide (TEAOH), tetrabutylammonium hydroxide (TBAOH), tetramethylammonium hydroxide (TMAOH), and tetrapropylammonium hydroxide (TPrAOH). The test was performed in a high-pressure hydrate reactor at temperatures of 274.0 K and 277.0 K, and a concentration of 1 wt.% using the isochoric cooling method. The kinetics results suggest that all the QAHs potentially delayed mixed CH₄ + CO₂ hydrates formation due to their steric hindrance abilities. The presence of QAHs reduced hydrate formation risk than the conventional hydrate inhibitor, PVP, at higher subcooling conditions. The findings indicate that increasing QAHs alkyl chain lengths increase their kinetic hydrate inhibition efficacies due to better surface adsorption abilities. QAHs with longer chain lengths have lesser amounts of solute particles to prevent hydrate formation. The outcomes of this study contribute significantly to current efforts to control gas hydrate formation in offshore petroleum pipelines.     

Detection of NMR signals with a radio-frequency atomic magnetometer

We demonstrate detection of proton NMR signals with a radio-frequency (rf) atomic magnetometer tuned to the NMR frequency of 62 kHz. High-frequency operation of the atomic magnetometer makes it relatively insensitive to ambient magnetic field noise. We obtain magnetic field sensitivity of 7 fT/Hz1/2 using only a thin aluminum shield. We also derive an expression for the fundamental sensitivity limit of a surface inductive pick-up coil as a function of frequency and find that an atomic rf magnetometer is intrinsically more sensitive than a coil of comparable size for frequencies below about 50 MHz.     

An optimization method for designing SENSE imaging RF coil arrays

An optimization method in RF coil array design for SENSE imaging is described. Using this method the optimized RF coil geometries can be calculated numerically given the required SENSE imaging performance. Although this method can be applied to optimize the RF coil arrays for both 1D and 2D SENSE imaging, to demonstrate the potential applications of this method, we designed RF coil arrays for 2D SENSE imaging and compared their performance by simulation. An optimized 4-channel receive-only RF coil array designed for 2D SENSE imaging was implemented and tested to demonstrate the feasibility of the proposed technique. Imaging results showed reasonable agreement with the simulations, thus the method can be applied to RF coil array designs for SENSE imaging when optimum imaging performance is desired.     

4T split TEM volume head and knee coils for improved sensitivity and patient accessibility

Split RF coils offer improved patient access by eliminating the need for the coil to be slid over the region of interest. For unshielded birdcage coils, the presence of end ring currents necessitates a direct electrical connection between two halves of the coil. For high-field (>3T) shielded birdcage coils, both the shield and the coil must be split and reliably connected electrically. This problem can be circumvented by the use of split TEM volume coils. Since the elements of a TEM coil are coupled inductively, no direct electrical connection between the halves is necessary. In this work we demonstrate that the effects of splitting the shield for head and knee TEMs can be compensated for, and performance retained. For the knee, the improved access allowed the coil diameter to be reduced, enhancing the sensitivity by 15-20%.     

Reception pattern influence on magnetoacoustic tomography with magnetic induction

Based on the acoustic radiation theory of a dipole source,the influence of the transducer reception pattern is studied for magnetoacoustic tomography with magnetic induction(MAT-MI).Numerical studies are conducted to simulate acoustic pressures,waveforms,and reconstructed images with unidirectional,omnidirectional,and strong directional transducers.With the analyses of equivalent and projection sources,the influences of the model dimension and the layer effect are qualitatively analyzed to evaluate the performance of MAT-MI.Three-dimensional simulation studies show that the strong directional transducer with a large radius can reduce the influences of equivalent sources,projection sources,and the layer effect effectively,resulting in enhanced pressure and improved image contrast,which is beneficial for boundary pressure extraction in conductivity reconstruction.The reconstructed conductivity contrast images present the conductivity boundaries as stripes with different contrasts and polarities,representing the values and directions of the conductivity changes of the scanned layer.The favorable results provide solid evidence for transducer selection and suggest potential practical applications of MAT-MI in biomedical imaging.     

Analytical and empirical studies on the characteristic resistances of no-insulation GdBCO racetrack pancake coil under various operating currents

This paper presents the effects of the Lorentz force on the electrical behaviors of the no-insulation (NI) GdBCO racetrack pancake (RP) coil without turn-to-turn insulation by performing charging/discharging and sudden-discharging tests. The simulation results of the 2-dimensional finite element method showed that the Lorentz forces were generated towards the center of the winding pack consisting of 60-turn GdBCO CCs, which could enhanced the turn-to-turn contact within the RP coil. The charging/discharging test results indicated that the characteristic resistance (R_c) of the NI RP coil decreased with increasing operating current, which was caused by an increase of the Lorentz force. Further, the results of the sudden-discharging tests exhibited that the Lorentz force was dissipated instantly during the sudden-discharge of the coil, since the operating current immediately decreased to zero. Overall, this study clearly demonstrated that the Lorentz force induced by the operating current exerts the electrical behaviors of an NI RP coil.     

Chiral Sulfinimines in Asymmetric Synthesis of Enantiomeric Aminophosphonic Acids

Abstract

Aminophosphonic acids have become important in different fields of chemistry, medicine and agriculture. In this review article, we highlight a new strategy developed in the author's laboratory of asymmetric synthesis of enantiomeric aminophosphonic acid that users chiral sulfinimines as reagents. A key reaction in the synthesis of enantiopure α-, β- and γ-aminophosphonic acids is a highly or fully diastereoselective addition of trivalent phosphorus nucleophiles and α-phosphonate carbanions to enantiopure sulfinimines. The steric course of these addition reactions is rationalized. The usefulness of the sulfinimine methodology is demonstrated by the synthesis of biologically active enantiopure 2-amino-3-phosphonopropanoic acid (AP3), 2-amino-4-phosphonobutanoic acid (AP4) and phosphoemeriamine.     

An Antibody with a Variable‐Region Coiled‐Coil “Knob” Domain

The X‐ray crystal structure of a bovine antibody (BLV1H12) revealed a unique structure in its ultralong heavy chain complementarity determining region 3 (CDR3H) that folds into a solvent‐exposed β‐strand “stalk” fused to a disulfide crosslinked “knob” domain. We have substituted an antiparallel heterodimeric coiled‐coil motif for the β‐strand stalk in this antibody. The resulting antibody (Ab‐coil) expresses in mammalian cells and has a stability similar to that of the parent bovine antibody. MS analysis of H–D exchange supports the coiled‐coil structure of the substituted peptides. Substitution of the knob‐domain of Ab‐coil with bovine granulocyte colony‐stimulating factor (bGCSF) results in a stably expressed chimeric antibody, which proliferates mouse NFS‐60 cells with a potency comparable to that of bGCSF. This work demonstrates the utility of this novel coiled‐coil CDR3 motif as a means for generating stable, potent antibody fusion proteins with useful pharmacological properties.