Slowing magnetic relaxation with open-shell diluents.

Strategies for slowing magnetic relaxation via local environmental design are vital for developing next-generation spin-based technologies (e.g., quantum information processing). Herein, we demonstrate a technique to do so via chemical design of a local magnetic environment. We show that embedding the open-shell complex (Ph4P)2[Co(SPh)4] in solid-state matrices of the isostructural, open-shell species (Ph4P)2[M(SPh)4] (M = Ni2+, S = 1; M = Fe2+, S = 2; M = Mn2+, S = 5 2 ) will slow magnetic relaxation for the embedded [Co(SPh)4]2- ion by three orders of magnitude. Magnetometry, electron paramagnetic resonance (EPR), and computational analyses reveal that integer spin and large, positive zero-field splitting (D) values for the diluent produce a quiet, local magnetic field that slows relaxation rates for the embedded Co molecules. These results will enable the investigation of magnetic systems for which strictly diamagnetic congeners are either synthetically inaccessible or are not isostructural.

Human olfactory detection of packaged cannabis.

Olfactory detection of cannabis aroma by police officers can be the basis for warrantless searches of motor vehicles in many jurisdictions in the United States. The odor source in these cases is often dried cannabis flower contained in various casual wrappings as well as in more elaborate packaging. Here we investigate whether packaging format alters the detectability of the cannabis. Two cannabis strains and five packaging formats were evaluated. Untrained observers were presented with two containers and asked to identify, based only on smell, the container that held a sample of packaged cannabis (the other container held identical, but empty, packaging material). The results showed that open and casually packaged cannabis was identified with high accuracy, while material packaged in doubly vacuum-sealed plastic was correctly identified at rates no different from chance. The results may help address issues involving the detectability of cannabis aroma in law enforcement and other scenarios.

Consumer perceptions of strain differences in Cannabis aroma.

The smell of marijuana (Cannabis sativa L.) is of interest to users, growers, plant breeders, law enforcement and, increasingly, to state-licensed retail businesses. The numerous varieties and strains of Cannabis produce strikingly different scents but to date there have been few, if any, attempts to quantify these olfactory profiles directly. Using standard sensory evaluation techniques with untrained consumers we have validated a preliminary olfactory lexicon for dried cannabis flower, and characterized the aroma profile of eleven strains sold in the legal recreational market in Colorado. We show that consumers perceive differences among strains, that the strains form distinct clusters based on odor similarity, and that strain aroma profiles are linked to perceptions of potency, price, and smoking interest.

The Surface of Nanoparticle Silicon as Studied by Solid-State NMR.

The surface structure and adjacent interior of commercially available silicon nanopowder (np-Si) was studied using multinuclear, solid-state NMR spectroscopy. The results are consistent with an overall picture in which the bulk of the np-Si interior consists of highly ordered ("crystalline") silicon atoms, each bound tetrahedrally to four other silicon atoms. From a combination of ¹H, 29Si and ²H magic-angle-spinning (MAS) NMR results and quantum mechanical 29Si chemical shift calculations, silicon atoms on the surface of "as-received" np-Si were found to exist in a variety of chemical structures, with apparent populations in the order (a) (Si-O-)3Si-H > (b) (Si-O-)3SiOH > (c) (HO-)nSi(Si)m(-OSi)4-m-n ≈ (d) (Si-O-)2Si(H)OH > (e) (Si-O-)2Si(-OH)2 > (f) (Si-O-)4Si, where Si stands for a surface silicon atom and Si represents another silicon atom that is attached to Si by either a Si-Si bond or a Si-O-Si linkage. The relative populations of each of these structures can be modified by chemical treatment, including with O2 gas at elevated temperature. A deliberately oxidized sample displays an increased population of (Si-O-)3Si-H, as well as (Si-O-)3SiOH sites. Considerable heterogeneity of some surface structures was observed. A combination of ¹H and ²H MAS experiments provide evidence for a substantial population of silanol (Si-OH) moieties, some of which are not readily H-exchangeable, along with the dominant Si-H sites, on the surface of "as-received" np-Si; the silanol moieties are enhanced by deliberate oxidation. An extension of the DEPTH background suppression method is also demonstrated that permits measurement of the T2 relaxation parameter simultaneously with background suppression.

Saving transverse magnetization.

A magnetization storage sequence, ALT-1 (alternating longitudinal and transverse components), is reported. The ALT-1 sequence is a hybrid of two types of storage sequences, the Carr-Purcell type and store-and-restore sequences. During incremental storage periods within the ALT-1 sequence, essentially half of the initially transverse magnetization is stored along the z-axis and the other half is prolonged by an echo-generating pulse. The portions of initial magnetization that are stored as longitudinal components or transverse components are alternated by a pi/2 pulse during the cycle. Both transverse components of the initial magnetization are treated the same in the ALT-1 sequence and orientational (phase) information of the initial magnetization is kept during the storage period. The ALT-1 sequence can preserve magnetization more effectively than a published class of modified Carr-Purcell type sequences, because essentially half of the magnetization during incremental storage periods is not subjected to relaxation from T2 effects.

Wood used by Stradivari and Guarneri.

Whether or not the great Italian violin-makers used wood that had been chemically processed in order to preserve it and enhance the instrument's sound quality has long been a contentious issue. Here we use nuclear magnetic resonance and infrared spectroscopy to analyse organic matter in wood taken from antique instruments made by Stradivari and Guarneri del Gesu. Our results indicate that the wood used by the masters could indeed have been chemically treated, a technique that may inspire an approach to violin making that is more chemistry-based.

Chemistry of the silica surface: liquid-solid reactions of silica gel with trimethylaluminum.

The reaction of trimethylaluminum and dry, high-surface-area (500 m2/g) silica gel in a mixed slurry was studied using multinuclear, solid-state NMR spectroscopy. The products of the initial reaction were characterized, and their progress through subsequent washing with diethyl ether and reactions with measured amounts of water was followed. The quantitative distribution of different chemical forms of carbon deposited on the silica surface by the initial reaction was measured. The products of the initial reaction are dominated by methyl species of the types Al(CH3)n (with Si-O-Al linkages), Si-O-CH3, and (Si-O)4-nSi(CH3)n; aluminum is seen to exist predominantly as a five-coordinate species. Subsequent treatment with diethyl ether fails to remove any surface species, but instead the ether becomes strongly associated with the surface and highly resistant to removal. Stepwise additions of water hydrolyze the Al-CH3 and Si-O-CH3 moieties, leading to conversion of five-coordinate aluminum to four- and six-coordinate aluminum, and affect the partial release of the surface-associated diethyl ether; Si-CH3 moieties remain. The effect of aromatic and saturated solvents on the initial reaction was examined and found to cause a small but significant change in the distribution of products. Structures of aluminum-centered species on the silica surface consistent with the spectroscopic data are proposed.

Chemistry of the silica surface: reaction with phosphorus pentachloride.

Solid-state 31P and 29Si NMR experiments, with Magic-Angle Spinning (MAS), were used to elucidate the chemistry that occurs when silica gel is treated with phosphorus pentachloride. A low-loading regime (in which the molar ratio of initial PCl5 to surface silanols sites is <<1) and a high-loading regime (in which this ratio is approximately 1) were examined. For each regime, the results for limited and intentional exposure to moisture are presented. The occurrence of phosphorus bridging between two adjacent silanols sites is observed. Bridging structures based on Si-O-P-O-P-O-Si linkages are also indicated.