化学•材料最新文献

Although exogenous chemicals frequently exhibit a biphasic response in regulating plant growth, characterized by low-dose stimulation and high-dose inhibition, the underlying mechanisms remain elusive. This study demonstrates, for the first time, the compensatory function of rhizosphere microbiota in assisting plants to withstand pesticide stress. It was observed that pak choi plants, in response to foliar-spraying imidacloprid at both low and high doses, could increase the total number of rhizosphere bacteria and enrich numerous beneficial bacteria. These bacteria have capabilities for promoting plant growth and degrading the pesticide, such as Nocardioides, Brevundimonas, and Sphingomonas. The beneficial bacterial communities were recruited by stressed plants through increasing the release of primary metabolites in root exudates, such as amino acids, fatty acids, and lysophosphatidylcholines. At low doses of pesticide application, the microbial compensatory effect overcame pesticide stress, leading to plant growth promotion. However, with high doses of pesticide application, the microbial compensatory effect was insufficient to counteract pesticide stress, resulting in plant growth inhibition. These findings pave the way for designing improved pesticide application strategies and contribute to a better understanding of how rhizosphere microbiota can be used as an eco-friendly approach to mitigate chemical-induced stress in crops.

Protein-protein interactions (PPIs) differ when measured in test tubes and cells due to the complexity of the intracellular environment. Free amino acids (AAs) and their derivatives constitute a significant fraction of the intracellular volume and mass. Recently, we have found that AAs have a generic property of rendering protein dispersions more stable by reducing the net attractive part of PPIs. Here, we study the effects on PPIs of different AA derivatives, AA mixtures, and short peptides. We find that all the tested AA derivatives modulate PPIs in solution as effectively as AAs. Furthermore, we show that the modulation effect is additive when AAs form mixtures or are bound into short peptides. Therefore, this study demonstrates the additive effects of a class of small molecules (i.e., AAs and their biological derivatives) on PPIs and provides insights into rationally designing biocompatible molecules for stabilizing protein interactions and consequently tuning protein functions.

To use transition metal ions for spin-based applications, it is essential to understand fundamental contributions to electron spin relaxation in different ligand environments. For example, to serve as building blocks for a device, transition metal ion-based molecular qubits must be organized on surfaces and preserve long electron spin relaxation times, up to room temperature. Here we propose monovalent group 12 ions (Zn⁺ and Cd⁺) as potential electronic metal qubits with an ns¹ ground state. The relaxation properties of Zn⁺ and Cd⁺, stabilized at the interface of porous aluminosilicates, are investigated and benchmarked against vanadium (3d¹) and copper (3d⁹) ions. The spin-phonon coupling has been evaluated through DFT modeling and found to be negligible for the ns¹ states, explaining the long coherence time, up to 2 μs, at room temperature. These so far unexplored metal qubits may represent viable candidates for room temperature quantum operations and sensing.

To understand the reactivity of resonantly stabilized radicals, often found in relevant concentrations in gaseous environments, it is important to determine their main reaction pathways. Here, it is investigated whether the fulvenallenyl radical (C₇H₅^·) reacts preferentially with closed-shell molecules or radicals. Electronic structure calculations on the C₁₀H₉ potential energy surface accessed by the reactions of C₇H₅^· with methylacetylene (CH₃CCH) and allene (H₂CCCH₂) were combined with RRKM-ME calculations of temperature- and pressure-dependent rate constants using the automated EStokTP software suite and kinetic modeling to assess the reactivity of C₇H₅^· with closed-shell unsaturated hydrocarbons. Experimentally, the reactions were attempted in a chemical microreactor heated to 998 ± 10 K by preparing fulvenallenyl radicals via pyrolysis of trichloromethylbenzene (C₇H₅Cl₃) and seeding the radicals in methylacetylene or allene carrier gas, with product identification by means of photoionization mass spectrometry. The measured photoionization efficiency curve of m/z = 128 was assigned to a linear combination of the reference curves of two C₁₀H₈ isomers, azulene (minor) and naphthalene (major), presumably resulting from the C₇H₅^· plus C₃H₄ reactions. However, the calculations demonstrated that these reactions are too slow, and kinetic modeling of processes in the reactor allowed us to conclude that the observation of naphthalene and azulene is due to the C₇H₅^· plus C₃H₃^· reaction, where propargyl is produced by direct hydrogen atom abstraction by chlorine (Cl) atoms from allene or methylacetylene and Cl stem from the pyrolysis of C₇H₅Cl₃. Modeling results under the copyrolysis conditions of toluene and methylacetylene in high-temperature shock tube experiments confirmed the prevalence of the fulvenallenyl reaction with propargyl over its reactions with C₃H₄ even when the concentrations of allene and methylacetylene largely exceed that of propargyl. Overall, the reactions of fulvenallenyl with both allene and methylacetylene were found to be noncompetitive in the formation of naphthalene and azulene thus attesting the inefficiency of the fulvenallenyl radical reactions with the prototype closed-shell hydrocarbon species. In the meantime, the new reaction pathways revealed, including H-assisted isomerizations between C₁₀H₈ isomers and decomposition reactions of various C₁₀H₉ isomers, emerge as relevant and are recommended for inclusion in combustion kinetic models for naphthalene formation.

Liquid crystal monomers (LCMs) are biphenyl- or cyclohexane-based organic chemicals used in electronic digital displays, and several of them possess bioaccumulative and toxic properties. Little is known about their occurrence in indoor dust from the United States. We analyzed 60 LCMs in 104 residential indoor dust samples collected from 16 states across the United States. Forty-seven of 60 LCMs were detected in dust samples at a median ∑LCM concentration of 402 ng/g (range: not detected to 4300 ng/g). Trans-4-propylcyclohexyl trans,trans-4'-propylbicyclohexyl-4-carboxylate (MPVBC) and (trans,trans)-4-fluorophenyl 4'-pentyl-[1,1'-bi(cyclohexane)]-4-carboxylate (FPeBC) were frequently detected in dust samples. We investigated potential sources of LCMs in dust by determining concentrations and profiles of these chemicals in smartphone screens, desktop and laptop computer monitors, and displays of other electronic devices and found that profiles in smartphones matched closely with those found in dust. The calculated median daily intake of ∑LCM through dust ingestion was 1.19 ng/kg bw/d for children, whereas that through dermal absorption was 0.18 ng/kg bw/d for adults in the United States.

A silver-catalyzed protocol for the intermolecular radical umpolung cross-coupling protocol of silyl enol ethers with activated methylene compounds is disclosed. The protocol exhibits excellent functional group tolerance, enabling the expedient preparation of a variety of tricarbonyl compounds. Preliminary mechanistic investigations suggest that the reaction proceeds through a process involving free radicals in which silver oxide has a dual role, acting as both a catalyst and a base.

β-l-5-((E)-2-Bromovinyl)-1-((2S,4S)-2-(hydroxymethyl)-1,3-(dioxolane-4-yl) uracil (l-BHDU, 17) is a potent and selective inhibitor of the varicella-zoster virus (VZV). l-BHDU (17) has demonstrated excellent anti-VZV activity and is a preclinical candidate to treat chickenpox, shingles (herpes zoster), and herpes simplex virus 1 (HSV-1) infections. Its monophosphate prodrug (POM-l-BHDU-MP, 24) demonstrated an enhanced pharmacokinetic and antiviral profile. POM-l-BHDU-MP (24), in vivo, effectively reduced the VZV viral load and was effective for the topical treatment of VZV and HSV-1 infections. Therefore, a viable synthetic procedure for developing POM-l-BHDU-MP (24) is needed. In this article, an efficient approach for the synthesis of l-BHDU (17) from a readily available starting material is described in 7 steps. An efficient and practical methodology for both chiral pure l- & d-dioxolane 11 and 13 were developed via diastereomeric chiral amine salt formation. Neutralization of the amine carboxylate salt of l-dioxolane 10 provides enantiomerically pure l-dioxane 11 (ee ≥ 99%). Optically pure 11 was utilized to construct the final nucleoside l-BHDU (17) and its monophosphate ester prodrug (POM-l-BHDU-MP, 24). Notably, the reported process eliminates expensive chiral chromatography for the synthesis of chiral pure l- & d-dioxolane, which offers avenues for the development and structure-activity relationship studies of l- & d-dioxolane-derived nucleosides.

A retrospective is presented highlighting the synthesis of selected "first-in-kind" natural products, their synthetic analogues, structure elucidations, and rationally designed bioactive synthetic compounds that were accomplished because of collaborations with past and present pharmaceutical and agrochemical companies. Medicinal chemistry projects involving structure-based design exploiting cocrystal structures of small molecules with biologically relevant enzymes, receptors, and bacterial ribosomes with synthetic small molecules leading to marketed products, clinical candidates, and novel drug prototypes were realized in collaboration. Personal reflections, historical insights, behind the scenes stories from various long-term projects are shared in this retrospective article.

A novel and efficient fragment-based assembly of symmetrical bis-peptidotraizoles has been developed based on double Sharpless azide-alkyne click chemistry. A new Cu(II) catalyzed protocol with a wide substrate scope was developed for accessing the symmetrical alkylidene bis-azidoamide fragment that yields the products in very good yields at room temperature without employing column purifications. The propargylated β-acetamido ketone fragment was accessed using another Cu(II) catalyzed room temperature MCR protocol. A fast double-click reaction (2 h) of symmetrical alkylidene bis-azidoamides with propargylated β-acetamido ketone fragments leads to the formation of unusual symmetrical bis-peptidotriazoles.

A visible-light-initiated C-H trifluoromethylation of quinoxalin-2(1H)-ones was established using a Z-scheme V₂O₅/g-C₃N₄ heterojunction as a recyclable photocatalyst in an inert atmosphere at room temperature under additive-free and mild conditions. A variety of trifluoromethylated quinoxalin-2-(1H)-one derivatives were heterogeneously generated in moderate to high yields, exhibiting good functional group tolerance. Remarkably, the recyclable V₂O₅/g-C₃N₄ catalyst could be reused five times with a slight loss of catalytic activity.