Precise Modulation Research Articles

Donor-Acceptor MOF Enabling Efficient Electrochemiluminescence Based on TSCT-TADF.

Electrochemiluminescence (ECL) is an extensively studied luminescence technique recognized for its efficacy in investigating surface energy states. Effective utilization of ECL to explore and probe the charge transfer mechanisms facilitated by novel luminescent materials is crucial. In this study, we demonstrate thermally activated delayed fluorescence (TADF) based on spatial charge transfer through the precisely controlled synthesis of luminescent materials, which is achieved by incorporating phenyl-carbazole derivatives as donor guests within acceptor-hosted metal-organic frameworks (D-A MOFs). These hybrid structures exhibit superior ECL intensities compared with their monomeric counterparts. Mechanistic investigation by DFT calculation reveals that the physically separated yet spatially closed D-A configuration induces efficient intermolecular through-spatial charge transfer (TSCT), leading to efficient ECL through tuning of the dihedral angle of the guest molecules to enhance π-π interactions. This study introduces a strategy for precise modulation of spatial charge transfer at the molecular level in the programmable synthesis of ECL luminophores.

Systematic Evaluation and Application of IDR Domain-Mediated Transcriptional Activation of NUP98 in Saccharomyces cerevisiae.

Implementing dynamic control over gene transcription to decouple cell growth is essential for regulating protein expression in microbial cells. However, the availability of efficient regulatory elements in Saccharomyces cerevisiae remains limited. In this study, we present a novel β-estradiol-inducible gene expression system, termed DEN. This system combines a DNA-binding domain with an estradiol-binding domain and an intrinsically disordered region (IDR) from NUP98. Comparative analysis shows that the DEN system outperforms IDRs from other proteins, achieving an approximately 60-fold increase in EGFP expression upon β-estradiol induction. Moreover, our system is tightly controlled; nontoxic gene expression makes it a powerful tool for rapid and precise modulation of target gene expression. This system holds great potential for unlocking new functionalities from existing proteins in future research.

Customized Heteronuclear Dual Single‐Atom and Cluster Assemblies via D‐Band Orchestration for Oxygen Reduction Reaction

AbstractAdvanced oxygen reduction reaction (ORR) catalysts, integrating with well‐dispersed single atom (SA) and atomic cluster (AC) sites, showcase potential in bolstering catalytic activity. However, the precise structural modulation and in‐depth investigation of their catalytic mechanisms pose ongoing challenges. Herein, a proactive cluster lockdown strategy is introduced, relying on the confinement of trinuclear clusters with metal atom exchange in the covalent organic polymers, enabling the targeted synthesis of a series of multicomponent ensembles featuring FeCo (Fe or Co) dual‐single‐atom (DSA) and atomic cluster (AC) configurations (FeCo‐DSA/AC) via thermal pyrolysis. The designed FeCo‐DSA/AC surpasses Fe‐ and Co‐derived counterparts by 18 mV and 49 mV in ORR half‐wave potential, whilst exhibiting exemplary performance in Zn‐air batteries. Comprehensive analysis and theoretical simulation elucidate the enhanced activity stems from adeptly orchestrating dz2‐dxz and O 2p orbital hybridization proximate to the Fermi level, fine‐tuning the antibonding states to expedite OH* desorption and OOH* formation, thereby augmenting catalytic activity. This work elucidates the synergistic potentiation of active sites in hybrid electrocatalysts, pioneering innovative targeted design strategies for single‐atom‐cluster electrocatalysts.

Controllable Regulation of CO2 Adsorption Behavior via Precise Charge Donation Modulation for Highly Selective CO2 Electroreduction to Formic Acid.

The synthesis of value-added products via CO2 electroreduction (CO2ER) is of great significance, but the development of efficient and versatile strategies for the controllable selectivity tuning is extremely challenging. Herein, the tuning of CO2ER selectivity through the modulation of CO2 adsorption behavior is proposed. Using the constructed zeolitic MOF (SNNU-339), CO2 adsorption behavior is controllably changed from *CO2 to CO2* via the precise ligand-to-metal charge donation (LTMCD) regulation. It is confirmed that the high electronegativity of the coordinate ligand directly restricts the LTMCD, reduces the charge density on the metal sites, lowers the Gibbs free energy for CO2* adsorption, and leads to the transformation of CO2 adsorption mode from *CO2 to CO2*. Owing to the modulated CO2 adsorption behavior and regulated kinetics, SNNU-339 exhibits superior HCOOH selectivity (≈330% promotion, 85.6% Faradaic efficiency) and high CO2ER activity. The wide applicability of the proposed approach sheds light on the efficient CO2ER. This study provides a competitive strategy for rational catalyst design and underscores the significance of adsorption behavior tuning in electrocatalysis.

Modulating the cavity micro-environments of Fe-MOFs for high-performance gas chromatographic separations

Precise modulation of cavity micro-environment in metal-organic frameworks (MOFs) is important for achieving significant separation performance. Herein, the Fe-MOF (MIL-142-BTB-BDC) with different tridentate and bidentate ligands to form cavities, was chosen as the platform to precisely modulate the cavity micro-environment and investigate the influence of cavity windows and cavity walls on gas chromatographic separations. Changing tridentate ligands on the cavity walls led to MIL-142-TATB-BDC while changing bidentate ligands on the cavity windows produced MIL-142-BTB-BDC-NH2. Mechanism investigation revealed that for MIL-142-BTB-BDC and MIL-142-TATB-BDC, altering the ligands of cavity walls had little influence on the thermodynamic interactions between MOFs and analytes while slightly reducing the kinetic diffusion rate of analytes. On the contrary, introducing amino groups on cavity windows in MIL-142-BTB-BDC-NH2 not only increased the thermodynamic interactions with analytes but also slowed down the kinetic diffusion of analytes, which resulted in poor separation performance of the MIL-142-BTB-BDC-NH2 coated column. This work provides a guide to precisely modulating the cavity micro-environment and analyzing the relationship between the cavity micro-environment and application properties of MOFs.

Effects of Different LED Spectra on the Antioxidant Capacity and Nitrogen Metabolism of Chinese Cabbage (Brassica rapa L. ssp. Pekinensis)

Light quality optimization is a cost-effective method for increasing leafy vegetable quality in plant factories. Light-emitting diodes (LEDs) that enable the precise modulation of light quality were used in this study to examine the effects of red-blue (RB), red-blue-green (RBG), red-blue-purple (RBP), and red-blue-far-red (RBF) lights on the growth, antioxidant capacity, and nitrogen metabolism of Chinese cabbage leaves, while white light served as the control (CK). Results showed that the chlorophyll, carotenoid, vitamin C, amino acid, total flavonoid, and antioxidant levels of Chinese cabbage were all significantly increased under RBP combined light treatment. Meanwhile, RBG combined light treatment significantly increased the levels of amino acids but decreased the nitrite content of Chinese cabbage. In addition, RBF combined light treatment remarkably increased the amino acid levels but decreased the antioxidant capacity of Chinese cabbage. In conclusion, the addition of purple light to red-blue light was effective in improving the nutritional value and antioxidant capacity of Chinese cabbage. This light condition can be used as a model for a supplemental lighting strategy for leafy vegetables in plant factory production.

Facilitating Ion Storage and Transport Pathways by In Situ Constructing 1D Carbon Nanotube Electric Bridges between 2D MXene Interlayers.

Multiple van der Waals (vdW) gaps invoke abundant opportunities for contriving artificial architectures and tailoring desired properties via the intercalation route beyond the reach of conventional concepts. Intriguingly, the electrochemical intercalation strategy can precisely and reversibly tune the intercalation stage of charged functional species. This study presents a valid structural editing protocol facilitated by electrochemical intercalation to engineer MXene interlayers, ultimately incorporating in situ constructed carbon nanotube (CNT) electric bridges for enhanced ion storage and transport pathways. The method allows for the precise modulation of electrochemical forces to tailor materials for specific applications. Deep intercalation and in situ growth processes establish robust anchoring sites and connectivity hubs between MXenes and CNTs, ensuring structural homogeneity and stability in advanced electrode materials. The results demonstrate the effectiveness of electrochemistry-mediated interlayer nanoengineering in MXenes, offering a versatile approach to design vdW heterostructures with tailored functionalities for energy storage and conversion applications. This work highlights the potential of electrochemical modulation in advancing materials engineering strategies for next-generation energy storage technologies.

Precise modulation of the debonding behaviours of ultra-thin wafers by laser-induced hot stamping effect and thermoelastic stress wave for advanced packaging of chips

Abstract Laser debonding technology has been widely used in advanced chip packaging, such as fan-out integration, 2.5D/3D ICs and MEMS devices. Typically, laser debonding of bonded pairs (R/R separation) is typically achieved by completely removing the material from the ablation region within the release material layer at high energy densities. However, this R/R separation method often results in a significant amount of release material and carbonized debris remaining on the surface of the device wafer, severely reducing product yields and cleaning efficiency for ultra-thin device wafers. Here, we propose an interfacial separation strategy based on laser-induced hot stamping effect and thermoelastic stress wave, which enables stress-free separation of wafer bonding pairs at the interface of the release layer and the adhesive layer (R/A separation). By comprehensively analyzing the micro-morphology and material composition of the release material, we elucidate the laser debonding behavior of bonded pairs under different separation modes. Additionally, we have calculated the ablation threshold of the release material in the case of wafer bonding and established the processing window for different separation methods. This work offers a fresh perspective on the development and application of laser debonding technology. The proposed R/A interface separation method is versatile, controllable and highly reliable, and does not leave release materials and carbonized debris on device wafers, demonstrating strong industrial adaptability, which greatly facilitates the application and development of advanced packaging for ultra-thin chips.

Supramolecular Catalyzed Cascade Reduction of Azaarenes Interrogated via Data Science.

Catalysis of multicomponent transformations requires controlled assembly of reactants within the active site. Supramolecular scaffolds possess synthetic microenvironments that enable precise modulation over noncovalent interactions (NCIs) engaged by reactive, encapsulated species. While molecular properties that describe the behavior of single guests in host cavities have been studied extensively, multicomponent transformations remain challenging to design and deploy. Here, simple univariate regression and threshold analyses are employed to model reactivity in a cascade reduction of azaarenes catalyzed by water-soluble metal organic cages. Yield and stereoselectivity models help deduce unknown mechanisms of reactivity by the multicomponent, host-guest complexes. Furthermore, a comprehensive model is established for NCIs driving stereoselectivity in the reported host-guest adducts.

Airway macrophage glycolysis controls lung homeostasis and responses to aeroallergen.

The lungs represent a dynamic microenvironment where airway macrophages (AMs) are the major lung-resident macrophages. AMs dictate the balance between tissue homeostasis and immune activation and thus have contradictory functions by maintaining tolerance and tissue homeostasis, as well as initiating strong inflammatory responses. Emerging evidence has highlighted the connection between macrophage function and cellular metabolism. However, the functional importance of these processes in tissue-resident specialized macrophage populations such as those found in the airways, remain poorly elucidated. Here, we reveal that glycolysis is a fundamental pathway in AMs which regulates both lung homeostasis and responses to inhaled allergen. Using macrophage specific targeting in vivo, and multi-omics approaches, we determined that glycolytic activity in AMs is necessary to restrain type 2 (T2) immunity during homeostasis. Exposure to a range of common aeroallergens, including house dust mite (HDM), drove AM-glycolysis and furthermore, AM-specific inhibition of glycolysis altered inflammation in the airways and HDM-driven airway metabolic adaptations in vivo. Additionally, allergen sensitised asthmatics had profound metabolic changes in the airways, compared to non-sensitised asthmatic controls. Finally, we found that allergen driven AM-glycolysis in mice was TLR2 dependent. Thus, our findings demonstrate a direct relationship between glycolysis in AMs, AM-mediated homeostatic processes, and T2 immune responses in the lungs. These data suggest that glycolysis is essential for the plasticity of AMs. Depending on the immunological context, AM-glycolysis is required to exert homeostatic activity but once activated by allergen, AM-glycolysis influences inflammatory responses. Thus, precise modulation of glycolytic activity in AMs is essential for preserving lung homeostasis and regulating airway inflammation.

Theory-driven design of local spin-state modulation at atomically dispersed iron sites for enhanced CO2 electroreduction

Herein, density functional theory (DFT) was used to guide the systematic design of highly efficient single-atom electrocatalysts to improve the kinetics of the CO2 reduction reaction (CO2RR). We present a novel class of catalysts that exhibit magnetic-proximity-induced exchange splitting (spin polarization). The design of these catalysts involved the precise modulation of d-shell energy levels at metallic sites and the subsequent alteration of the atomic/molecular orbitals of the adsorbed intermediates. To validate the effectiveness of our design strategy, we introduced neighboring nitrogen (N) doping near the Fe-N4 coordination environment, demonstrating the successful manipulation of the local spin state of the active sites. The results of the theoretical calculations align with the experimental results, with remarkable selectivity exceeding 90 % at low potentials (<-0.5 V vs. RHE) and sustained electrocatalytic activity for over 24 h. In situ characterization further revealed that a modulated local spin state led to a decrease in the occupation of the Fe 3d spin-down electronic states below the Fermi level. Concurrently, electrons migrated to the frontier antibonding orbitals of *COOH. This dual effect resulted in a lower reaction energy (ΔG), representing a thermodynamic benefit, and accelerated proton transfer to *COOH, representing a kinetic benefit, collectively enhancing the electrocatalytic process.

Unraveling the Fundamentals of Axial Coordination FeN4+1 Sites Regulating the Peroxymonosulfate Activation for Fenton-Like Activity.

Precise modulation of the axial coordination microenvironment in single-atom catalysts (SACs) to enhance peroxymonosulfate (PMS) activation represents a promising yet underexplored approach. This study introduces a pyrolysis-free strategy to fabricate SACs with well-defined axial-FeN4+1 coordination structures. By incorporating additional out-of-plane axial nitrogen into well-defined FeN4 active sites within a planar, fully conjugated polyphthalocyanine framework, FeN4+1 configurations are developed that significantly enhance PMS activation. The axial-FeN4+1 catalyst excelled in activating PMS, with a high bisphenol A (BPA) degradation rate of 2.256 min-1, surpassing planar-FeN4/PMS systems by 6.8 times. Theoretical calculations revealed that the axial coordination between N and the Fe sites forms an optimized axial FeN4+1 structure, disrupting the electron distribution symmetry of Fe and optimizing the electron distribution of the Fe 3d orbital (increasing the d-band center from -1.231 to -0.432eV). Consequently, this led to an enhanced perpendicular adsorption energy of PMS from -1.79 to -1.82eV and reduced energy barriers for the formation of the key reaction intermediate (O*) that generates 1O2. This study provides new insights into PMS activation through the axial coordinated engineering of well-defined SACs in water purification processes.

Atomically dispersed iron sites from eco-friendly microbial mycelium as highly efficient hydrogenation catalyst

Iron, one of the most abundant elements on earth and an essential element for living organisms, plays a crucial role in our daily metabolism. In the field of catalysis, the development of high-performance catalysts based on less toxic iron element is also of significant importance for green chemistry and a sustainable future. To construct Fe-based heterogeneous catalysts with excellent hydrogenation performance, precise modulation of the atomic coordination structure is a key strategy for enhancing catalytic activity. In this study, we present an in-situ coating method for applying a zeolitic imidazolate framework (ZIF) onto the surface of fungal hyphae. The asymmetric coordination structure of Fe1-N3P1 was precisely tailored by utilizing the phosphorus source from the fungus and the nitrogen source in the ZIFs. Detailed characterizations and density functional theory calculations revealed that the incorporation of ZIFs not only increased the specific surface area of catalysts, but also facilitated the dispersion of Fe2P nanoparticles into the Fe1-N3P1 center, making the lowest reaction energy barrier and resulting in the best performance for nitrobenzene hydrogenation when compared to the Fe2P nanoparticles and clusters. This research introduces a novel design concept for constructing asymmetric monoatomic configuration based on the inherent characteristics of natural microorganisms and the exogenous porous coordination polymers.

Toward Strong UV-Vis-NIR Second-Harmonic Generation by Dimensionality Engineering of Zinc Thiocyanates.

The precise modulation of the spatial orientations and connection modes of primitives is vital for certain critically important optical functions for nonlinear optical (NLO) materials (specifically, second-harmonic generation (SHG) and optical bandgap); however, we are yet to achieve a sufficient level of control for the designed construction of efficient broadband NLO materials. Exploiting the changes in microscopic polarization that may result from dimensional increase, we propose herein a zero-dimensional (0D)-to-three-dimensional (3D) dimensionality-increase strategy to realize strong broadband SHG responses for the first time. The novel 3D pseudo diamond-like Zn(SCN)2 has been synthesized by removing SHG-inactive [NH4]+ counter cations and H2O molecules that are located between the adjacent discrete [Zn(SCN)4] building blocks within the 0D (NH4)2Zn(SCN)4·3H2O. The 0D-to-3D dimensionality engineering, proceeding from (NH4)2Zn(SCN)4·3H2O to Zn(SCN)2, results in significantly enhanced SHG responses and efficient broadband activity (8 × KH2PO4 @ 1064 nm, 4.18 eV bandgap for the former c.f. 2 × β-BaB2O4 @ 380 nm, 30 × KH2PO4 @ 1064 nm, 2 × KTiOPO4 @ 2100 nm, 4.78 eV bandgap for the latter) from the UV to the NIR regions (SHG@300-1050 nm). Theoretical calculations and crystal structure analyses reveal that the coordination-bond-connected [Zn(SCN)4] building blocks within the diamond-like structure of Zn(SCN)2 are responsible for its giant broadband SHG responses.

Amorphous Nanobelts for Efficient Electrocatalytic Ammonia Production.

One-dimensional (1D) amorphous nanomaterials combine the advantages of high active site concentration of amorphous structure, high specific surface area and efficient charge transfer and mass transport of 1D materials, so they present promising opportunities for catalysis. However, a significant challenge involves achieving a balance between the high orientation of 1D morphology and the isotropy of amorphous structure, which severely obstructs the controllable preparation of 1D amorphous materials. Guided by the hard-soft acids-bases theory, here we develop a general strategy for preparing 1D amorphous nanomaterials through the precise modulation of bond strength between metal ions and organic ligands for a moderated fastness. The soft base dodecanethiol (DT) is multifunctionally served as both structure-regulating agent and morphology-directing agent. Compared with the borderline acids (e.g. Fe2+, Co2+, Ni2+) to construct amorphous structure, soft acid of Cu+ which produced crystalline nanobelts can still be amorphized by reducing the hardness of Cu ions through redox reaction to weak Cu-SR bond. Due to the combined advantages of amorphous structure and one-dimensional morphology, amorphous CuDT nanobelts exhibited excellent electrocatalytic activity in electrochemical nitrate reduction, outperformed the most of the reported Cu-based catalysts. This work will effectively bridge the gap between traditional 1D crystalline nanomaterials and amorphization preparation.

Precise Modulation of Protein Degradation by Smart PROTACs.

Proteolysis-targeting chimera (PROTAC)hasemergedas an attractive therapeutic modalityin drug discovery.PROTACs are bifunctional moleculesthat effectivelybridge proteins of interest(POIs)withE3 ubiquitin ligases, such that,the target proteinsaretagged with ubiquitin and subsequently degraded viathe proteasome. Despite significant progressin the field of targeted protein degradation (TPD), the application of conventional PROTAC degradersstill faces significantchallenges,includingsystemic toxicity induced by non-tissue-specific targeting.To address this issue, a variety ofsmart PROTACs that can be activated byspecific stimuli, have been developed for achievingconditional andspatiotemporal modulationof protein levels.Here, on the basis of our contributions, we overview recent advances of smart PROTACs, including tumor microenvironment-, photo-, and X-ray radiation-responsivePROTACs, that enable controllableTPD. The design strategy, case studies, potential applications and challengeswill be focused on.

Random incidence absorption characteristics and parameterized design of micro-perforated panel absorbers with parallel-arranged backing cavities at different depths

Micro-perforated panel absorbers (MPAs) are recognized as efficient and environmentally friendly materials for sound absorption, prompting significant research efforts to expand their frequency ranges. This study investigates the acoustic performance of MPAs with parallel-arranged backing cavities at different depths (PCD) under random incidence conditions. Initially, an analytical model is proposed to predict the acoustic performance of PCD-MPA. The model exhibits significant consistency with finite element simulations and experimental measurements, validating its reliability in calculating absorption coefficients within the primary frequency band of concern (500~4000 Hz) in architectural acoustics applications. Subsequently, a thorough discussion of the key parameters, including the depth sequence and perforation parameters, which influence the random incidence absorption characteristics of PCD-MPA is presented based on the proposed model. These discussions lead to the development of an enhanced parameterized design method aimed at improving the absorption performance of PCD-MPA, enabling precise modulation of parameter combinations to meet specific application requirements and design nearly perfect absorbers.

Ultrahighly Sensitive Flexible Pressure Sensors with Dual-Mode Response Based on Monolayer Films of Calcium Niobate Nanosheets.

Flexible pressure sensors present enormous potential for applications in health monitoring, human-machine interfacing, and electronic skins (e-skin). However, at the cost of flexibility, the design of flexible pressure sensors has been facing the trade off between high sensitivity and wide sensing range. Herein, we propose a sandwiched structure composed of monolayer films of calcium niobate nanosheets to endow the device with both ultrahigh sensitivity and a wide sensing range. Tunable contact between the two electrodes of the pressure sensor through the gaps in the insulative monolayer film and precise thickness modulation of the monolayer films at the nanoscale result in an ultrahigh sensitivity and wide sensing range of the sensors. By virtue of these two traits, the pressure sensor distinguishes itself with unprecedented performances of ultrahigh sensitivity (6.43 × 104 kPa-1), a wide sensing range (1.94-60.00 kPa), a fast response time (<165 ms), and reliable repeatability. In addition, the sensor has a sensing mechanism transition from capacitive mode to piezoresistive mode from low pressure to high pressure. The sensors demonstrates the ability for motion detection of the human body. This work sheds light on the development of highly sensitive flexible pressure sensors.

Hierarchically structured nanofibrous scaffolds spatiotemporally mediate the osteoimmune micro-environment and promote osteogenesis for periodontitis-related alveolar bone regeneration

Periodontitis suffer from inflammation-induced destruction of periodontal tissues, resulting in the serious loss of alveolar bone. Controlling inflammation and promoting bone regeneration are two crucial aspects for periodontitis-related alveolar bone defect treatment. Herein, we developed a hierarchically structured nanofibrous scaffold with a nano-embossed sheath and a bone morphogenetic protein 2-loaded core to match the periodontitis-specific features that spatiotemporally modulated the osteoimmune environment and promoted periodontal bone regeneration. We investigated the potential of this unique scaffold to treat periodontitis-related alveolar bone defects in vivo and in vitro. The results demonstrated that the hierarchically structured scaffold effectively reduced the inflammatory levels in macrophages and enhanced the osteogenic potential of bone mesenchymal stem cells in an inflammatory microenvironment. Moreover, in vivo experiments revealed that the hierarchically structured scaffold significantly ameliorated inflammation in the periodontium and inhibited alveolar bone resorption. Notably, the hierarchically structured scaffold also exhibited a prolonged effect on promoting alveolar bone regeneration. These findings highlight the significant therapeutic potential of hierarchically structured nanofibrous scaffolds for the treatment of periodontitis, and their promising role in the field of periodontal tissue regeneration. Statement of Significance: We present a novel hierarchically structured nanofibrous scaffold of coupling topological and biomolecular signals for precise spatiotemporal modulation of the osteoimmune micro-environment. Specifically, the scaffold was engineered via coaxial electrospinning of the poly(ε-caprolactone) sheath and a BMP-2/polyvinyl alcohol core, followed by surface-directed epitaxial crystallization to generate cyclic nano-lamellar embossment on the sheath. With this unique hierarchical structure, the cyclic nano-lamellar sheath provided a direct nano-topographical cue to alleviate the osteoimmune environment, and the stepwise release of BMP-2 from the core provided a biological cue for bone regeneration. This research underscores the potential of hierarchically structured nanofibrous scaffolds as a promising therapeutic approach for periodontal tissue regeneration and highlights their role in advancing periodontal tissue engineering.

Tuning the selectivity of catalytic hydrogenation of fumaric acid with supercritical CO2

The catalytic hydrogenation of fumaric acid, a prominent bioplatform molecule, was evaluated over PdRe/SiO2 within a variety of reaction media compositions comprising methanol, water, supercritical CO2, and their assorted combinations with H2, across a range of temperature and pressure regimes. Meticulous manipulation of the reaction media composition facilitated the precise modulation of catalytic activity to favor specific hydrogenation products. For instance, within a water-saturated supercritical CO2 medium, γ-butyrolactone exhibited a noteworthy 89 % selectivity at 188°C under 250 bar total pressure, whereas in the methanol-containing supercritical CO2 system, hydrogenation displayed a remarkable 91 % selectivity towards tetrahydrofuran at 175°C and 250 bar. This investigation underscores the multifaceted influence of CO2, extending beyond its pressure-derived effects - it functions as a solvent, selectively favoring catalytic pathways and enhancing product selectivity.