Unwanted Side Reactions Research Articles

Programmable Plasma-Microdroplet Cascade Reactions for Multicomponent Systems.

The concept of programmable cascade reactions in charged microdroplets is introduced using carbon-carbon (C-C) bond formation via uncatalyzed Michael addition in a three-tier study culminating in programmable Hantzsch multicomponent, multistep reactions. In situ generated reactive oxygen species (ROS) from nonthermal plasma discharge are fused with charged water microdroplets (devoid of ROS) in real time for accelerated chemical reactions. This plasma-microdroplet fusion platform utilizing a coaxial spray configuration enabled product selection while avoiding unwanted side reactions. Hydrogen abstraction via ROS facilitated the formation of enolate anions without strong base use. Reaction enhancement factors >103 were calculated for plasma-microdroplet fusion versus microdroplet-only reactions. The platform programmability was showcased through (i) uncatalyzed 1,4-Michael addition of α,β-unsaturated carbonyls, (ii) novel C-C bond formation via the use of pro-electrophilic amine and alcohol substrates─activated through collisions in the microdroplet environment to serve as Michael acceptors, and (iii) selective Hantzsch cascade reaction with cross-coupling products, avoiding side reactions including N-alkylation and self-coupling product formation. Milligram quantity product collection is achieved, showcasing plasma-microdroplet fusion as an effective tool for preparative-scale synthesis. Thus, the controlled generation of ROS via plasma discharge during charged water microdroplet evolution establishes a green synthetic method for uncatalyzed C-C bond formation.

Synthetic Challenges toward Modeling Formate Dehydrogenases Using [WVI≡S] Complexes Supported by a Tetradentate [N2S2]4- Ligand.

This report documents our attempts at synthesizing a terminal [WVI≡S] complex supported by a tetradentate, diamido/dithiolate ligand ([N2S2]4-). The target compound was selected because it would serve as a synthetic model for the active sites of formate dehydrogenase (FDH) enzymes. Although the desired [N2S2]WVI≡S species was observed as an NEt3 adduct by mass spectrometry in one case, generally unwanted side reactions prevented isolation and definitive characterization of the target compound. Instead, isolated products characterized by X-ray crystallography included {[N2S2]H}WVI(S2)Cl from redox chemistry of the terminal sulfide, ([N2S2]WVI)2(μ-[N2S2]) from dissociation of the terminal sulfide, ({[N2S2]H}WV)2(μ-S)2 from metal reduction and μ-sulfide bridge formation, and {[N2S2]H}2 from disulfide bond formation via thiolate redox chemistry. A product formed from adventitious exposure to air/moisture, {[N2S2]H2}WVI(O)2, was also characterized. The diverse range of products formed simply from attempted metalation of the [N2S2]4- ligand with Cl4WVI≡S highlights the synthetic challenges toward building active sites that are structurally faithful to FDH.

N-doped polyacrylonitrile carbon fiber interlayer for uniform and dendrite free Zn metal battery

The aqueous zinc-ion battery’s (AZBs) inherent safety and inexpensive cost make it an attractive prospect for next-generation energy storage. Nevertheless, AZBs are presently troubled by the formation of Zn dendrites and unwanted side-reactions, which can lead to cycling instability and premature collapse. This study demonstrates the fabrication of an N-doped polyacrylonitrile (PAN) carbon fiber (PCF) network with ionic conductivity using the electrospinning of a PAN solution followed by thermal treatment. Zn plating and stripping behavior can be controlled by using a three-dimensional PCF with a polar functional group as an interlayer covering on the zinc anode. This allows for partially deposited zinc to be accommodated, which ultimately results in zinc dendrite-free deposition on the zinc anode. This phenomenon is initially proven in Zn@PCF symmetric cells, and then it is demonstrated further in Zn@PCF/MnO2 whole cells, where the dendritic Zn anode surfaces become completely smooth and devoid of any features. This results in a charging and discharging cycle that is far longer than one would normally experience. The findings of this study offer a viable path toward the development of dendrite-free AZBs with great performance.

Overview and Toxicity Assessment of Ultrasound-Assisted Extraction of Natural Ingredients from Plants.

In different food technology unit operations, toxicity can be increased due to unwanted side reactions and is typically associated with the increased thermal energy that facilitates the latter. Authorities in food technology have not provided clear guidelines on using ultrasound (US), but they also have not prohibited its use in food processing. In this study, the source materials and ultrasound-assisted reactions reported in the literature were reviewed to investigate potential side reactions in ultrasound-assisted extraction (UAE). Industrial or pilot-scale processes published in the open literature and in industry patents were also examined. UAE is a highly effective extraction method that significantly increases extraction yields. According to the literature, there is no direct evidence of the formation of toxic compounds from natural food ingredients caused by UAE. However, experimental studies are urgently needed to assess the potential accumulation of toxic substances, especially in the case of certain plants.

Electrochemical Engineering of Anode with Zincophilic Polymer Interface for Reversible Zinc Battery

AbstractAqueous rechargeable zinc‐ion batteries are emerging as green and safe energy devices owing to their high energy density and eco‐friendliness. The bottleneck is the inhomogeneous nucleation resulting in the growth of Zn dendrites and the parasitic side reactions at the anode. Herein, an electrochemical anode engineering strategy is demonstrated to curb the uncontrolled dendritic growth and side reactions. It involves the in situ generation of a solid‐electrolyte interface based on a Zn nanoparticle‐embedded poly(acrylic acid) hybrid layer (PAA‐nZn) on the anode. The homogeneously distributed polar functionalities and porous nature of the polymer regulate the uniform zinc ion flux, and the embedded zinc particle serves as nucleation sites for zinc plating. The hybrid layer reduces the nucleation overpotential and promotes instantaneous nucleation. The symmetrical cell made with PAA‐nZn@Zn has a lifecycle of >860 h with a voltage gap of 28 mV. The full cell fabricated by pairing the engineered anode with α‐MnO2 cathode showed a high discharge specific capacity of 238.3 mAh g−1 at 0.2 A g−1 with a capacity retention of 81.76% after 200 cycles and a long lifecycle. The electrochemical engineering of the anode suppresses the dendritic growth and protects the anode from unwanted side reactions and passivation.

Conducting LixPOy Interface Generated From Insulating Residual Lithium Compounds on LiNi0.8Mn0.1Co0.1O2 Surface Improves Cycle Life and Assists in Fast Cycling.

LiNi0.8Mn0.1Co0.1O2 (NMC811) is the most promising cathode material for future Li-ion batteries (LIBs). However, the bulk and surface structural instabilities retard its commercial success. Surface chemical instability toward exposure to moisture (H2O and CO2) leads to the formation of residual lithium compounds (RLCs: Li2CO3, LiOH) on the surface. The alkaline RLCs form a resistive layer on the surface of NMC811 by undergoing parasitic side reactions with electrolytes. Herein, an "Adverse-to-Beneficial" approach is proposed to eliminate RLCs by chemically transforming them into a LixPOy (Li3PO4 and LiPO3) interface. The interface protects the NMC811 surface from moisture attack and unwanted side reactions with electrolytes. It enhances the cycle life by retaining 70% of the initial capacity after 300 cycles at a 0.5C rate and 60% after 500 cycles, even at a 5C rate in a voltage window of 3.0-4.3V versus Li+/Li. The coexistence of two Li-conducting phases lowers the voltage polarization of the kinetically sluggish H1 → M phase transition to unlock fast cycling, reduces cationic disorder, improves coulombic efficiency, enhances ion diffusion kinetics, and minimizes particle crack formation after long-term cycling. Hence, the LixPOy interface yields multifaceted benefits in the storage, processing, and electrochemistry of NMC811.

Decoupling Charge Carrier Electroreduction and Enzymatic CO2 Conversion to Formate Using a Dual-Cell Flow Reactor System.

With an efficient atom economy, low activation energy, and valuable applications for fuel cells and hydrogen storage, formic acid (FA) is a useful fuel product to convert CO2 and reduce emissions. Although metal catalysts are typically used for this conversion, unwanted side reactions remain a concern, particularly when products are attempted to be recovered long-term. In this study, an enzymatic catalyst is used to enable the selective conversion of CO2 to FA, as a formate ion. A dual-cell flow reactor system is used to first reduce a charge mediator electrochemically (reduction cell), which then activates a catalyst to selectively convert CO2 to formate (production cell). This approach minimizes enzyme degradation by avoiding direct contact with increased voltages and improves the quantity of formate produced. The system produced 25 mM of formate and reached over 50% Coulombic efficiency. The larger volume of this dual-cell system increases the quantity of formate produced beyond that of a batch cell. Additional design configurations are employed, including a pH control pump to maintain catalyst activity and a packed bed reactor to improve contact of the charge carrier with the catalyst. Both configurations retained higher production and efficiency long-term (∼168 h). The results highlight the challenges of developing a system where many parameters play a role in optimizing performance. Nevertheless, the ability of the system to produce formate from CO2 demonstrates the potential to improve upon this configuration for a variety of electrochemical CO2 conversion applications.

Temperature‐Responsive Formation Cycling Enabling LiF‐Rich Cathode‐Electrolyte Interphase

AbstractFormation of LiF‐rich cathode‐electrolyte interphase is highly desirable for wide‐temperature battery, but its application is hindered by the unwanted side reactions associated with conventional method of introducing fluorinated additives. Here, we developed an additive‐free strategy to produce LiF‐rich cathode electrolyte interphase (CEI) by low‐temperature formation cycling. Using LiNi0.33Mn0.33Co0.33O2 as a model cathode, the atomic ratio of LiF in the CEI formed at −5 °C is about 17.7 %, enhanced by ~550 % compared to CEI formed at 25 °C (2.7 %). The underlying mechanism is uncovered by both experiments and theoretic simulation, indicating that the decomposition of LiPF6 to LiF is transformed into spontaneous and exothermic on positively charged cathode surface and lowering the temperature shift chemical equilibrium towards the formation of LiF‐rich CEI. Superior to conventional fluorinated additives, this approach is free from unwanted side reactions, imparting batteries with both high‐temperature (60 °C) cyclability and low‐temperature rate performance (capacity enhanced by 100 % at 3 C at −20 °C). This low‐temperature formation cycling to construct LiF‐rich CEI is extended to various cathode systems, such as LiNi0.8Mn0.1Co0.1O2, LiCoO2, LiMn2O4, demonstrating the versatility and potential impact of our strategy in advancing the performance and stability of wide‐temperature batteries and beyond.

Peptide Bond Formation Between Unprotected Amino Acids: Convergent Synthesis of Oligopeptides.

In the history of peptide chemical synthesis, amino acid-protecting groups have become basic, essential, and common moieties. As the use of protecting groups for amino acids effectively suppresses unwanted side reactions and enables the desired reaction to proceed selectively, their use continues regardless of the complexities of the protection processes and the waste generated by the deprotection residues. We developed peptide bond formation between unprotected amino acids to form silacyclic dipeptides. This is the first report of the proceeding cross-condensation between an unprotected amino acid and another unprotected amino acid. The selectivity, reaction yields, and purity of the products were satisfactory. In addition, we demonstrated further elongation of these compounds and achieved convergent synthesis with peptide-peptide elongation without the use of coupling reagents. Thus, these methods showed the potential to unlock a new, more efficient synthetic path toward polypeptides.

Mastering Proton Activities in Aqueous Batteries.

Advanced aqueous batteries are promising solutions for grid energy storage. Compared with their organic counterparts, water-based electrolytes enable fast transport kinetics, high safety, low cost, and enhanced environmental sustainability. However, the presence of protons in the electrolyte, generated by the spontaneous ionization of water, may compete with the main charge-storage mechanism, trigger unwanted side reactions, and accelerate the deterioration of the cell performance. Therefore, it is of pivotal importance to understand and master the proton activities in aqueous batteries. This Perspective commentson the following scientific questions: Why are proton activities relevant? What are proton activities? What doweknow about proton activities in aqueous batteries? How dowebetter understand, control, and utilize proton activities?

In-situ formed Li2O and an artificial protective layer on copper current collectors to enhance the cycling stability of lithium metal anode batteries

In this study, we present a facile one-step method for the thermal treatment of commercial Cu foils, leading to the growth of Cu2O and CuO nanoparticles in an air atmosphere, resulting in the coating of an artificial protective layer on the copper foil surface. The as-prepared CuO/Cu2O nanoparticles exhibit a spherical morphology, providing ample active sites to improve uniform lithium plating and cyclic stability by building a highly stable In-situ Li2O-rich solid-electrolyte interphase (ISEI). The artificial solid-electrolyte interphase (ASEI) protective layer contains graphene oxide (GO) as a filler with PVDF-HFP and lithium Nafion polymers, enhances Li+ ion migration, which reduces volume expansion and stabilizes the interface, preventing unwanted side reactions between active lithium and electrolytes by facilitating controlled lithium deposition underneath. For integration into an anode-less full cell based on a 2032-type coin cell, alongside a lithium iron phosphate (LFP) cathode, the ISEI oxide layer was grown on a Cu foil electrode (denoted as Cu-30) via a thermal treatment at 320 °C in air for 30 min and coated ASEI (denoted as GO@Cu-30). This cell demonstrated remarkable electrochemical performance. After 250 cycles at 0.5C, it exhibited an outstanding capacity retention of 93.12 % with 99.92 % CE, significantly surpassing the performance of a bare Cu foil, which showed a capacity retention of only 9.54 % with CE of 98.77 %. This work highlights the potential of a simple thermally treated Cu foil as a current collector to overcome the Anode-less lithium metal battery (ALMB) challenges associated with high-energy-density demand.

Temperature-Responsive Formation Cycling Enabling LiF-Rich Cathode-Electrolyte Interphase.

Formation of LiF-rich cathode-electrolyte interphase is highly desirable for wide-temperature battery, but its application is hindered by the unwanted side reactions associated with conventional method of introducing fluorinated additives. Here, we developed an additive-free strategy to produce LiF-rich cathode electrolyte interphase (CEI) by low-temperature formation cycling. Using LiNi0.33Mn0.33Co0.33O2 as a model cathode, the atomic ratio of LiF in the CEI formed at -5 °C is about 17.7 %, enhanced by ~550 % compared to CEI formed at 25 °C (2.7 %). The underlying mechanism is uncovered by both experiments and theoretic simulation, indicating that the decomposition of LiPF6 to LiF is transformed into spontaneous and exothermic on positively charged cathode surface and lowering the temperature shift chemical equilibrium towards the formation of LiF-rich CEI. Superior to conventional fluorinated additives, this approach is free from unwanted side reactions, imparting batteries with both high-temperature (60 °C) cyclability and low-temperature rate performance (capacity enhanced by 100 % at 3 C at -20 °C). This low-temperature formation cycling to construct LiF-rich CEI is extended to various cathode systems, such as LiNi0.8Mn0.1Co0.1O2, LiCoO2, LiMn2O4, demonstrating the versatility and potential impact of our strategy in advancing the performance and stability of wide-temperature batteries and beyond.

Construction of a Composite Sn‐DLC Artificial Protective Layer with Hierarchical Interfacial Coupling Based on Gradient Coating Technology Toward Robust Anodes for Zn Metal Batteries

AbstractDeveloping a robust zinc (Zn) anode, free from Zn dendrites and unwanted side reactions, relies on designing a durable and efficient interfacial protection layer. In this study, gradient coating technology is employed to construct a hierarchically structured composite of Sn with diamond‐like carbon (DLC/Sn‐DLC) as an artificial protective layer. The DLC framework endows DLC/Sn‐DLC layer with high stability and adaptability, achieving long‐term stability of the anode–electrolyte interface. The gradual‐composite Sn, with its Sn─O─C interface chemical bonds, facilitates rapid charge transfer and offers ample zincophilic sites at the base, promoting uniform Zn2+ reduction reaction and deposition. Additionally, the DLC/Sn‐DLC composite exhibits a “lotus effect” and favorable hydrophobic properties, preventing water‐reduced side reactions. Leveraging this structural design and the synergistic cooperation of DLC and Sn, the DLC/Sn‐DLC@Zn electrode demonstrates remarkable Zn plating/stripping reversibility, eliminating Zn dendrites and side reactions. Notably, under a high current density of 10 mA cm−2, the DLC/Sn‐DLC@Zn anode‐based symmetrical cell exhibits stable operation for over 1550 h, with a low nucleation overpotential of 101 mV. The DLC/Sn‐DLC@Zn||Mn3O4‐CNTs full battery delivers a high capacity of 109.8 mAh cm−2 after 5800 cycles at 2 A g−1, and the pouch cell shows potential for energy storage applications.

Self‐Assembled Protection Layer Induced by Bifunctional Additive for Reversible Aqueous Zinc Metal Battery

AbstractAqueous zinc metal battery (AZMB) has received widespread attention due to the advantages of low cost and high safety. However, challenges of dendritic growth, hydrogen evolution reaction, and other side‐reaction impede the performance of the Zn anode. Herein, 4‐amino‐benzene‐sulfonic acid (ABSA) is proposed as an additive to the ZnSO4 electrolyte for improving the performance of AZMB. Combined analyses of theoretical calculations and experiment results, ABSA assumes a pivotal function in constructing an adsorptive layer, facilitating the subsequent formation of a stable sulfur‐rich solid‐electrolyte interphase (SEI). Consequently, the SEI layer modulates the pathway of Zn2+ electrodeposition/dissolution and effectively hinders the deleterious growth of dendrites and unwanted side reactions. As a result, the Zn||Zn cells stably cycles for 2500 h at 1 mAh cm−2/1 mA cm−2 and over 1000 h at 10 mAh cm−2/10 mA cm−2. Significantly, the pouch cell of Zn||VO2 can obtain the specific capacity of 151 mAh g−1 after 100 cycles. This work may provide a new perspective for designing advanced electrolytes from the prospect of interface protection for the AZMB and other metal ion batteries.

A study of the molecular interactions of hemoglobin with diverse classes of therapeutic agents

Investigation of the interaction of hemoglobin (Hb) with therapeutic agents may be useful from three perspectives. First, there are a few therapeutic agents targeting precisely Hb. Second, the high concentration in the blood makes it a likely target for (often unwanted) side reactions of drugs targeting other systems in the body. Third, with its complex and well-studied reactivity, Hb offers itself as a useful model protein for understanding the interactions of therapeutic molecules with proteins via various mechanisms that include allosteric effects, coordination chemistry, metal- or aminoacid-based redox processes, and solution-based oxidative and nitrosative stress chain reactions. Presented here is a review of the molecular interactions described for hemoglobin with various therapeutic agents of organic, coordinative, or organometallic types. These interactions are typically studied by spectroscopy (fluorescence, UV–vis, circular dichroism, infrared, NMR), X-rays diffraction and molecular modeling (especially docking). Classes of therapeutic agents whose molecular interactions with Hb have been described include antioxidants (e.g., ascorbate, tocopherol, glutathione, carotenoids), anti-sickling agents, various organic chemotherapeutics, and metallodrugs.

Heat flows enrich prebiotic building blocks and enhance their reactivity

The emergence of biopolymer building blocks is a crucial step during the origins of life1–6. However, all known formation pathways rely on rare pure feedstocks and demand successive purification and mixing steps to suppress unwanted side reactions and enable high product yields. Here we show that heat flows through thin, crack-like geo-compartments could have provided a widely available yet selective mechanism that separates more than 50 prebiotically relevant building blocks from complex mixtures of amino acids, nucleobases, nucleotides, polyphosphates and 2-aminoazoles. Using measured thermophoretic properties7,8, we numerically model and experimentally prove the advantageous effect of geological networks of interconnected cracks9,10 that purify the previously mixed compounds, boosting their concentration ratios by up to three orders of magnitude. The importance for prebiotic chemistry is shown by the dimerization of glycine11,12, in which the selective purification of trimetaphosphate (TMP)13,14 increased reaction yields by five orders of magnitude. The observed effect is robust under various crack sizes, pH values, solvents and temperatures. Our results demonstrate how geologically driven non-equilibria could have explored highly parallelized reaction conditions to foster prebiotic chemistry.

Polarizability Engineering of Surface Flattening Molecular Dipoles for Fast and Long Lithium Metal Battery Operation

To overcome the energy limitations of conventional Li‐ion batteries (LIB), renewed attention has been given to Li‐metal anodes, which provide the highest capacity and lowest anode potential. To realize Li‐metal batteries (LMBs), it is crucial to stabilize unwanted side reactions on the surface and to inhibit problematic dendrite growth, which causes short‐circuit issues. Herein, diverse pyrrolidone‐based molecular dipole additives controlled by different functional groups are introduced as trifunctional surface stabilizers. It is discovered that the Li–Li symmetric cell improves proportionally with the molar volume and corresponding polarizability values of the molecular dipoles. The highly polarizable pyrrolidone‐based molecular dipoles offer exceptional benefits, including surface flattening of the Li metal anode, controlling the growth direction of crystalline Li, and forming durable solid electrolyte interface (SEI) components. The study is based on polarizability‐controlled molecular dipoles, and offers an effective approach for designing advanced surface stabilizers to develop of high‐performance LMBs.

1,4-Dihydropyridine Anions as Potent Single-Electron Photoreductants.

We report the use of simple 1,4-dihydropyridine anions as a general platform for promoting single-electron photoreductions. In the presence of a mild base, 1,4-dihydropyridines were shown to effectively promote the hydrodechlorination and borylation of aryl chlorides and the photodetosylation of N-tosyl aromatic amines under visible light irradiation. Our studies also demonstrate that the C4 substituent can influence the reactivity of these anions, reducing unwanted side reactions like hydrogen atom transfer and back-electron transfer.

Synergistic interaction between amphiphilic ion additive groups for stable long-life zinc ion batteries

The uneven deposition of zinc and hydrogen generation at the zinc anode interface constitute major impediments to the lifespan of aqueous zinc-ion batteries. Herein, an amphoteric ion additive, choline phosphate (CP), is proposed to stabilize the battery anode interface. The remarkable interplay between choline ions and phosphate groups assumes a pivotal role in homogenizing zinc ion deposition and regulating the behavior of free water molecules. Due to the negative electric field adsorption on the surface of the zinc anode, the positively charged choline ions will be adsorbed on its surface preferentially and prevent the approach of water molecules. The phosphate group interacts strongly with the zinc ion, permeating the solvated structure of these ions, regulating zinc ion flux, and immobilizing free water molecules through hydrogen bonding to impede unwanted side reactions. In summary, using CP additives yields a profound enhancement in enabling significantly extended cycle lifespans of both Zn//Zn symmetric batteries and LiFePO4 full batteries.

Aqueous Zinc Metal Batteries with Anode Stabilized by Plasma Treatment

Aqueous Zn batteries have recently attracted significant attention due to the various benefits offered by Zn metal anodes. However, the formation of dendrites and unwanted side reactions between the Zn anode and the aqueous electrolyte remain challenging problems. Herein, a straightforward plasma treatment that converts the surface of the Zn metal into ZnF2 is proposed. Calculations using density function theory reveal that the diffusion energy barrier for Zn atoms on the ZnF2 surface (0.02 eV) is considerably lower than that on the regular Zn surface (0.25 eV). As a result, the Zn anode treated with plasma (referred to as Plasma‐Zn) exhibits a highly reversible Zn plating/stripping process and significantly suppresses dendrite formation for more than 1300 h. Furthermore, when combined with polyaniline (PANi)‐intercalated V2O5 in a full cell configuration (Plasma‐Zn//PANi‐intercalated V2O5), it demonstrates enhanced rate capability, delivering a discharge capacity of 258 mAh g−1 at 2000 mA g−1, along with improved long‐term stability, retaining 72% of its capacity after 1000 cycles at 1000 mA g−1.