An official website of the United States government
Tuning strained alkyne reactivity via organic synthesis has evolved into a burgeoning field of study largely focused on cyclooctyne, wherein physical organic chemistry helps guide rational molecular design to produce molecules with intriguing properties. Concurrent research in the field of carbon nanomaterials has produced new types of strained alkyne macrocycles, such as cycloparaphenyleneacetylenes, that possess uniquely curved aromatic π systems but hover on the edge of stability. In 2018, we introduced a strained alkyne scaffold that marries the synthetic accessibility and stability of cyclooctyne with the curved π system of carbon nanomaterials. These molecules are strained alkyne-containing cycloparaphenylenes (or [n+1]CPPs), which have been shown to possess size-dependent reactivity as well as the classic characteristics of the unfunctionalized parent CPP, such as a tunable HOMO–LUMO gap and bright fluorescence for large sizes. Herein, we elaborate further on this scaffold, introducing two modifications to the original design and fully characterizing the kinetics of the strain-promoted azide–alkyne cycloaddition (SPAAC) for each [n+1]CPP with a model azide. Additionally, we explain how electronic (the incorporation of fluorine atoms) and strain (a meta linkage which heightens local strain at the alkyne) modulations affect SPAAC reactivity via the distortion–interaction computational model. Altogether, these results indicate that through a modular synthesis and rational chemical design, we have developed a new family of tunable and inherently fluorescent strained alkyne carbon nanomaterials.
more »
« less
Size and Strain of Zinc Sulfide Nanoparticles Altered by Interaction with Organic Molecules
Nanosized zinc sulfides (nano-ZnS) have size-dependent and tunable physical and chemical properties that make them useful for a variety of technological applications. For example, structural changes, especially caused by strain, are pronounced in nano-ZnS < 5 nm in size, the size range typical of incidental nano-ZnS that form in the environment. Previous research has shown how natural organic matter impacts the physical properties of nano-ZnS but was mostly focused on their aggregation state. However, the specific organic molecules and the type of functional groups that are most important for controlling the nano-ZnS size and strain remain unclear. This study examined the size-dependent strain of nano-ZnS synthesized in the presence of serine, cysteine, glutathione, histidine, and acetate. Synchrotron total scattering pair distribution function analysis was used to determine the average crystallite size and strain. Among the different organic molecules tested, those containing a thiol group were shown to affect the particle size and size-induced strain most strongly when added during synthesis but significantly reduced the particle strain when added to as-formed nano-ZnS. The same effects are useful to understand the properties and behavior of natural nano-ZnS formed as products of microbial activity, for example, in reducing environments, or of incidental nano-ZnS formed in organic wastes.
more »
« less
- Award ID(s):
- 1652237
- PAR ID:
- 10467707
- Publisher / Repository:
- ACS Environmental Science and Technology
- Date Published:
- Journal Name:
- Environmental Science & Technology
- Volume:
- 56
- Issue:
- 23
- ISSN:
- 0013-936X
- Page Range / eLocation ID:
- 16831 to 16837
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Marine boundary layer (MBL) clouds are an important, though uncertain, part of Earth’s radiative budget. Previous studies have shown sources of aerosol particles in the remote MBL consist of primary sea spray, the oxidation of organic and inorganic vapors derived from the ocean, entrainment from the free troposphere, and anthropogenic pollution. The potential for these particles to become cloud condensation nuclei (CCN) varies largely dependent on their hygroscopic properties. Furthermore, when clouds form, physical processes can alter the optical properties of the cloud. This dissertation aims to identify variations in aerosol sources that affect MBL CCN concentrations and physical processes throughout the cloud lifetime that influence cloud optical properties. Ambient measurements of marine particles and clouds were made throughout two campaigns in the north Pacific and four campaigns in the north Atlantic. Both clean marine and polluted clouds were sampled. In addition, dry MBL particles were measured to identify their chemical composition and size distribution, which is necessary to identify their potential to be CCN active. The organic hygroscopicity influenced CCN concentrations and cloud optical properties significantly for particles that were mostly organic, such as ship stack and generated smoke particles. For a typical range of organic hygroscopicity the amount of reflected solar radiation varied by 2-7% for polluted conditions and less than 1% for clean conditions. Simulated droplet spectral width was shown to be more representative of observations when using a weighted distribution of cloud base heights and updraft velocities, and increased the cloud reflectivity up to 2%. Cloud top entrainment and decoupling of the MBL were found to account for a decrease in cloud radiative forcing. Cloud top entrainment was corrected for homogeneous entrainment and accounted for a decrease in radiative forcing of up to 50 Wm-2. Clustering of individual marine aerosol particles resulted in the identification of particle types derived from dimethyl-sulfide (DMS) oxidation. Two particle types were identified to come from DMS oxidation products and accounted for approximately 25% and 65% of CCN at 0.1% supersaturation during the winter and summer, respectively. One of the particle types was found to be entrained from the free troposphere.more » « less
-
null (Ed.)Atmospheric new-particle formation (NPF) affects climate by contributing to a large fraction of the cloud condensation nuclei (CCN). Highly oxygenated organic molecules (HOMs) drive the early particle growth and therefore substantially influence the survival of newly formed particles to CCN. Nitrogen oxide (NO x ) is known to suppress the NPF driven by HOMs, but the underlying mechanism remains largely unclear. Here, we examine the response of particle growth to the changes of HOM formation caused by NO x . We show that NO x suppresses particle growth in general, but the suppression is rather nonuniform and size dependent, which can be quantitatively explained by the shifted HOM volatility after adding NO x . By illustrating how NO x affects the early growth of new particles, a critical step of CCN formation, our results help provide a refined assessment of the potential climatic effects caused by the diverse changes of NO x level in forest regions around the globe.more » « less
-
The methylation of mercury is known to depend on the chemical forms of mercury (Hg) present in the environment and the methylating bacterial activity. In sulfidic sediments, under conditions of supersaturation with respect to metacinnabar, recent research has shown that mercury precipitates as β-HgS(s) nanoparticles (β-HgS(s) nano ). Few studies have examined the precipitation of β-HgS(s) nano in the presence of marine dissolved organic matter (DOM). In this work, we used dynamic light scattering (DLS) coupled with UV-Vis spectroscopy and transmission electron microscopy (TEM) to investigate the formation and fate of β-HgS(s) nano formed in association with marine DOM extracted from the east and west of Long Island Sound, and at the shelf break of the North Atlantic Ocean, as well as with low molecular weight thiols. We found that while the β-HgS(s) nano formed in the presence of oceanic DOM doubled in size after 5 weeks, those forming in solutions with coastal DOM did not grow over time. In addition, when the Hg II : DOM ratio was varied, β-HgS(s) nano only rapidly aggregated at high ratios (>41 μmol Hg II per mg C) where the concentration of thiol groups was determined to be substantially low relative to Hg II . This suggests that functional groups other than thiols could be involved in the stabilization of β-HgS(s) nano . Furthermore, we showed that β-HgS(s) nano forming under anoxic conditions remained stable and could therefore persist in the environment sufficiently to impact the methylation potential. Exposure of β-HgS(s) nano to sunlit and oxic environments, however, caused rapid aggregation and sedimentation of the nanoparticles, suggesting that photo-induced changes or oxidation of organic matter adsorbed on the surface of β-HgS(s) nano affected their stability in surface waters.more » « less
-
null (Ed.)Study of the permeability of small organic molecules across lipid membranes plays a significant role in designing potential drugs in the field of drug discovery. Approaches to design promising drug molecules have gone through many stages, from experiment-based trail-and-error approaches, to the well-established avenue of the quantitative structure–activity relationship, and currently to the stage guided by machine learning (ML) and artificial intelligence techniques. In this work, we present a study of the permeability of small drug-like molecules across lipid membranes by two types of ML models, namely the least absolute shrinkage and selection operator (LASSO) and deep neural network (DNN) models. Molecular descriptors and fingerprints are used for featurization of organic molecules. Using molecular descriptors, the LASSO model uncovers that the electro-topological, electrostatic, polarizability, and hydrophobicity/hydrophilicity properties are the most important physical properties to determine the membrane permeability of small drug-like molecules. Additionally, with molecular fingerprints, the LASSO model suggests that certain chemical substructures can significantly affect the permeability of organic molecules, which closely connects to the identified main physical properties. Moreover, the DNN model using molecular fingerprints can help develop a more accurate mapping between molecular structures and their membrane permeability than LASSO models. Our results provide deep understanding of drug–membrane interactions and useful guidance for the inverse molecular design of drug-like molecules. Last but not least, while the current focus is on the permeability of drug-like molecules, the methodology of this work is general and can be applied for other complex physical chemistry problems to gain molecular insights.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.est.2c05268
