Infrared spectroscopy of closed s-shell gas-phase M+(N2O)n (M = Li,Al) ion-molecule complexes*

ABSTRACT

We present the results of a combined experimental and computational study of the structures of gas-phase M⁺(N₂O)_n (M?=?Li, Al) complexes. Infrared spectra were recorded in the region of the N₂O asymmetric (N?=?N) stretch using photodissociation spectroscopy employing the inert messenger technique. Unlike in our previous studies on M⁺(N₂O)_n (M?=?Cu, Ag, Au and M?=?Co, Rh, Ir) complexes, N– and O–bound isomers in this case are near isoenergetic and are not distinguished spectroscopically at this resolution. In the case of Li⁺ complexes, there is, however, evidence for the presence of bound N₂ moieties, indicating the presence of inserted, OLi⁺N₂(N₂O)_n–type structures. The weak N₂ band lies to the blue of the signature of molecularly N– and O–bound ligands and is well–reproduced in the simulated spectra of energetically low-lying structures computed from density functional theory. No such inserted isomers are observed in the case of Al⁺(N₂O)_n complexes whose infrared spectra can be understood on the basis of molecularly-bound N₂O ligands. The differences in M⁺(N₂O)_n structures observed for these closed–shell, ns², metal centres relative to other metal cations are discussed in terms of the likely bonding motifs.     

Total synthesis and biochemical characterization of mirror image barnase

In this study we synthesized and characterized mirror image barnase (B. amyloliquefaciens ribonuclease). d-Barnase was identical to l-barnase, when analyzed by liquid chromatography and mass-spectrometry. Proteolysis of the mirror image enzyme revealed that in contrast to its native counterpart, d-barnase was completely stable to digestive proteases. In enzymatic assays, d-barnase had the reciprocal chiral specificity and was fully active towards mirror image substrates. Interestingly, d-barnase also hydrolyzed the substrate of the native chirality, albeit 4000 times less efficiently. This effect was further confirmed by digesting a native 112-mer RNA with the enzyme. Additional studies revealed that barnase accommodates a range of substrates with various chiralities, but the prime requirement for guanosine remains. These studies point toward using mirror image enzymes as modern agents in biotechnology.     

Impact of woven fabric: Experiments and mesostructure-based continuum-level simulations

Woven fabric is an increasingly important component of many defense and commercial systems, including deployable structures, restraint systems, numerous forms of protective armor, and a variety of structural applications where it serves as the reinforcement phase of composite materials. With the prevalence of these systems and the desire to explore new applications, a comprehensive, computationally efficient model for the deformation of woven fabrics is needed. However, modeling woven fabrics is difficult due, in particular, to the need to simulate the response both at the scale of the entire fabric and at the meso-level, the scale of the yarns that compose the weave. Here, we present finite elements for the simulation of the three-dimensional, high-rate deformation of woven fabric. We employ a continuum-level modeling technique that, through the use of an appropriate unit cell, captures the evolution of the mesostructure of the fabric without explicitly modeling every yarn. Displacement degrees of freedom and degrees of freedom representing the change in crimp amplitude of each yarn family fully determine the deformed geometry of the mesostructure of the fabric, which in turn provides, through the constitutive relations, the internal nodal forces. In order to verify the accuracy of the elements, instrumented ballistic impact experiments with projectile velocities of 22-550 m/s were conducted on single layers of Kevlar^® fabric. Simulations of the experiments demonstrate that the finite elements are capable of efficiently simulating large, complex structures.     

Biomimetic Chiral Pyridoxal and Pyridoxamine Catalysts

Vitamin B₆ serves as universal co‐enzymes in biological systems. However, its catalytic power has not been applied into the area of asymmetric catalysis. Based on the core structure of vitamin B₆, we have developed several types of pyridoxal and pyridoxamine catalysts with different structural skeletons and different electronic properties. With these pyridoxals and pyridoxamines as catalysts, we have realized biomimetic asymmetric transamination of α‐keto acids and biomimetic asymmetric Mannich reaction of glycinate, respectively, to give various chiral α‐amino acids and α,β‐diamino acids in good yields with excellent diastero‐ and/or enantioselectivities. Both of the reactions have perfectly mimicked the corresponding biological transformations.     

Dependence of Pressure,Combustion and Frequency Characteristics on Valved Pulsejet Combustor Geometries

An experimental analysis of valved pulsejets based on the Curtis-Dyna design and the concomitant results are discussed in the current paper. By altering the combustor length, the tail pipe length and by adding a flare at the aft-end, twelve different pulsejet configurations are tested. An axially-distributed array of piezoelectric pressure sensors and ion probes reveal the pressure and combustion dynamics inside these devices. Evidence is attained to support the claim that valved Curtis-Dyna pulsejets of the tested configurations behave like a Helmholtz resonator. Each cycle of a pulsejet is composed of temporally and spatially restrained combustion events. Altering the geometry induces an amplitude modulated low frequency instability inside the pulsejet that is characterized by sinusoidally-varying peak cycle pressures. The operating frequency, peak pressures and combustion activity of the pulsejets are characterized to reveal that reliable pulsejet operation requires proper amount of coupling — defined by low time lags — between the pressure peaks and combustion events.     

Exploring Microfluidic Routes to Microgels of Biological Polymers

Polymer microgels in the size range from several micrometers to hundreds of micrometers are used in the pharmaceutical, cosmetics, nutrition, pesticide, and food industries, as well as in the encapsulation of cells. To date, a broad range of strategies for the generation of polymer microgels exist, however, these methods involve multistage processes, do not utilize biocompatible components or do not allow precise control of the dimensions and internal structure of the microgels. Recently, microfluidic strategies for the production of polymer particles have offered precise control over the shapes, morphologies, and size distributions of polymer colloids. This paper discusses the most recent results obtained by the authors in the area of the microfluidic production of biopolymer microgels. It provides a brief review of the microfluidic methods for the continuous synthesis and fabrication of microgels, sets the criteria for the successful microfluidic generation of biomicrogels, and describes two methods for the preparation of microgels by microfluidic means. The article concludes with a summary and an outlook.

     

Novel Solventless Extraction Technique to Preserve Cannabinoid and Terpenoid Profiles of Fresh Cannabis Inflorescence

Despite its use by humans for thousands of years, the technology of cannabis usage and extraction is still evolving. Given that the primary pharmacological compounds of interest are cannabinoid and terpenoids found in greatest abundance in capitate glandular trichomes of unfertilized female inflorescences, it is surprising that older techniques of hashish making have received less technological advancement. The purpose of this study was to employ organically grown cannabis and to isolate pure trichomes from freshly picked flowers via exposure to vapor from solid CO₂, commonly known as “dry ice”, followed by their isolation via sifting through a 150 µ screens while maintaining the cold chain. Biochemical analysis was undertaken on fresh flower, frozen-sifted flower by-products, treated trichomes (Kryo-Kief™), dried flower, dried sifted flower by-product and dried kief. The dry ice process successfully concentrated cannabinoid content as high as 60.7%, with corresponding concentration and preservation of monoterpenoids encountered in fresh flower that are usually lost during the conventional cannabis drying and curing process. The resulting dried sifted flower by-product after dry ice processing remains a usable commodity. This approach may be of interest to pharmaceutical companies and supplement producers pursuing cannabis-based medicine development with an eye toward full synergy of ingredients harnessing the entourage effect.