Construction and Demonstration of a 6–18 GHz Microwave Three-Wave Mixing Experiment using Multiple Synchronized Arbitrary Waveform Generators

This manuscript details the construction and demonstration of the first known microwave three-wave mixing (M3WM) experiment utilizing multiple arbitrary waveform generators (AWGs) completely operable in the 6–18 GHz frequency range for use in chirality determination and quantification. Many M3WM techniques, which involve two orthogonal, subsequent Rabi π/2 and π microwave pulses, suffer from flexibility in pulse types and timings as well as frequency due to most instruments only using one, one-channel AWG and the M3WM probability decreasing with an increasing quantum number, J. In this work, we presented an M3WM instrument that allows that flexibility by introducing multiple, synchronized AWGs and adheres to the high probability transition loop pathways in carvone. The functionality and reliability of the instrument were demonstrated using a series of experiments and mixtures of the R and S enantiomers and determined to be of similar accuracy to other reported M3WM setups with the additional benefit of flexibility in pulsing schemes

Solid State NMR Spectroscopy/Imaging in Situ Measuring Devices and Methods for Calibration and Determining One or More Quantitative Properties of a Target SampleAbstract

In situ measuring devices, methods of making the same, and methods of using the same are provided herein. The in situ measuring devices can include a capillary tube having a reference material sealed inside the capillary tube, where the capillary tube is positioned inside of a solid state or MAS NMR rotor. A target sample can also be positioned in the interior of the solid state or MAS NMR rotor but is sequestered from the reference material by a capillary tube wall. The in situ measuring devices can be used in solid state MAS NMR spectroscopy to quantify one or more parameters of a target sample, such as the quantity of a sample, chemical identity of a sample, or temperature of a sample

Solid State NMR Spectroscopy/Imaging in Situ Measuring Devices and Methods for Calibration and Determining One or More Quantitative Properties of a Target Sample

In situ measuring devices, methods of making the same, and methods of using the same are provided herein. The in situ measuring devices can include a capillary tube having a reference material sealed inside the capillary tube, where the capillary tube is positioned inside of a solid state or MAS NMR rotor. A target sample can also be positioned in the interior of the solid state or MAS NMR rotor but is sequestered from the reference material by a capillary tube wall. The in situ measuring devices can be used in solid state MAS NMR spectroscopy to quantify one or more parameters of a target sample, such as the quantity of a sample, chemical identity of a sample, or temperature of a sample

Method and Apparatus for Jet-Assisted Drilling or Cutting

An abrasive cutting or drilling system, apparatus and method, which includes an upstream supercritical fluid and/or liquid carrier fluid, abrasive particles, a nozzle and a gaseous or low-density supercritical fluid exhaust abrasive stream. The nozzle includes a throat section and, optionally, a converging inlet section, a divergent discharge section, and a feed section

NMR Studies of Loaded Microspheres

Porous-wall hollow glass microspheres (PWHGMs) are a novel form of glass materials that consist of 1-μm-thick porous silica shells, 20-100 μm in diameter, with a hollow cavity in the center. Utilizing the central cavity for material storage and the porous walls for controlled release is a unique combination that renders PWHGMs a superior vehicle for targeted drug delivery. In this study, NMR spectroscopy was used to characterize PWHGMs for the first time. A vacuum-based loading system was developed to load PWHGMs with various compounds followed by a washing procedure that uses solvents immiscible with the target material. Immiscible binary model systems (chloroform/water, n-dodecane/water), as well as the hydrolysis of isopropyl acetate, were investigated to obtain NMR evidence for material loading into PWHGMs and their subsequent release to the surrounding solutions. The NMR peaks of the loaded materials were distinguishable from the NMR peaks of the materials in the surrounding solution. The formation of the reaction product isopropanol provided evidence of encounters of isopropyl acetate in the microspheres and concentrated H2SO4 added to the surrounding solution. Also, microspheres loaded with H2O were suspended in D2O and monitored to obtain quantitative release kinetics of H2O encapsulated in PWHGMs. A five-parameter double-exponential curve fit of experimental signal intensity data as a function of time indicated two release rates for H2O encapsulated in PWHGMs with time constants of 18 - 20 minutes and 160 minutes. The results demonstrate that NMR is a particularly useful tool to study developments and applications of PWHGMs in targeted drug delivery

In Situ NMR Parameter Monitoring Systems and Methods for Measuring PH and Temperature

Devices and methods are provided for measuring temperatures and pHs of a sample in situ using NMR spectroscopy, and for sealing one or more ends of a capillary tube after a reference material has been added to the capillary tube, which is used in an in situ NMR temperature measurement device. A method for measuring a pH of a sample in situ using NMR spectroscopy includes providing an in situ NMR pH measurement device. This device includes a sample housing member configured to house a target sample, at least one pH sensor configured to exhibit an NMR spectral change due to a change in pH value of the target sample, and a pH sensor containment member configured to house the at least one pH sensor. The target sample is added to the sample housing member. NMR spectra are obtained to then determine the pH of the target sample

Capillary-Tube Package Devices for the Quantitative Performance Evaluation of Nuclear Magnetic Resonance Spectrometers and Pulse Sequences

With the increased sensitivity of modern nuclear magnetic resonance (NMR) spectrometers, the minimum amount needed for chemical-shift referencing of NMR spectra has decreased to a point where a few microliters can be sufficient to observe a reference signal. The reduction in the amount of required reference material is the basis for the NMR Capillary-tube Package (CapPack) platform that utilizes capillary tubes with inner diameters smaller than 150 µm as NMR-tube inserts for external reference standards. It is shown how commercially available electrophoresis capillary tubes with outer diameters of 360 µm are filled with reference liquids or solutions and then permanently sealed by the arc discharge plasma of a commercially available fusion splicer normally employed for joining optical fibers. The permanently sealed capillaries can be used as external references for chemical-shift, signal-to-noise, resolution, and concentration calibration. Combining a number of permanently sealed capillaries to form CapPack devices leads to additional applications such as performance evaluation of NMR spectrometers and NMR pulse sequences. A 10-capillary-tube side-by-side Gradient CapPack device is used in combination with one or two constant gradients, produced by room-temperature shim coils, to monitor the excitation profiles of shaped pulses. One example illustrates the performance of hyperbolic secant (sech) pulses in the EXponentially Converging Eradication Pulse Train (EXCEPT) solvent suppression sequence. The excitation profile of the pulse sequence is obtained in a single gradient NMR experiment. A clustered T1 CapPack device is introduced consisting of a coaxial NMR-tube insert that holds seven capillary tubes filled with aqueous solutions of different concentrations of the paramagnetic relaxation agent copper(ii) sulfate (CuSO4). The different CuSO4 concentrations lead to spin-lattice relaxation times in the seven capillary tubes that cover a range which extends to more than an order of magnitude. Clustered T1 CapPack devices are best suited to quantify the effects that relaxation has on magnetizations and coherences during the execution of NMR experiments, which is demonstrated for the order-of-magnitude T1 insensitivity of signal suppression with EXCEPT

Theranostic Copolymers Neutralize Reactive Oxygen Species and Lipid Peroxidation Products for the Combined Treatment of Traumatic Brain Injury

Traumatic brain injury (TBI) results in the generation of reactive oxygen species (ROS) and lipid peroxidation product (LPOx), including acrolein and 4-hydroxynonenal (4HNE). The presence of these biochemical derangements results in neurodegeneration during the secondary phase of the injury. The ability to rapidly neutralize multiple species could significantly improve outcomes for TBI patients. However, the difficulty in creating therapies that target multiple biochemical derangements simultaneously has greatly limited therapeutic efficacy. Therefore, our goal was to design a material that could rapidly bind and neutralize both ROS and LPOx following TBI. To do this, a series of thiol-functionalized biocompatible copolymers based on lipoic acid methacrylate and polyethylene glycol monomethyl ether methacrylate (FW ∼950 Da) (O950) were prepared. A polymerizable gadolinium-DOTA methacrylate monomer (Gd-MA) was also synthesized starting from cyclen to facilitate direct magnetic resonance imaging and in vivo tracking of accumulation. These neuroprotective copolymers (NPCs) were shown to rapidly and effectively neutralize both ROS and LPOx. Horseradish peroxidase absorbance assays showed that the NPCs efficiently neutralized H2O2, while R-phycoerythrin protection assays demonstrated their ability to protect the fluorescent protein from oxidative damage. 1H NMR studies indicated that the thiol-functional NPCs rapidly form covalent bonds with acrolein, efficiently removing it from solution. In vitro cell studies with SH-SY5Y-differentiated neurons showed that NPCs provide unique protection against toxic concentrations of both H2O2and acrolein. NPCs rapidly accumulate and are retained in the injured brain in controlled cortical impact mice and reduce post-traumatic oxidative stress. Therefore, these materials show promise for improved target engagement of multiple biochemical derangements in hopes of improving TBI therapeutic outcomes

Leibhafte Kunst. Statuen und kulturelle Identität

Dreidimensionale lebensgroße Figuren gehören zu den wirkmächtigen und auffälligsten Artikulationsformen der griechischen und römischen Antike. Wegen ihrer Anschaulichkeit sowie wegen ihrer dauernden und körperhaften Präsenz sind sie besonders einflussreiche Konkretisierungen von religiösen Auffassungen, Machtverhältnissen und Wissensordnungen. Spätere Epochen der europäischen Kulturgeschichte haben sich in immer neuen Rückbezügen daran orientiert. Der vorliegende Band untersucht die Leistung der Statu­en als eine Konkretisierungsform von politischen, sozia­len und religiösen Vorstellungen. Den Ausgangspunkt bilden Phänomene der griechischen und römischen Antike, doch machen Beiträge aus der Kunstgeschichte, Ethnologie und Germanistik deutlich, dass das Thema weit über die Altertumswissenschaften hinaus interessant und wichtig ist. Gerade der Blick auf außereuropäische Ausdrucksformen macht deutlich, dass die Entwicklung der antiken Skulptur, die aus einer europäischen Per­spektive konsequent und selbstverständlich erscheint, nur eine unter vielen möglichen Optionen darstellte

Positive Selection Results in Frequent Reversible Amino Acid Replacements in the G Protein Gene of Human Respiratory Syncytial Virus

Human respiratory syncytial virus (HRSV) is the major cause of lower respiratory tract infections in children under 5 years of age and the elderly, causing annual disease outbreaks during the fall and winter. Multiple lineages of the HRSVA and HRSVB serotypes co-circulate within a single outbreak and display a strongly temporal pattern of genetic variation, with a replacement of dominant genotypes occurring during consecutive years. In the present study we utilized phylogenetic methods to detect and map sites subject to adaptive evolution in the G protein of HRSVA and HRSVB. A total of 29 and 23 amino acid sites were found to be putatively positively selected in HRSVA and HRSVB, respectively. Several of these sites defined genotypes and lineages within genotypes in both groups, and correlated well with epitopes previously described in group A. Remarkably, 18 of these positively selected tended to revert in time to a previous codon state, producing a “flip-flop” phylogenetic pattern. Such frequent evolutionary reversals in HRSV are indicative of a combination of frequent positive selection, reflecting the changing immune status of the human population, and a limited repertoire of functionally viable amino acids at specific amino acid sites