Comprehensive Summary:Aluminum nanoparticles (Al NPs) have significant potential applications in various fields due to their unique LSPR. Significant advancements have been achieved in controlling the size and morphology of Al NPs. However, the efficient modification of Al NPs with polymers has not been implemented. Herein, we report a facile and efficient free-radical polymerization induced grafting-to (FRPIGt) method for grafting polymer chains onto Al NPs. By optimizing polymerization conditions, we were able to achieve a polymer brush layer with a weight loss fraction of up to 43.3%, which was higher than those of other polymers with carboxyl or primary amine end groups. Moreover, a broad range of vinyl monomers, including styrene, methacrylate, and methyl methacrylate, can be applied using the FRPIGt method to modify Al NPs. In addition, the FRPIGt method can be extended to photoinduced organocatalyzed atom-transfer-radical polymerization. This work paves a new path for the preparation of a wide range of polymer-functionalized Al NPs and their polymer composites to be utilized in various fields.

Comprehensive Summary:Electron transfer is an important way to activate persulfate. Currently, the electrons for persulfate activation mainly originate from organic contaminants or the catalyst itself, which can lead to selective activation of persulfate or oxidation of the catalyst, respectively, and thus become a bottleneck restricting its application. In this work, Cu–doped FeVO ₄ (Cu–FVO) was prepared, and the results showed that Cu doping can significantly improve the photocatalytic activity and stability of FVO for peroxymonosulfate (PMS) activation. The optimized Cu–FVO/PMS/light system exhibited a high BPA degradation rate that is 4.3 times higher than that of the FVO/PMS/light. This system manifested a broad applicability to various organic contaminants even with complex matrix. Photoelectrochemical analysis and DFT theoretical calculations revealed that Cu doping boosted the photogenerated charge separation and the adsorption of PMS on FVO. Furthermore, Cu doping led to the establishment of an electron transfer channel from Cu–FVO to PMS, through which photogenerated electrons achieved an efficient PMS activation. Meanwhile, holes were consumed by organic contaminants to avoid the oxidation of catalyst. These collectively enhanced the photocatalytic activity and stability of Cu–FVO, which also maintained high catalytic activity even after 20 cycling degradation reactions.

Comprehensive Summary:Five unreported and oxygenated ent-rosane diterpenoids ( ent-RDs), Euphomillanols A—E ( 1— 5), were isolated from Euphorbia milii. Among them, compounds 1 and 2 are unprecedented 7/7/6-fused tricyclic 5, 10-seco- ent-RDs and possess a unique 11-oxabicyclo[4.4.1]undeca-1(10), 5-diene moiety, while 3 is characterized by a 1-methyl-6-oxabicyclo[3.2.1]oct-2-ene motif of ring A. Their structures with absolute configurations were unambiguously determined by the extensive spectroscopic methods, X-ray crystallography, and ECD calculation. Putative biosynthetic pathways for compounds 1— 3 are proposed. All compounds exhibited antiadipogenic effects in 3T3-L1 adipocytes, and the most potent compound 4 showed an EC ₅₀ value of 3.92 µmol/L with low cytotoxicity (IC ₅₀ > 89.54 µmol/L).

Comprehensive Summary:How to obtain organic electro-optic materials with large electro-optic coefficients, high glass transition temperature, and good optical transparency remains a challenge in this field. To solve this problem, we introduce groups that can undergo Huisgen cycloaddition reactions into the donor and electron bridge of chromophores with large hyperpolarizability using tetrahydroquinoline as the donor. Binary cross-linkable chromophores TLD1-2 with CF ₃-TCF as the acceptor and chromophores TLD3-4 with 5Fph-TCF as the acceptor were synthesized. After poling and crosslinking, the T _g of TLD1/TLD2 and TLD3/TLD4 were raised to 152 and 174°C, respectively. The electro-optical coefficients of chromophores TLD1/TLD2 and TLD3/TLD4 were as high as 312 pm/V and 287 pm/V, respectively. The long-term alignment stability test showed that after being left at 85°C for 500 h, the cross-linked film TLD3/TLD4 can still maintain more than 98% of the original electro-optical coefficient value, which is higher than that of TLD1/TLD2 (93%). The chromophore TLD3-4 exhibited much blue-shifted maximum absorption wavelengths (˜40 nm) compared to TLD1-2 which was beneficial for reducing optical loss in the device. The combination of high electro-optic coefficient, strong stability, and excellent optical transparency makes the TLD series of binary cross-linked materials very promising for practical high-performance electro-optic devices.

Comprehensive Summary:An amide-substituted quinuclidine-borane has been identified as a more efficient hydridic hydrogen atom transfer (HAT) catalyst for the hydroalkylation of unactivated olefins under visible-light irradiation. ¹H NMR titration experiments reveal that the amide moiety of the quinuclidine-borane catalyst forms stronger hydrogen bonds with the carbonyl substrates, thereby improving the reaction yields. Furthermore, it was found that the reaction yields correlate well with the association constant between the quinuclidine-borane catalyst and the carbonyl substrate. A scale-up reaction using a continuous-flow photoreactor has also been demonstrated.

Comprehensive Summary:Given the crucial role of film morphology in determining the photovoltaic parameters of organic solar cells (OSCs), solvent or solid additives have been widely used to realize fine-tuned film morphological features to further improve the performance of OSCs. However, most high-performance OSCs are processed only using single component additive, either solvent additive or solid additive. Herein, a simple molecular building block, namely thieno[3, 4- b]thiophene (TT), was utilized as the solid additive to coordinate with the widely used solvent additive, 1-chloronaphthalene (CN), to modulate the film morphology. Systematical investigations revealed that the addition of TT could prevent the excessive aggregation to form a delicate nanoscale phase separation, leading to enhanced charge transport and suppressed charge recombination, as well as superior photovoltaic performance. Consequently, the PM6:Y6 based OSCs with the addition of hybrid additive of CN + TT demonstrated the optimal PCE of 18.52%, with a notable FF of 79.6%. More impressively, the PM6:Y6:PC ₇₁BM based ternary OSCs treated with the hybrid additives delivered a remarkable efficiency of 19.05%, which ranks among the best values of Y6-based OSCs reported so far. This work highlights the importance of the hybrid additive strategy in regulating the active layer morphology towards significantly improved performance.

Comprehensive Summary:A mechanistically distinctive visible-light-promoted metal-free aerobic oxidation of alkenyl silanes with alcohols was disclosed to efficiently construct α-alkoxy ketones under mild conditions. The primary, secondary, and tertiary alcohols could be used as reactants. The protocol could be carried out on a gram-scale. Various derivatizations of products could be conducted. Mechanistic studies indicated the reaction was initiated by single-electron oxidation of the alkenyl silanes, rather than radical addition to alkenyl silanes.

Comprehensive Summary:Catalytic methylative coupling of internal alkynes and aldehydes/aldimines through regioselective oxidative cyclization promoted by a phosphine–Co complex is presented. Such process constitutes an unprecedented and unique approach for Co-catalyzed generation of metallacycles that reversed inherent regiochemical biases to furnish a wide range of allylic alcohols and allylic amides bearing a tetrasubstituted alkene in up to 98% yield with high regioselectivity, representing a novel and general strategy for reversal of substrate-controlled regioselectivity in metal-catalyzed oxidative cyclization.

Comprehensive Summary:Chiral phosphorescent materials have received extensive research owing to the unique properties of optical activity in recent years. Many phosphorescent carbon dots (CDs) materials have been reported, but the research on chiral phosphorescence is still in the exploratory stage. This work designs multi-color room temperature phosphorescent (RTP) CDs with chiral signals, which are fully mixed with aromatic aldehyde precursors and chiral amino compounds precursors in a boric acid (BA) matrix and can be easily prepared by solvent-free thermal method. The prepared ( R)-GCDs, ( R)-YCDs and ( R)-RCDs achieved phosphorescence emission at 545 nm, 582 nm, and 654 nm, respectively, and exhibited corresponding circular dichroism (CD) signals at 341 nm, 394 nm, 384 nm, and 380 nm, 448 nm, and 435 nm, respectively. The longest phosphorescence lifetime is up to 946 ms. Specifically, YCDs exhibit time-dependent phosphorescence under UV excitation, and the afterglow time under white light excitation can reach 40 s. This article provides a new approach to the study of chiral phosphorescence.

Comprehensive Summary:With protoescigenin as starting material and through orchestrated application of Yu and Schmidt glycosylation protocols, the synthesis of acyl group-free escin derivatives was achieved for the first time. As the undesired non-specific toxicity, originating from the existence of acyl groups on aglycone, prohibits the wide application of escins, the established strategies toward non-acylated protoescigenin-type saponins would dramatically ease the access to escin derivatives dispense of acyl groups, thereby speeding up the pace of pharmaceutical use of these valuable compounds.

Comprehensive Summary:Chiral phosphine-catalyzed asymmetric (4+2) annulation of the amide-based Morita–Baylis–Hillman (MBH) carbonates with β, γ-unsaturated butenolides has been developed to give enantiomer-enriched bicyclic δ-lactam γ-butyrolactone compounds. The amide-based MBH carbonates were first used as acceptor and aza-C4 synthon in phosphine catalysis. Under mild reaction conditions, a variety of amide-based MBH carbonates and unsaturated butenolides were well tolerated to provide chiral bicyclic δ-lactam γ-butyrolactone derivatives in high yields with excellent enantioselectivities as well as diastereoselectivities. A plausible reaction mechanism was also proposed based on control experiments and DFT calculations.

Comprehensive Summary:A new gelator ( BAzo-Chol) comprising a diazocine core and two cholesterol units linked via carbamate groups has been designed and synthesized. Its gelation ability in several kinds of organic solvents is identified. Investigations with scanning electron microscopy (SEM), transmission electron microscopy (TEM), rheological measurements, and UV -vis absorption and ¹H NMR spectroscopy reveal that BAzo-Chol can self-assemble into elastically interpenetrating one-dimensional nanostructures in organogels through a cooperative effect of the π-π interactions, hydrogen-bonding, and van der Waals forces. Moreover, the unconventional Z/ E conformational transitions of these organogels, due to the inclusion of diazocine, endow the BAzo-Chol gels with excellent photo-responsive gel-sol transition and remarkable visible light-induced chromic properties. Lastly, due to its sensitive response to visible light accompanied by distinct changes in both colour and transparency of the gel-sol transitions, the potential application of the current gelator in smart windows is signified.

Comprehensive Summary:A chemical investigation of the deep-sea-derived fungus Penicillium allii-sativi MCCC 3A00580 resulted in the discovery of four new meroterpenoids ( 1— 4) and one related known co-metabolite ( 5). These meroterpenoids showcase unique carbon skeletons featuring a common drimane sesquiterpene part with highly diverse polyketide units. Particularly, compound 1 incorporates a salicylic acid moiety while 2 possesses a rare peroxide bridge in the polyketide part. The structures of new compounds were assigned by extensive spectroscopic analysis, quantum calculations, and biogenetic considerations. Notably, 3 significantly blocked the mTOR signaling pathway, resulting in the arrest of cell cycle at G0-G1 phase and triggering mitochondrial apoptosis in Hela cells. While the previously reported co-metabolite macrophorin A (MPA) effectively triggered cell death in MDA-MB-231 cancer cells by activating apoptosis pathways involving death receptors, mitochondria, mTOR, and TNF.

Comprehensive Summary:Given the lack of systematic polyprenylated acylphloroglucinols (PPAPs) research on traditional Chinese medicine of Hypericum kouytchense, this plant was applied for the phytochemical study, which led to fifteen new PPAPs ( 1— 15, PPAPs), along with 36 known PPAP derivatives. Their structures and absolute configurations were established by comprehensive spectral analysis and theoretical ECD and NMR calculations. Structurally, compound 1 possesses a rare fused 6/6/6/5/5 pentacyclic ring system. Eleven compounds exhibited good multidrug resistance reversal activity (RF ranging from 5 to 53) in HepG2/ADR cells. Importantly, compound 34, the most potential MDR modulator, showed better reversal effect (RF: 53) than positive control, verapamil. The primary mechanistic study of compound 34, implied that this compound could prohibit the function of P-gp transport rather than its expression. The possible recognition mechanism between compound 34 and P-gp was predicted by molecular docking.

Comprehensive Summary:With the rapid development of solid-state batteries, solid-state polymer electrolytes (SPEs) have attracted widespread attention due to their excellent environmental friendliness, designability, and forming film ability. However, due to the limited conductive path of polymers, lithium-ion diffusion kinetics are limited, and low ion conductivity is a huge challenge for SPEs in practical applications. This work provides a polyethylene oxide (PEO) based polymer electrolyte, which has multiple paths of ion diffusion caused by organic polymer framework of poly(hexaazatrinaphthalene) (PHATN). The unique porous channel, the specific surface characteristics, the coordination of -C=N- groups in PHATN with Li ⁺, combined with the mobility of PEO segments, make the SPEs have a good ability to conduct Li ⁺. Interestingly, the PHATN-PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) composite electrolytes exhibit excellent electrochemical properties. At room temperature, the conductivity of PHATN-PEO electrolyte can reach 1.03 × 10 ^–4 S·cm ^–1, which is greatly improved compared with 3.9 × 10 ^–6 S·cm ^–1 of PEO. Delightedly, the lithium-ion transference number of PHATN-PEO electrolyte achieves 0.61, and the electrochemical window increases to 4.82 V. The LFP/1%PH-PEO/Li solid-state batteries show good electrochemical cycles. This work reveals an efficient stratagem for the design of polymer solid-state electrolytes.

Comprehensive Summary:Herein, an unprecedented nickel-catalyzed regioselective hydroalkynylation of unsymmetrical internal alkynes was realized with steric hindered resistance selectivity via the cyano-directing group strategy. Significantly, the resulting 1, 3-enyne products could be effectively employed in the synthesis of novel nitrogen-containing tricyclics compounds, that provided the potential candidate compound 8a (IC ₅₀ = 2.6—6.1 µmol/L) for the anti-tumor cell proliferation activity. Therefore, this work not only improves the transition-metal- catalyzed hydroalkynylation strategy of internal alkynes, but also exhibits versatility of 1, 3-enynes in the construction of the complex bioactive chemical space.

Comprehensive Summary:Regulating brain iron metabolism and reducing neuronal ferroptosis is proven to be a potential method for treating Alzheimer’s disease (AD). However, gastric juice has a pH of 1.1—2.2 where a large number of interfering ions are dissociated from the food, which in turn causes traditional oral iron chelators to be saturated and inactivated. Herein, poly(4-vinylbenzoic acid) polymer chains were introduced as guided by Fe ³⁺ ion template into the porous network (TpPa-1) via molecularly imprinted technology to obtain porous iron chelators, COOH@TpPa-1. The COOH@TpPa-1 maintains a multiple hydrogen bonding structure to block the channels in the stomach (pH ˜1.1—2.2) with a strongly acidic environment, so just a small amount of active sites have been occupied. As COOH@TpPa-1 enters the colon, the alkaline environment disrupts the original hydrogen-bonded structure and forms anionic fragments, the bonding affinity for Fe ³⁺ ions was ˜4.0 times that in the stomach, and also gave a high selective coefficient 4.2 times higher than that of conventional iron chelators. These designable “on” and “off” states promote the effective enrichment of iron ions within the colon by the porous chelator and produce a favorable therapeutic effect on Alzheimer’s symptoms caused by ferroptosis in mice.

Comprehensive Summary:pH is an important stimuli-responsive signal because deprotonation-protonation process is crucial for many life functions. Photoacid is a kind of photoresponsive group that can release protons upon irradiation. This property makes invasive pH control can be replaced by noninvasive light control. However, photoacid is rare. In this work, macrocyclic calixpyridinium was found to be used as a photoacid to release protons from acidic methylene under the irradiation of a 254 nm UV lamp. When the solution of calixpyridinium–disulfonated xantphos aggregates were irradiated by a 254 nm portable UV lamp, disulfonated xantphos was able to receive the protons released from calixpyridinium. This noninvasive photocontrolled proton transfer not only replaces an invasive pH regulation but also achieves a synergistic function. The deprotonation of calixpyridinium and the protonation of disulfonated xantphos can occur simultaneously to disrupt the aggregates. Moreover, the photoresponsive disassembly is reversible by heating. This photoresponsive material was further applied as a photocontrolled release model. In addition, a dissipative assembly was successfully designed based on this photoresponsive disassembly. This study supplies a generalized strategy to construct pH-responsive biocompatible materials with light-control properties by using macrocyclic calixpyridinium and its matched various guests in water.

A new fluorescent fingerprint powder ( DFF-MMT) was formulated by blending cyclic chalcone dye DFF with montmorillonite (MMT), which can develop latent fingerprints (LFPs) with exceptional resolution and contrast on various surfaces, including ordinary glass, tin foil, marble, LED screens, and materials with distinct colors and fluorescent backgrounds. The fluorescence of DFF-MMT transforms from orange to bright yellow with LFPs, allowing for a flawless visualization of fingerprints on uneven surfaces or materials with static electricity. Impressively, fingerprints developed by DFF-MMT can be stored for over 21 months and conveniently duplicated. The developed LFPs by DFF-MMT still keep high quality under the influence of aquatic condition, illumination and thermal effects. DFF-MMT also exhibits benefits, such as affordability, real-time, high-resolution, high-contrast development and no damage to DNA, making it an ideal choice for sophisticated criminal investigations.

Comprehensive Summary:To address the stereoselective synthesis challenge in π-stacked grids with four chiral centers, we utilized coplanar and highly rigid 11, 12-dihydroindeno[2, 1- a]fluorene-11, 12-diol and 2, 2’-bithiophene as synthons, employing Friedel-Crafts gridization (FCG). Leveraging the supramolecular interactions of S···S and π···π within the thiophene moiety, along with the steric effect of the 11, 12-dihydroindeno[2, 1- a]fluorene scaffold, we successfully achieved the exclusive generation of a single isomer of Ladder-type π-stacked grids (LGs-IF) containing six theoretical isomers. By subsequently substituting 2, 2’-bithiophene with thiophene/bithiophene derivatives as synthons, we maintained an exceptionally high level of stereoselectivity. This study introduces a novel approach for the stereo-controlled preparation of grids involving multi-chiral centers.

Comprehensive Summary:Photocatalysis is a promising green approach for water purification. The diversity of water pH values is a key factor that restricts its practical application since pH affects the adsorption of organic molecules, the stability of catalysts and photocatalytic performance. Here, we report a pH–independent, efficient and stable photocatalytic system with a liquid (water)–liquid (oil)–solid (semiconductor) (L–L–S) triphase interface microenvironment. The system is fabricated by coating a thin layer of silicon oil on the surface of ZnO nanowire arrays, a model chemically unstable semiconductor in both acidic and alkaline solutions. We show that the unique interface makes the dye adsorption pH independent and prevents the semiconductor from being corroded by strong acidic/alkaline solutions, leading to a stable and efficient photocatalytic reaction over a wide pH range (1—14). These findings reveal a promising path for the development of high-performance catalysis systems applicable in complex water environments.

Comprehensive Summary:Two reaction modes for metal-free [3 + 2] cyclization of N-aminopyridinium derivatives with β-alkoxyvinyl trifluoromethylketones have been described through selective C—O or C—O/C—C bond cleavage. This strategy can also be extended to the [3 + 2] cyclization of N-aminopyridinium derivatives with enaminones and bromoalkynes. A broad range of N-aminopyridinium, N-aminoquinolinium, and N-aminoisoquinolinium salts are well tolerated, enabling the divergent synthesis of trifluoroacylated, non-substituted, acylated, and brominated pyrazolo[1, 5- a]pyridine derivatives (62 examples).

Comprehensive Summary:An efficient asymmetric [4+2] cyclization of hydroxyphenyl indolinone with azlactone for the synthesis of spirooxindole δ-lactone has been developed, which realized the first asymmetric reaction of hydroxyphenyl indolinone. A series of intricate structures with congested vicinal quaternary chiral centers were provided in good yields with excellent enantioselectivities via the in situ generated o-QM from hydroxyphenyl indolinone.

Comprehensive Summary:The simultaneous construction of two vicinal C—C bonds in a molecule remains a significant challenge. In this work, we disclose an electroreductive carboarylation of activated alkenes under mild, transition metal-free conditions. Utilizing readily available starting materials (electron-deficient aryl bromides, activated alkenes, and CO ₂), this method demonstrates broad substrate scope and good functional group tolerance. Notably, this strategy enables the addition of two distinct electrophiles across an alkene in a highly chemo- and regioselective manner.

Comprehensive Summary:A visible-light-induced decarboxylative radical cascade cyclization reaction between N-(2-cyanoaryl)-acrylamides and alkyl N-(acyloxy)phthalimide (NHPI esters) for the construction of phenanthridine derivatives has been developed. This approach utilizes lithium iodide (LiI) and triphenylphosphine (PPh ₃) as the redox catalysts and the alkyl radical is produced through the photoactivation of the electron donor-acceptor (EDA) complex. A series of primary, secondary, and tertiary alkyl-substituted phenanthridines are prepared in up to 82% yield without transition-metal catalysts, chemical oxidants, or metal-/organic dye-based photocatalysts.

Comprehensive Summary:Considering their oriented crystalline structure and high luminescent efficiency, the exploration of multi-component organic cocrystal systems with tunable supramolecular nanostructures and potential RGB light emission has emerged as a captivating but challenging subject. Here, we propose a straightforward synthetic strategy to precisely govern the assembly, structure and structure-property relationship of organic cocrystals. By employing the single-crystalline template-assisted epitaxial growth (SCT-EG) method, the two-dimensional (2D) highly-aligned cocrystal nanomeshes are firstly developed to afford an exceptional RGB trichromatic system, triggering cross-modulation white light emission (WLE) with remarkable stability and regeneration capacity over six months. The transformation from random 1D microstructures to uniformly-oriented 2D nanomeshes can be attributed to the regulatory competitive intermolecular π-π, CT interactions, and partial H bond interactions among cocrystals. Moreover, the successful construction of 2D RGB trichromatic cocrystal nanomeshes system holds promise to generate full-color display, which can function as multicolor inks for photonic dynamic recognition, information encryption, and decryption.

Comprehensive Summary:Chiral α-tertiary aminonitriles are valuable synthetic intermediates. They are also found in various structures of biologically active molecules. Therefore, numerous reports of catalytic asymmetric synthesis of chiral α-aminonitriles continuously emerged during the past few decades. Great strides have been made for the synthesis of chiral α-aryl and α-branched alkyl aminonitriles. However, efficient methods for catalytic asymmetric synthesis of chiral α-linear alkyl aminonitriles remain limited. We herein report a new synthetic approach to chiral α-tertiary alkyl aminonitriles via catalytic asymmetric isomerization of cyanoketimines. The synthetic value of this method was illustrated by application to a concise catalytic asymmetric synthesis of vildagliptin.

Comprehensive Summary:We report a palladium-catalyzed asymmetric [4+4] cycloaddition reaction between 2-alkylidenetrimethylene carbonate and electron-deficient indole-2, 3-quinodimethanes ( IQDMs). This reaction features exclusive regioselectivity, high yield (up to 98%), excellent enantioselectivity (up to 95% ee), and easy scale-up without any loss of efficiency, making it valuable for the synthesis of indole-fused eight-membered oxa-rings.

Comprehensive Summary:The difunctionalization of bicyclo[1.1.0]butanes is an under-explored transformation that accesses to moieties that are otherwise difficult to prepare. Herein, a new oxidative radical alkylarylation of N-aryl bicyclobutyl amides with C(sp ³)–H feedstocks is achieved in an atom-economic and photocatalyst- and light-free manner. This protocol follows a sequential C(sp ³)–H/C(sp ²)–H functionalization, providing an efficient route for diversity-oriented synthesis of functionalized 3-spirocyclobutyl oxindoles. In particular, a wide range of C(sp ³)–H feedstocks, including ether, alcohol, amine, thioether, polychlorinated methane, silane, acetone, acetonitrile, toluene, and alkane are all suitable for the C(sp ³)–H functionalization, demonstrating the broad applicability of this transformation.

Comprehensive Summary:The industrialization of organic solar cells (OSCs) faces challenges due to complex synthesis routes and high costs of organic photovoltaic materials. To address this, we designed and synthesized a series of polythiophene-based donor materials, PTVT-T- xCl (20%Cl, 50%Cl and 100%Cl), by introducing different degrees of chlorine substitution within their conjugated skeletons. The incorporation of chlorine atoms does not change the planar conformation of the conjugated main chain of the control polymer, PTVT-T, but effectively reduces their HOMO energy levels (≤ –5.3 eV) and alters the crystallinity of the polymers. In addition, when preparing OSC by blending with non-fused electron acceptor A4T-16, the non-radiative energy loss of the three photovoltaic devices gradually decreased with the increase of chlorine content (0.343, 0.278 and 0.189 eV, respectively). Notably, PTVT-T-20%Cl exhibited a more moderate nanoscale phase separation with the acceptor, leading to efficient exciton dissociation, lower bimolecular recombination, and thus a favorable current in the OSCs. Consequently, the photovoltaic device based on PTVT-T-20%Cl:A4T-16 achieved a remarkable photovoltaic efficiency of 11.8%. In addition, the PTVT-T-xCl series polymers show much lower material-only-cost (MOC) values than the other reported photoactive material systems. This work provides the way for the development of low-cost photovoltaic materials and the industrial application of OSC, overcoming previous limitations posed by high energy losses in polythiophene-based donors.

Comprehensive Summary: In the past two decades, the development of asymmetric radical reactions has achieved tremendous progress, which has emerged as a powerful tool for the synthesis of chiral molecules in synthetic chemistry. Among the diverse array of radical processes, the transfer of hydrogen atoms to tertiary carbon radicals offers the potential for constructing chiral tertiary carbon centers in a stereoselective fashion. Notwithstanding the challenges associated with the reactive and evanescent nature of radical species, the use of chiral reagents or mediators has enabled the stereocontrol of the asymmetric hydrogen atom transfer (AHAT), which provides novel avenues for advancing the field of asymmetric synthesis.

Comprehensive Summary: Boronate esters are highly valued in synthetic and pharmaceutical industries for their versatility in creating C—C and C—X bonds. They also find applications as catalysts in chemical transformations as well as stimuli-responsive materials in materials science. Some alkyl boronates themselves also show promising applications in medicinal chemistry. In the past few decades, chemists have been devoted to developing new methods or new starting materials for synthesizing boronate esters. Carboxylic acids and their derivatives are privileged chemical entities due to their readily availability or natural abundance, structural diversity, and chemical stability. Hence, the transformation of carboxylic acid and their derivatives to alkyl/aryl boronate esters has seen its fast development in the past decade. This review summarized the state-to-art development of decarboxylative and decarbonylative borylation of carboxylic acids and their derivatives to aryl and alkyl boronate esters.

Key Scientists: The decarboxylative and decarbonylative borylation of carboxylic acids and their derivatives started only in the past decade. In 2016, the decarbonylative borylation of carboxylic esters and amides was reported by Zhuangzhi Shi and Magnus Reuping’s groups. Then, in 2017, studies on the decarboxylative borylation of redox-active esters such as NHPI esters started to receive increasing attention by Aggarwal, Baran, Fu, Glorius, and Li’s groups. From 2018 to 2023, large numbers of studies on the decarboxylative and decarbonylative borylation of carboxylic acids and their derivatives using transition-metal-catalyst, organo-catalyst, or under photochemical or electrochemical conditions emerged. Due to space limitations, only pictures of scientists who have contributed more than two works in this area are shown herein.

Comprehensive Summary:Urea plays a vital role in human society, which has various applications in organic synthesis, medicine, materials chemistry, and other fields. Conventional industrial urea production process is energy–intensive and environmentally damaging. Recently, electrosynthesis offers a greener alternative to efficient urea synthesis involving coupling CO ₂ and nitrogen sources at ambient conditions, which affords an achievable way for diminishing the energy consumption and CO ₂ emissions. Additionally, urea electrolysis, namely the electrocatalytic urea oxidation reaction (UOR), is another emerging approach very recently. When coupling with hydrogen evolution reaction, the UOR route potentially utilizes 93% less energy than water electrolysis. Although there have been many individual reviews discussing urea electrosynthesis and urea electrooxidation, there is a critical need for a comprehensive review on urea electrocatalysis. The review will serve as a valuable reference for the design of advanced electrocatalysts to enhance the electrochemical urea electrocatalysis performance. In the review, we present a thorough review on two aspects: the electrocatalytic urea synthesis and urea oxidation reaction. We summarize in turn the recently reported catalyst materials, multiple catalysis mechanisms and catalyst design principles for electrocatalytic urea synthesis and urea electrolysis. Finally, major challenges and opportunities are also proposed to inspire further development of urea electrocatalysis technology.

Key Scientists: For urea electrosynthesis, Furuya et al. firstly investigated the electrochemical coreduction of CO ₂ and NO ₃ ^–/NO ₂ ^– using gas-diffusion electrodes in 1995. Then, Wang et al. effectively achieved C—N bond formation and urea synthesis on PdCu alloy nanoparticles in 2020. Shortly, Yan and Yu et al. proposed the formation of *CO ₂NO ₂ from *NO ₂ and *CO ₂ intermediates at early stage on In(OH) ₃ electrocatalyst in 2021, and employed defect engineering strategy to facilitate the *CO ₂NH ₂ protonation in 2022. Amal et al. Investigated the role that Cu-N-C coordination plays for both the CO ₂RR and NO ₃RR. After that, Zhang’s group developed In-based electrocatalysts with artificial frustrated Lewis pairs for urea, and they offered a systematic screening approach for catalyst design in urea electrosynthesis in 2023. And sargent et al. reported a strategy that increased selectivity to urea using a hybrid catalyst.

For urea electrooxidation, Stevenson et al. investigated the effect of Sr substitution toward the urea oxidation reaction. Wang et al. provided insights into the urea electrooxidation process using a β-Ni(OH) ₂ electrode and Qiao et al. elucidated a two-stage reaction pathway for UOR in 2021.

Comprehensive Summary: Electron-rich alkynes, such as ynol and thioynol ethers, have proven to be versatile and appealing partners in catalytic cycloaddition reactions, and thus have raised considerable attentions owing to the practical application in the modular assembly of valuable carbo- and heterocycles. The past decades have witnessed inspiring advances in this emerging field, and an increasing number of related discoveries have been exploited. Divided into two main sections on the basis of substrate type, in each section this comprehensive review will initially summarize their synthetic preparations and subsequently examine their reactivity in every sort of catalytic cycloaddition with emphasis on the methodology development, aimed at providing an access to this burgeoning area and encouraging further innovations in the near future.

Key Scientists: For the cycloaddition of ynol ethers, in 2004, Kozmin et al. firstly developed a silver-catalyzed [2 + 2] cycloaddition of siloxy alkynes with electron-poor olefins. In 2012, Hiyama et al. realized a palladium-catalyzed formal [4 + 2] annulation of alkynyl aryl ethers with internal alkynes. In the same year, Sun et al. discovered an efficient [6 + 2] cyclization between siloxy alkynes and 2-(oxetan-3-yl)benzaldehydes by applying HNTf₂ as catalyst. In 2017, Wender et al. first utilized vinylcyclopropanes (VCPs) as coupling partners in the [5 + 2] annulation of ynol ethers. In 2018 and 2020, Ye et al. reported zinc-catalyzed formal [3 + 2] and [4 + 3] cycloaddition, respectively. For the cycloaddition of thioynol ethers, in 2004, Hilt et al. realized a [4 + 2] cycloaddition by employing the alkynyl sulfides and acyclic 1, 3-dienes. In 2006, a ruthenium-catalyzed [2 + 2] cycloaddition of thioynol ethers with bicyclic alkenes was accomplished by Tam. In 2014, Sun et al. reported an elegant iridium-catalyzed click reaction of thioalkynes with azides.

Comprehensive Summary:Organoborons are commonly used building blocks for rapidly increasing molecular complexity. Although significant progress has been made in the selective functionalization of mono-organoborons, the site-selective functionalization of poly(organoborons) has attracted substantial interest in organic synthesis, pharmaceuticals, and agrochemicals due to the presence of multiple potential reaction sites. This review discusses various activation modes of the target C–B bond, with diverse transformations being achieved in both a selective and efficient manner. Recent advances in the catalytic selective transformations of 1, n-diboronates through ionic and radical pathways are highlighted. Furthermore, we summarize the existing challenges and future research directions in this field.

Key Scientists: In 1993, Suzuki, Miyaura and coworkers developed a pioneering example of selective arylation towards cis-1, 2-bis(boryl) alkenes, marking the inception of this field. The Morken group has made significant contributions to the asymmetric diboration of alkenes and realized elegant catalytic functionalization of these compounds since 2004. In 2016, Fernández and colleagues achieved the selective arylation of the internal C–B bond of tri(boronates). Since 2019, the Aggarwal group has developed efficient Giese-type addition and selective arylation at the more substituted C–B bond of 1, 2-bis(boronic) esters through photoredox catalysis. The controllable regiodivergent alkynylation of 1, 3-bis(boronic) esters was developed by Gao and coworkers in 2023. Recently, Qin conducted elegant research on the programmable late-stage functionalization of bridge-substituted bicyclo[1.1.1]pentane (BCP) bis-boronates. Since 2013, catalytic stereoselective transformations have been developed by several groups, including those led by Morken and Chen. This review summarizes the latest and most significant developments in this field since 1993.

Comprehensive Summary:Organofluorine compounds have attracted substantial interest in life and materials sciences due to the unique properties of fluorine atom(s) that often change the physicochemical and biological properties of organic molecules. Transition-metal-mediated cross-electrophile coupling between carbon electrophiles and fluoroalkyl electrophiles has emerged as a straightforward and efficient route for the synthesis of a wide range of fluoroalkylated compounds because of its synthetic convenience without the tedious synthesis of organometallic reagents. Moreover, alkenes or alkynes-involved three-component cross-electrophile couplings provide rapid and effective access to carbonfunctionalized fluoroalkylated alkanes and alkenes. Herein, we comprehensively summarize the transition-metal-mediated reductive fluoroalkylation of diverse carbon electrophiles through a historical perspective, including trifluoromethylation, difluoroalkylation, monofluoroalkylation, and so on. Different transition metals (Cu, Ni, etc.) and strategies are discussed, in which nickel-catalyzed reductive fluoroalkylation reactions represent an attractive and efficient synthetic route to site-selectively access organofluorine compounds.

Key Scientists: As early as 1965, McLoughlin and Thrower finished the first stoichiometric copper-mediated fluoroalkylation of aromatic iodides with fluoroalkyl iodides. However, excess aromatic iodides and elevated temperature were used for this method. In 1969, Kobayashi and Kumadaki reported studies on the copper-mediated trifluoromethylation of aromatic halides with excess trifluoromethyl iodide. After more than four decades, the Zhang group developed a nickel-catalyzed β-fluorinated alkylation of (hetero)aryl iodides with fluoroalkylated secondary alkyl bromides in 2015, and a nickel-catalyzed difluoromethylation of (hetero)aryl chlorides with chlorodifluoromethane ClCF ₂H in 2017. The Zhang group also developed enantioselective nickel-catalyzed reductive alkyl-arylation of 3, 3, 3-trifluoropropene with (hetero)aryl and tertiary alkyl iodides. In 2018, the MacMillan group developed a novel copper/photoredox dual catalytic system for the trifluoromethylation of aryl bromides or alkyl bromides with ( S)-(trifluoromethyl) dimesitylsulfonium triflate in the presence of tris-(trimethylsilyl) silanol. They also developed a nickel/photoredox catalyzed difluoromethylation of aryl bromides in the presence of silane. During this time, the Wang group reported a nickel-catalyzed monofluoroalkylation of aryl halides with monofluoroalkyl halides. From 2021 to 2023, the same group further developed a series of enantioselective nickel-catalyzed trifluoroalkylation of aryl, alkenyl, and acyl halides. Moreover, nonfluorinated alkenes or alkynes could also be used in three-component cross-electrophile couplings. In 2018, the Chu group reported a nickel-catalyzed fluoroalkyl-acylation of alkenes with acyl chlorides and fluoroalkyl iodides. Later, they developed a nickel-catalyzed enantioselective fluoroalkyl-arylation of unactivated alkenes tethering with a pendant chelating group. In 2019, the Chaładaj group reported a palladium-catalyzed reductive perfluoroalkyl-arylation of alkynes with perfluoroalkyl and aryl iodides.

Comprehensive Summary: Cross-electrophile couplings (XEC), a crucial subset of cross-coupling reactions, center on the formation of robust C—C bonds through the union of two electrophiles. Usually, such reactions have primarily been catalyzed by transition metals. However, with the steady advancements in photochemical and electrochemical technologies, XEC reactions have significantly progressed and broadened their scope, allowing for the utilization of a wider array of tolerable functional groups, thus revealing vast application prospects. This review aims to systematically summarize the current prevalent types of electrophiles and delve into their specific application examples within XEC reactions involving electrophiles with identical functional groups. Specifically, XECs between the same type of halides have received considerable attention, whereas carboxylic acids and alcohols are still in the early stages of investigation. Furthermore, certain other common electrophiles remain unexplored in this context. Moreover, this review underscores the remarkable contributions of photochemistry and electrochemistry in the field of XEC reactions, aiming to provide valuable insights and inspiration for researchers. Also, this review hopes to spark further interest in XEC reactions, thereby fueling the continuous development and advancement of this exciting area of research.

Key Scientists: Since the 1960s, advancements in the XEC reaction have been substantial, driven primarily by the application of transition metal catalysts. In this area, many distinguished scientists have contributed their wisdom and efforts. Particularly noteworthy is that, during the systematic study of XEC reactions with the identical functional groups, in 2016, MacMillan achieved a photocatalytic XEC reaction between aryl bromides and alkyl bromides; in 2020, Weix successfully realized a nickel-catalyzed XEC reaction between aryl chlorides and alkyl chlorides. Concurrently, contributions from researchers such as Mei, Wolf, Sevov, Lin, Shen, Browne, Zhang, and Qiu have expanded the scope of XEC reactions to various halides. By 2022, MacMillan and Baran achieved a significant milestone in the XEC between carboxylic acids, further broadening the scope of research in this area. Also, advancements in the XEC of alcohols have been noted, with researchers including Weix, Lian, Tu, and Stahl conducting pioneering work and successfully executing the XEC of protective groups. It is foreseen that the ongoing research endeavors will primarily concentrate on the expansion of diverse electrophiles.

Comprehensive Summary: Tuning electrolyte properties is a widely recognized strategy to enhance activity and selectivity in electrocatalysis, drawing increasing attention in this domain. Despite extensive experimental and theoretical studies, debates persist about how various electrolyte components influence electrocatalytic reactions. We offer a concise review focusing on current discussions, especially the contentious roles of cations. This article further examines how different factors affect the interfacial solvent structure, particularly the hydrogen-bonding network, and delves into the microscopic kinetics of electron and proton-coupled electron transfer. We also discuss the overarching influence of solvents from a kinetic modeling perspective, aiming to develop a robust correlation between electrolyte structure and reactivity. Lastly, we summarize ongoing research challenges and suggest potential directions for future studies on electrolyte effects in electrocatalysis.

Key Scientists: In 1956, Marcus theory was developed to describe the mechanism of outer-sphere electron transfer (OS-ET). In 1992, Nocera et al. directly measured proton-coupled electron transfer (PCET) kinetics for the first time, and their subsequent research in 1995 investigated the effects of proton motion on electron transfer (ET) kinetics. In 1999 and 2000, Hammes-schiffer et al. developed the multistate continuum theory for multiple charge reactions and deduced the rate expressions for nonadiabatic PCET reactions in solution, laying the theoretical foundation for the analysis of PCET kinetics in electrochemical processes. In 2006, Saveant et al. verified the concerted proton and electron transfer (CPET) mechanism in the oxidation of phenols coupled with intramolecular amine-driven proton transfer (PT). Their subsequent work in 2008 reported the pH-dependent pathways of electrochemical oxidation of phenols.

Electrolyte effects in electrocatalysis have gained emphasis in recent years. In 2009, Markovic’s pioneering work proposed non-covalent interactions between hydrated alkaline cations and adsorbed OH species in oxygen reduction reaction (ORR)/hydrogen oxidation reaction (HOR). In 2011, Markovic et al. significantly enhanced hydrogen evolution reaction (HER) activity in alkaline solution by improving water dissociation, which was assumed to dominate the sluggish HER kinetics in such media. In comparation, Yan et al. applied hydrogen binding energy (HBE) theory in 2015 to explain the pH-dependent HER/HOR activity. Cations play a significant role in regulating the selectivity and activity of carbon dioxide reduction (CO₂RR). In 2016 and 2017, Karen Chan et al. introduced the electric field generated by solvated cations to explain the cation effects on electrochemical CO2RR. Conversely, in 2021, Koper et al. suggested that short-range electrostatic interactions between partially desolvated metal cations and CO₂ stabilized CO₂ and promoted CO₂RR.

Recent researches have combined the exploration of the electrical double layer (EDL) structure with theoretical analysis of PCET kinetics. In 2019, Huang et al. developed a microscopic Hamiltonian model to quantitatively understand the sluggish hydrogen electrocatalysis in alkaline media. In 2021, two meticulous studies from Shao-Horn’s group analyzed the effects of cations on reorganization energy and the impacts of hydrogen bonds between proton donors and acceptors on proton tunneling kinetics, respectively. Electrolyte effects on proton transport process were researched in recent years. In 2022, Hu et al. and Chen et al. proposed that the cation-induced electric field distribution and pH-dependent hydrogen bonding network connectivity played essential roles in proton transport, separately.

Enzymes are natural treasure troves that hold multiple superiority. Enzymatic catalysis has become a powerful tool for asymmetric synthesis, though it is typically limited to a relatively narrow range of reaction types. By integrating the advantages of enzymatic catalysis with photocatalysis, photoenzymatic catalysis not only expands the catalytic capabilities of enzymes but also provides an effective strategy for the stereo-control of photochemical reactions, thereby emerging as a significant research field. Herein, we focus on new-to-nature photoenzymatic catalysis by repurposing naturally occurring enzymes with visible light. We highlight the seminal work in reshaping various classes of enzymes, emphasizing their catalytic mechanism and synthetic potentials.

Comprehensive Summary:Near-infrared (NIR)-absorbing polymerized small molecule acceptors (PSMAs) based on a Y-series backbone (such as PY-IT) have been widely developed to fabricate efficient all-polymer solar cells (all-PSCs). However, medium-bandgap PSMAs are often overlooked, while they as the third component can be expected to boost power conversion efficiencies (PCEs) of all-PSCs, mainly due to their up-shifted lowest unoccupied molecular orbital (LUMO) energy level, complimentary absorption, and diverse intermolecular interaction compared to the NIR-absorbing host acceptor. Herein, an IDIC-series medium-bandgap PSMA (P-ITTC) is developed and introduced as the third component into D18/PY-IT host, which can not only form complementary absorption and cascade energy level, but also finely optimize active layer morphology. Therefore, compared to the D18/PY-IT based parental all-PSCs, the ternary all-PSCs based on D18/PY-IT:P-ITTC obtain an increased exciton dissociation, charge transport, carrier lifetime, as well as suppressed charge recombination and energy loss. As a result, the ternary all-PSCs achieve a high PCE of 17.64% with a photovoltage of 0.96 V, both of which are among the top values in layer-by-layer typed all-PSCs. This work provides a method for the design and selection of the medium-bandgap third component to fabricate efficient all-PSCs.

Comprehensive Summary:Twelve new limonoids ( 1— 12), named trichilitins A—L, were isolated from the leaves and twigs of Trichilia connaroides, together with ten known compounds ( 13— 22). The structures were elucidated by extensive spectroscopic investigations, X-ray diffraction analyses, and ECD calculations. Compound 1, which belongs to a unique class of ring B- seco limonoid, has been identified as 6/7/6/5 tetracyclic due to a key Baeyer-Villiger oxidation. Compounds 2— 7 were identified as ring intact limonoids, while compounds 8— 10 were established as ring D- seco ones, and 11 and 12 were determined to be rearranged ones. All of the compounds were tested for cytotoxicity against three human tumor cell lines (HCT-116, NCl-H1975, and SH-SY5Y). Compounds 6, 7, 13, 14, and 19 exhibited significant cytotoxic effects, especially 7 exhibited significant cytotoxic effects against HCT-116 with an IC ₅₀ value of 0.035 µmol·L ^–1 and was more active than the positive control, doxorubicin with an IC ₅₀ value of 0.20 µmol·L ^–1. Compound 7 effectively induced apoptosis of HCT-116, which was associated with S-phase cell cycle arrest. Furthermore, the Western blot analysis showed that compound 7 could induce cell cycle arrest by promoting the expression levels of p53 and p21.

Comprehensive Summary:Layer-by-layer (LbL) solution processing is an efficient method to realize high performance organic solar cells (OSCs). One of the drawbacks of the LbL-processed active layer is the large difference in the crystallinity of the donor and acceptor, which will lead to imbalance charge transfer and result in unfavorable charge recombination. Herein, we combined a novel volatile additive 3, 5-dichloro-2, 4, 6- trifluorobenzotrifluoride (DTBF) with the LbL method to realize high-efficiency OSCs. DTBF interacts with the non-fullerene acceptor BTP-4F by non-covalent bonding, which enhances the crystallinity and compact stacking of BTP-4F. DTBF doped OSC has balanced and efficient electron transport properties, longer carrier lifetime, higher exciton dissociation and charge collection efficiencies, lower energetic disorder than the control OSC without any additives. Benefiting from the optimization of charge dynamics and micro-morphology by DTBF, the binary LbL-processed OSC achieved synergistic improvements in open-circuit voltage, short-circuit current density and fill factor. As a result, a champion power conversion efficiency ( PCE) of 19% is realized for DTBF-optimized OSC, which is superior to the control OSC (17.55%). This work demonstrates a promising approach to modulate active layer morphology and fabricate high performance OSCs.

Comprehensive Summary:Vicinal stereogenic centers are ubiquitous structural scaffolds in both natural products and synthetic compounds, yet their enantioselective construction remains a significant challenge in organic synthesis. Organoboron compounds are of paramount importance in synthetic chemistry due to their ability to undergo facile transformations, yielding diverse essential chemical bonds such as carbon-carbon, carbon-oxygen, carbon-nitrogen, and carbon-halogen bonds. Transition-metal-catalyzed asymmetric borylative functionalizations of internal alkenes offer a promising strategy for the enantioselective installation of two adjacent chiral centers across carbon-carbon bonds. By leveraging the versatile transformations of the newly introduced boryl unit, this approach holds great potential for expanding the structural diversity of vicinal stereogenic scaffolds. In this concise review, we aim to highlight recent advancements in transition-metal-catalyzed asymmetric borylative functionalizations of internal alkenes, underscore their utility as a versatile approach for constructing vicinal stereogenic centers, and discuss unsolved challenges and future directions in this field.

Comprehensive Summary:Maleimide derivatives are well-established reactive intermediates also found in natural products, synthetic pharmaceuticals and functional polymers. Their specific reactivity found widespread applications in the field of bioconjugation and allowed for the development of highly selective functionalizations based on simple additions and cycloadditions with the possible control of central and C–N axial chirality. These multisite-reactive scaffolds have aroused a long-standing interest throughout the scientific community more particularly as powerful electrophilic partners and more recently as nucleophilic partners in some specific transformations. The persistent interest in these easily accessible synthetic platforms over the last decade has enabled the development of new enantioselective transformations and the major advancements in this field are presented in this review.