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Since its original publication in 1789, Vaccinium virgatum has been treated by most authors as an accepted species in V. sect. Cyanococcus. In the latest comprehensive taxonomic treatment of the section, however, it is treated as a synonym of the broadly circumscribed species V. corymbosum. Here we use a combination of morphology, ploidy assessment with flow cytometry, and previously published phylogenomic analysis based on high-throughput DNA sequencing to support the taxonomic status of V. virgatum as a species to be recognized. As circumscribed here, V. virgatum occurs in the southeastern U.S. Coastal Plain from Arkansas, Texas, and southeastern Oklahoma to northeastern Florida and southeastern North Carolina. An updated taxonomic treatment of the species, including an expanded description, distribution map by county, and a representative list of specimens examined by county is included. We provide a means of distinguishing V. virgatum from V. ashei, a similar species recently also segregated from V. corymbosum, and from presumed rabbiteye blueberry escapes from cultivation, which can occur both within and outside the native range of V. virgatum. We designate a neotype for V. virgatum and lectotypes for V. virgatum vars. angustifolium, parvifolium, and speciosum. 

The tuning of the luminescent properties of PtII complexes for possible use in organic light-emitting diodes (OLEDs) and sensing applications is commonly achieved by altering the electronic properties of the ligands. Our group recently demonstrated that the trifluoropropynyl ligand is strongly electron-withdrawing and possibly useful for blueshifting emission. Herein, we report the synthesis of two complexes of this trifluoropropynyl ligand, namely PtLC2CF3 and PtLFC2CF3 (L = 1,3-di(2-pyridyl)benzene; LF = 4,6-difluoro-1,3-di(2-pyridyl)benzene). The PtLC2CF3 complex crystallized in the monoclinic space group P21/n with Z = 4. The PtLFC2CF3 complex crystalized in the triclinic space group P-1 with Z = 2. Changing the tridentate ligand from L to LF resulted in a change in the packing structure, with the latter showing a metallophilic interaction (Pt-Pt distance = 3.3341(3) Å). The solution photophysics of the trifluoropropynyl complexes is compared with that of the corresponding Cl complexes, PtLCl and PtLFCl. Replacement of the chloro ligand with the trifluoropropynyl ligand blueshifted the monomer emission by less than 5 nm but blueshifted the excimer emission peaks by 15–20 nm. The complexes of the trifluoropropynyl ligand also favor the excimer emission more than the complexes of the chloro ligand. The excimer emission is quenched by dissolved oxygen significantly more than the corresponding monomer emission. The excimer emission and monomer emission are well separated, and the ratio of monomer to excimer emission is strongly dependent on oxygen concentration.

 

The luminescent properties of Au(I) and Pt(II) compounds are commonly tuned by exploiting the alkynyl ligand with varying electron density. Herein, we describe the synthesis of three new emissive transition metal compounds, tbpyPt(C2pym)2, Ph3PAuC2pym, and Cy3PAuC2pym (where HC2pym = 2-ethynylpyrimidine), verified by 1H-NMR, EA, and a single-crystal X-ray diffraction analysis. The tbpyPt(C2pym)2 complex crystallized as an Et2O solvate in the orthorhombic space group Pbca with Z = 24 with three unique Pt(II) species within the unit cell. The Cy3PAuC2pym species crystallizes in a monoclinic space group with one unique complex in the asymmetric unit. Changing the identity of the phosphine from Cy3P to Ph3P influences interactions within the unit cell. Ph3PAuC2pym, which also crystalizes in a monoclinic space group, has an aurophilic bonding interaction Au–Au distance of 3.0722(2) Å, which is not present in crystalline Cy3PAuC2pym. Regarding optical properties, the use of an electron-deficient heterocycle provides an alternate approach to blue-shifting the emission of Pt(II) transition metals’ compounds, where the aryl moiety is made more electron-deficient by exploiting nitrogen within this moiety instead of the typical strategy of decorating the aryl ring with electron withdrawing substituents (e.g., fluorines). This is indicated by the blue-shift in emission that occurs in tbpyPt(C2pym)2 (λmax, emission = 512 nm) compared to the previously reported tbpyPt(C22-py)2 (where HC22-py = 2-ethynylpyridine) complex (λmax, emission = 520 nm).

 

(1) Introduction. Although new particle formation (NPF) constitutes an important process in air, there are large uncertainties regarding which species participate in the formation of the first nanoclusters. Acid-base reactions are known generate new particles, with methanesulfonic acid (MSA) from the photooxidation of biogenic organosulfur compounds becoming more important with time relative to sulfuric acid as fossil-fuel related sources of the latter decline. Simultaneously, the use of alkanolamines in carbon capture and storage (CCS) is expected to result in increased atmospheric concentrations of these bases. This study applied a unique mass spectrometry method to examine the chemical composition of 2-10 nm particles from the MSA reaction with monoethanolamine and 4-aminobutanol, the most efficient system for NPF from MSA examined to date. (2) Methods. Thermal desorption chemical ionization mass spectrometry (TDCIMS, HToF mass analyzer, Tofwerk AG) was used to measure the size and acid-to-base molar ratios of nanoparticles formed from the reaction of MSA with multifunctional amines. A high-flow differential mobility analyzer (half-mini DMA, SEADM) was interfaced with the TDCIMS, which provides a high mobility resolution and high particle transmission in the diameter range 2-10 nm, where chemical composition measurements are the most challenging due to the very small amount of mass. With this novel combination of techniques we were able to examine MSA-amine systems either from nanoparticles exiting the outlet of a flow reactor or nanoclusters generated via electrospray. (3) Preliminary Data. These experiments show that MSA-driven acid-base reactions with monethanolamine or 4-aminobutanol are even more efficient in NPF than that of simple alkylamines, exhibiting to date the highest nanoparticle formation rates measured in laboratory flow tube studies. The observed enhancement is rooted in the presence of an -OH group on the parent molecules, which initiates a H-bond network throughout the nanoclusters. In these systems, water had only a minimal enhancing effect. We demonstrated that the nanoparticles formed in both systems are neutral (i.e. contain as much acid as base molecules) in the range 2-10 nm. This contrasts with MSA reactions from previous studies on the smallest alkylamine, methylamine, where particles smaller than 9 nm were more acidic. Investigations of reactions of MSA with a diamine (1,4-diaminobutane) showed a similar pattern of neutral particles across the diameter range studied and experiments with larger alkylamine, butylamine, are underway to probe the relationship between structure- and NPF potential from MSA. These findings highlight that there is no “one size-fits-all” regarding NPF from MSA reactions with amines and illustrates the need for studies of more complex amines to fully characterize the NPF potential of this atmospherically relevant strong acid. (4) Novel Aspect. The combination of TDCIMS with a novel particle sizing system provided the chemical composition of 2-10 nm particles. 

Electrical generation and transduction of polarized electron spins in semiconductors are of central interest in spintronics and quantum information science. While spin generation in semiconductors has been frequently realized via electrical injection from a ferromagnet, there are significant advantages in nonmagnetic pathways of creating spin polarization. One such pathway exploits the interplay of electron spin with chirality in electronic structures or real space. Here, utilizing chirality‐induced spin selectivity (CISS), we demonstrate efficient creation of spin accumulation inn‐doped GaAs via electric current injection from a normal metal (Au) electrode through a self‐assembled monolayer of chiral molecules (α‐helix L‐polyalanine, AHPA‐L). The resulting spin polarization is detected as a Hanle effect in then‐GaAs, which is found to obey a distinct universal scaling with temperature and bias current consistent with chirality‐induced spin accumulation. The experiment constitutes a definitive observation of CISS in a fully nonmagnetic device structure and demonstration of its ability to generate spin accumulation in a conventional semiconductor. The results thus place key constraints on the physical mechanism of CISS and present a new scheme for magnet‐free semiconductor spintronics.

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