skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


This content will become publicly available on December 23, 2025

Title: Neoteric solvents for exploratory catalysis: hydrophosphination catalysis with CHEM21 solvents
An analysis of CHEM21 solvent categories reveals that green solvents are viable and often superior to oft-used toxic and hazardous solvents for catalytic hydrophosphination regardless of mechanism, substrate, or catalyst.  more » « less
Award ID(s):
2348198
PAR ID:
10596134
Author(s) / Creator(s):
;
Publisher / Repository:
Royal Society of Chemsitry
Date Published:
Journal Name:
Green Chemistry
Volume:
27
Issue:
2
ISSN:
1463-9262
Page Range / eLocation ID:
432 to 437
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. We examine the microfluidic postprocessing soft colloidal dispersions and reveal a variety of microflow regimes between nanoscale emulsions and solvents. 
    more » « less
  2. Mixed solvents (i.e., binary or higher order mixtures of ionic or nonionic liquids) play crucial roles in chemical syntheses, separations, and electrochemical devices because they can be tuned for specific reactions and applications. Apart from fully explicit solvation treatments that can be difficult to parameterize or computationally expensive, there is currently no well-established first-principles regimen for reliably modeling atomic-scale chemistry in mixed solvent environments. We offer our perspective on how this process could be achieved in the near future as mixed solvent systems become more explored using theoretical and computational chemistry. We first outline what makes mixed solvent systems far more complex compared to single-component solvents. An overview of current and promising techniques for modeling mixed solvent environments is provided. We focus on so-called hybrid solvation treatments such as the conductor-like screening model for real solvents and the reference interaction site model, which are far less computationally demanding than explicit simulations. We also propose that cluster-continuum approaches rooted in physically rigorous quasi-chemical theory provide a robust, yet practical, route for studying chemical processes in mixed solvents. 
    more » « less
  3. Thiocyanates, nitriles, and azides represent a versatile set of vibrational probes to measure the structure and dynamics in biological systems. The probes are minimally perturbative, the nitrile stretching mode appears in an otherwise uncongested spectral region, and the spectra report on the local environment around the probe. Nitrile frequencies and lineshapes, however, are difficult to interpret, and theoretical models that connect local environments with vibrational frequencies are often necessary. However, the development of both more accurate and intuitive models remains a challenge for the community. The present work provides an experimentally consistent collection of experimental measurements, including IR absorption and ultrafast two-dimensional infrared (2D IR) spectra, to serve as a benchmark in the development of future models. Specifically, we catalog spectra of the nitrile stretching mode of methyl thiocyanate (MeSCN) in fourteen different solvents, including non-polar, polar, and protic solvents. Absorption spectra indicate that π-interactions may be responsible for the line shape differences observed between aromatic and aliphatic alcohols. We also demonstrate that a recent Kamlet–Taft formulation describes the center frequency MeSCN. Furthermore, we report cryogenic infrared spectra that may lead to insights into the peak asymmetry in aprotic solvents. 2D IR spectra measured in protic solvents serve to connect hydrogen bonding with static inhomogeneity. We expect that these insights, along with the publicly available dataset, will be useful to continue advancing future models capable of quantitatively describing the relation between local environments, line shapes, and dynamics in nitrile probes. 
    more » « less
  4. Abstract Deep eutectic solvents (DES) or eutectic mixtures prepared with a chiral component can lead to new chiral solvents with applications that include asymmetric synthesis and chiral light emitting materials. DES have low melting points, because of strong interactions, such as hydrogen bonding, between components of the mixture. Mixtures are prepared with ammonium salts, tetrabutylammonium chloride ([TBA]Cl) and choline chloride ([Ch]Cl), as hydrogen bond acceptor (HBA) and L‐lactic acid, L‐leucic acid, L‐ascorbic acid, R/S‐acetoxypropionic acid, and methyl‐(S)‐lactate as chiral hydrogen bond donors (HBD). Eight combinations of the HBAs and HBDs were prepared, and a racemic mixture of dissymmetric chiral europium complexes was dissolved in the mixtures. The circularly polarized luminescence (CPL) spectra were measured to determine the chiral discrimination by these chiral solvents. The CPL spectra show that the handedness of the chiral HBD is important to the chiral discrimination exhibited. However, the inversion of the sign of the CPL spectra in 1 : 3 [TBA]Cl:L‐lactic acid vs. 1 : 3 [Ch]Cl:L‐lactic acid, and 1 : 1.5 [Ch]Cl:L‐leucic acid vs. 1 : 1 [TBA]Cl:L‐leucic acid shows that the achiral HBA also plays a critical role in the handedness of the chiral discrimination by the chiral solvent. 
    more » « less
  5. Abstract Magnetic nanoparticles have continued to gain significant attention due to their unique magnetic properties and potential applications. However, it is still challenging to directly synthesize water-dispersible magnetic nanoparticles with controlled size for biomedical applications. This study investigates the influence of solvents on the continuous growth of magnetic nanoparticles, aiming to achieve controlled size and excellent water dispersibility via thermal decomposition in polyol solvents. The size of the nanoparticles gradually increases with longer polyol chain solvents. The increase in nanoparticles size is more significant under a higher reaction temperature (220 °C) compared to a lower temperature (190 °C). These monodispersed nanoparticles exhibit strong superparamagnetic properties, improving with longer solvent chain lengths at the same size. Magnetic resonance imaging (MRI) studies reveal higher relaxivities for magnetic nanoparticles synthesized in longer-chain polyols. This research offers valuable insights for synthesizing magnetic nanoparticles with precise sizes, magnetic properties, and biomedical applications. Graphical abstract 
    more » « less