Template Effect Research Articles

In Situ Construction of Hierarchical Nickel-Cobalt Hydroxides Derived from Metal-Organic Frameworks for High-Performance Nickel-Zinc Batteries.

Rechargeable nickel-zinc (Ni-Zn) batteries hold great promise for large-scale applications due to their relatively high voltage, cost-efficient zinc anode, and good safety. However, the commonly used cathode materials are susceptible to overcharging and experience irreversible capacity degradation, primarily as a result of low electrical conductivity and substantial limitations in volume-constrained proton diffusion. Here, we present a robust methodology for synthesizing hierarchical nickel-cobalt (Ni-Co) hydroxides characterized by hollow interiors and interconnected nanosheet shells with the help of in situ formed metal-organic frameworks (MOFs). The templating effect of the MOF induced the hierarchical structure, while the chemical etching of MOFs by Ni2+ ions resulted in a hollow structure, thereby enhancing the surface area. Theoretical calculations suggested that incorporation of cobalt reduces the band gap, thereby improving electronic conductivity, and lowered the deprotonation energy, which mitigated overcharge issues. These advantages conferred improved specific capacity, rate capability, and cyclic stability to the Ni-Co hydroxide. The Ni-Zn cell delivered specific energy values of 338 Wh kg-1 at 1.62 kW kg-1 and 142 Wh kg-1 at 29.89 kW kg-1. Our investigations undercoreed the critical role of MOFs as intermediates in the preparation of multi-component hydroxide and the construction of hiearchical structures to achieve superior performance.

Multifunctional Nacre-Like Nanocomposite Papers for Electromagnetic Interference Shielding via Heterocyclic Aramid/MXene Template-Assisted In-Situ Polypyrrole Assembly

HighlightsThe large-scale, high-strength, super-tough, and multifunctional nacre-like heterocyclic aramid (HA)/MXene@polypyrrole (PPy) (HMP) nanocomposite papers were fabricated using the in-situ assembly of PPy onto the HA/MXene hydrogel template.The "brick-and-mortar" layered structure and abundant hydrogen-bonding interactions among MXene, PPy, and HA respond cooperatively to external stress and effectively increase the mechanical properties of HMP nanocomposite papers.The templating effect from HA/MXene was utilized to guide the assembly of conducting polymers, leading to high electrical conductivity and outstanding electromagnetic interference shielding performance.

Modulation of biomineralization morphology by phosphorylated collagen peptides: insights into osteogenesis imperfecta pathophysiology.

Osteogenesis imperfecta (OI) is a hereditary skeletal disorder characterized by bone fragility and deformities, primarily attributed to defects in type I collagen, the most abundant structural protein in humans. Multiple phosphorylation sites have been detected within collagen, suggesting that phosphorylation may influence mineralization processes, thereby impacting the development of OI. In this study, we investigated the modulation of biomineralization morphology by phosphorylated collagen peptides mimicking Gly-Ser mutations in osteogenesis imperfecta. A series of collagen peptide sequences, including GPO13S, GPO13pS, GPO12S, GPO12pS, GPO11S, and GPO11pS, were synthesized to explore the role of phosphorylation in peptide stability and its templating effect on biomineralization. The CD results indicated that the phosphorylation of Gly-pSer mutants reduces the stability of collagen peptides. SEM images revealed that phosphorylated peptides acted as templates, guiding the morphology of calcium carbonate into either olive-like or spherical structures, depending on their conformational state of the peptides. Non-phosphorylated peptides maintained a calcite crystal structure. The XRD patterns predominantly exhibited peaks associated with calcite and vaterite for GPO13pS-CaCO3, GPO12pS-CaCO3, and GPO11pS-CaCO3, and peaks associated with calcite for GPO13S-CaCO3, GPO12S-CaCO3, and GPO11S-CaCO3, indicating a transformation of mesocrystals influenced by peptide phosphorylation. Our findings elucidate the crucial role of phosphorylated collagen peptides in mediating biomineralization morphology and polymorph selection, offering insights into the complex pathophysiology of OI.

Influence of Material, Sterilization, and Disinfection on the Accuracy of Three-Dimensional Printed Surgical Templates: An InVitro Study.

To evaluate the influence of the three-dimensional (3D) printing technology, material, sterilization, and disinfection on the accuracy of guided surgical templates. Fifty printed resin surgical templates were designed and fabricated using a digital light processing 3D printer with a photopolymerizing resin, and 50 printed metal surgical templates were designed and fabricated using a selective laser melting 3D printer with a titanium alloy. Templates from both groups were randomly divided into five subgroups involving different sterilization and disinfection procedures. The group without any sterilization or disinfection procedure served as the control group, whereas the other groups were used as the study groups (hydrogen peroxide gas plasma sterilization, 5% povidone-iodine disinfection, 75% ethyl alcohol disinfection, and steam autoclave sterilization). Implant simulations were performed on the 3D-printed resin models, and postoperative impressions were acquired with scan bodies attached to the implants. All surgical templates were digitally scanned. The root mean square was used to determine and quantify fabrication accuracy and reproducibility, and the definitive and planned implant positions were compared. The printed resin templates exhibited lower fabrication accuracy and reproducibility, as well as higher 3D deviations, after steam autoclave sterilization (p < 0.001); however, the printed metal templates were not affected by the different sterilization or disinfection procedures (p > 0.05). Printed metal surgical templates are viable alternatives for guided implant surgery. Preoperative steam or gas plasma sterilization is recommended, especially for metal templates, as resin templates show deformation and decreased accuracy after steam sterilization. chictr.org.cn number: ChiCTR2400081334.

Facile Synthesis of Rhodium-Based Nanocrystals in a Metastable Phase and Evaluation of Their Thermal and Catalytic Properties.

Controlling the polymorphism of metal nanocrystals is a promising strategy for enhancing properties and discovering new phenomena. However, previous studies on Rh nanocrystals have focused on their thermodynamically stable face-centered-cubic (fcc) phase. Herein, a facile synthesis of Rh-based nanocrystals featuring the metastable hexagonal close-packed (hcp) phase is reported by using Ru seeds in their native hcp phase to template the deposition of Rh atoms. The success of such phase-controlled synthesis relies on the templating effect promoted by the small lattice mismatch between Ru and Rh and the slow dropwise titration of the precursor at an elevated temperature, ensuring the layer-by-layer growth mode and thus the formation of a conformal hcp-Rh shell. Faster injection rate of Rh(III) precursor leads to the formation of a rough Rh shell in the conventional fcc phase due to accelerated reaction kinetics. Considering both thermodynamic and kinetic aspects of this system, the hcp-Rh phase is favored when the low surface energy from smooth overlayers balances the high bulk energy of the metastable phase, achieved through tight control of reaction rates and deposition patterns. These Ruhcp@Rhhcp core-shell nanocrystals demonstrate thermal stability up to 400°C, while exhibiting higher catalytic activity toward ethanol oxidation reaction compared to Ruhcp@Rhfcc counterparts.

Interwoven Trimeric Cage-Catenanes with Topological Chirality.

Catenanes have gained increasing attention for their unique features such as topological chirality. To date, the majority of works have focused on catenanes comprising monocyclic rings. Due to the lack of efficient synthetic strategy, catenanes of multiannulated monomers remain scarce. Here, we report the one-pot synthesis of an interwoven trimeric cage-catenane in high yield by dynamic imine condensation between diamine linkers of suitable length and trialdehyde panels in stoichiometry. The formation of cage-catenane is driven by the efficient 6-fold π-π stacking of panels. The monomeric cage and trimeric cage-catenane are interconvertible with reversible imine chemistry, with the latter thermodynamically being more favored. Using a topology-based statistical model, we first reveal that the formation probability of the interwoven catenane surpasses that of its chain-like isomer by 20%. When this pure mathematical model is refined by taking into account the strong template effect provided by the π-π stacking of aromatic panels, it shows that the interwoven structure emerges as the dominant species, almost ruling out the formation of the latter. Although composed of achiral cage monomers, the topological chirality of the interwoven trimeric catenane is unraveled by chiral-high-performance liquid chromatography (HPLC) and circular dichroism (CD) spectroscopy, and single-crystal X-ray diffraction (XRD) analysis of the interwoven cage-catenane also reveals a pair of two topological enantiomers. Our probability analysis-aided rationale would provide a design rationale for guiding the efficient synthesis of topologically sophisticated structures.

Implementing Lattice and Energy Level Matching to Optimize Buried Interfaces for High-Performance Perovskite Solar Cells.

In n-i-p type perovskite solar cells (PSCs), mismatches in energy level and lattice at the buried interface is highly detrimental to device performance. Here, thin PbS interconnect layer in situ coating on the SnO2 surface is grown. The function of PbS at the interface is different from the commonly used function of crystalline seeds in perovskite bulk. The theoretical calculation show that it helps construct an interconnect structure of SnO2/PbS/Perovskite with matched energy level and lattice. This not only increases conductivity of SnO2, but also upshifts Fermi energy levels (EF) of both SnO2 and buried perovskite due to charge transfer and perovskite's internal defect changes. Such a suitable energy level arrangement ensures a better energy level match at the interface, favoring efficient charge transfer and less open circuit voltage (Voc) loss. Additionally, in situ PL reveals that the template effect of PbS enable perovskite grain to grow bottom-up because of their highly matched lattice parameters. This growth mode optimizes buried interface contact and crystallinity of perovskite. Ultimately, after PbS modification, a remarkable power conversion efficiency (PCE) exceeding 24% and better device stability are obtained. This work demonstrates an effective interconnect layers strategy to realize ideal interface contact toward high-performance PSCs.

Immunomodulatory microneedle patch for enhanced Ferroptosis and immunogenic cell death in postoperative tumor therapy

Microneedle technologies have emerged as a promising transdermal drug delivery platform for postoperative tumor therapy. Despite their potential, enhancing intracellular drug delivery to tumor cells and boosting the therapeutic efficiency of microneedles pose significant challenges. Herein, we develop a nanomedicine-loaded microneedle to enhance the induction of ferroptosis and immunogenic cell death for postoperative tumor therapy. This advancement is achieved by pre-formulating small molecule drugs with transition metal and protein templates into nanomedicine. Upon insertion into the tumors, the microneedle rapidly dissolves, facilitating the release and subsequent cellular uptake of the nanomedicine by tumor cells. Notably, the nanomedicine can release Mn ions and ferroptosis-inducer sulfasalazine (SAS) under acidic conditions. Furthermore, the released Mn ions can produce reactive oxygen species, which decrease the levels of glutathione (GSH) and glutathione peroxidase 4 (GPX4) with increased lipid peroxidation and enhanced induction of ferroptosis. Besides, the treatment stimulates immunogenic cell death through the cell surface exposure of calreticulin (CRT) and release of high-mobility group box 1 (HMGB1), which further stimulates dendric cell maturation, T cell infiltration, and macrophage polarization towards the M1 phenotype. Consequently, this strategy significantly inhibits postoperative tumor regrowth and extends overall survival. Our study indicates the potential of the combination of nanomedicine and microneedle to improve postoperative therapeutic efficiency.

Comprehensive study of epitaxial (Nd,Eu,Gd)Ba2Cu3O7−δ films grown on textured templates

We report the successful epitaxial growth and comprehensive study of structural and superconducting properties of (Nd,Eu,Gd)Ba2Cu3O7−δ films with a thickness of up to 1.2 μm prepared by on-axis pulsed laser deposition on SrTiO3 (STO) single crystals as well as on ion-beam-assisted deposition (IBAD) and rolling-assisted biaxially textured substrate (RABiTS)-based metal templates. X-ray diffraction demonstrates the epitaxial quality of the grown films on both single crystalline substrates and metal-based templates. In addition, no significant changes in surface morphology were found with increasing thickness for films on all types of substrates. On all substrates, a T c value of about 89 K was observed, however, significant inhomogeneities indicating small superconducting volume were found for all films on STO. In general, the best transport characteristics over a wide range of magnetic fields and temperatures were observed for thicker films on IBAD-MgO and RABiTS templates, respectively. The J c values at 77 K for the films on IBAD-MgO templates are comparable to YBCO films, but inferior in the low temperature region and high magnetic fields, whereas the films on RABiTS and especially on STO showed much lower J c over the entire temperature and magnetic field range. A maximum pinning force of about 7 GN·m−3 at 65 K was found for the 900 nm thick films on IBAD-MgO template. In addition, the pinning mechanism seems to depend on both temperature and type of substrate. In general, no correlation between local microstructure and transport characteristics was revealed for NEG films on both metal templates.

Introducing a Controlled Interfacial Layer to Enhance the Template Effect of ZrO₂ in the ZrO₂/HfO₂/ZrO₂ Structure

Introducing a Controlled Interfacial Layer to Enhance the Template Effect of ZrO₂ in the ZrO₂/HfO₂/ZrO₂ Structure

Ultrasensitive lab-on-paper electrochemical device via heterostructure copper/cuprous sulfide@N-doped C@Au hollow nanoboxes as signal amplifier for alpha-fetoprotein detection

Rapid and accurate detection of tumor markers at extremely low levels is crucial for the early diagnosis of cancers. In this work, we developed a portable label-free sliding electrochemical paper-based analytical device (ePAD) using copper/cuprous sulfide@N-doped C@Au nanoparticles (Cu/Cu2S@NC@Au) hollow nanoboxes as the signal amplifier for the ultrasensitive detection of alpha-fetoprotein (AFP). Cu/Cu2S@NC nanoboxes were synthesized by sacrificial template and interface reaction methods, on which Au nanoparticles were electrodeposited to construct unique heterostructure for effectively capturing anti-AFP and serving as signal amplifier. The designed ePAD incorporates sliding microfluidic paper chips to form a flexible three-electrode system, enabling highly sensitive detection of AFP with a wide linear range of 0.005–50 ng mL−1 and a low detection limit of 0.62 pg mL−1. The practicality of the prepared ePAD was validated through AFP detection in clinical human serum, which was consistent with chemiluminescence immunoassay. In addition, the developed immunosensor demonstrates excellent specificity, repeatability and stability. This novel platform exhibits significant potential for rapid on-site analysis and point-of-care diagnosis.

N/O-functionalized ultrathin carbon nanosheets for zinc-ion hybrid capacitors

2D carbon materials have outstanding electrical properties and rich anchoring sites, and can be used as zinc ion storage electrodes. However, it remains a formidable challenge to fabricate these materials with tunable composition by a simple synthesis strategy. Herein, folic acid-derived N/O-functionalized ultrathin carbon nanosheets are synthesized via the activation effect of nano-ZnO template. The as-fabricated FACN-800 exhibits extremely thin thickness (∼1.6 nm), hierarchically porous structure and rich N/O heteroatoms (14.9 at.% of N and 8.4 at.% of O), which is conducive to accelerate ion transport and provide additional active sites for Zn-ion storage. Thus, the optimized FACN-800 based aqueous zinc-ion hybrid capacitor delivers excellent zinc-ion storage capabilities with high specific capacity (163.6 mAh g−1 at 0.1 A g−1), admirable energy density (130.8 Wh kg−1) and ultralong cycle stability (90.3 % capacity retention over 40,000 cycles) and FACN-800 has a specific surface area of 554.3 m2 g−1. Moreover, a series of ex-situ measurements and DFT theoretical calculations further elucidate the electrochemical mechanism between zinc ion storage and N/O dopants.

Cyclic Fatigue Resistance of Four Heat-Treated Nickel-Titanium Files in Severely Curved Simulated Canals: An In Vitro Study.

Background: Rotary Ni-Ti files are susceptible to sudden intra-canal separation due to cyclic fatigue stress, particularly in curved canals. To increase resistance to cyclic fatigue, new heat-treated files have been introduced. This study aimed to compare the performance of four heat-treated Ni-Ti files in two simulated curved root canals by evaluating the effect of the alloy, rotation speed, and diameter of the files on their resistance to cyclic fatigue. Methods: The Ni-Ti files included in the study were the ProTaper Gold® (Dentsply Sirona) F2, ProTaper Ultimate® (Dentsply Sirona) F2, FQ® (Komet) 25.06, and Blueshaper® (Zarc4Endo) Z4 25.06. Two groups of 30 files were selected for each system and were tested in two simulated canals milled in a specific metal template. One group was tested in a 60° curved canal and the other in a 90° curved canal. Results: In the 60° simulated canal, there were no instrument fractures within the 15 min time limit. In the 90° simulated canal, the Blueshaper Z4 demonstrated a lower resistance to cyclic fatigue, while FQ 25.06 showed statistically higher fatigue resistance based on both the Kruskal-Wallis and Games-Howell tests (p < 0.05). Conclusions: No differences were found between files when tested in a 60° curved canal for up to 15 min. However, in a 90° canal, the FQ® files showed significantly higher resistance to cyclic fatigue, especially compared to the Blueshaper® Z4. The ProTaper Ultimate and ProTaper Gold produced intermediate results, with the ProTaper Ultimate F2 slightly outperforming the ProTaper Gold F2.

Cholesterol Conformational Structures in Phospholipid Membranes.

Cholesterol is a major component of biomembranes that impacts membrane order, permeability, and lateral organization, but the precise molecular mechanisms of cholesterol's actions are still under investigation. Density functional theory (DFT) calculations have opened the fingerprint vibration bands of large molecules to detailed spectral analysis. For cholesterol, Raman spectral interpretation for conformational structure and hydrogen bonding is now possible. Here, DFT calculations of cholesterol conformers identify 10 structure types that also have unique low-frequency Raman spectra. By fitting experimental spectra to these types, the distribution of cholesterol structures present in phospholipid (PL) membrane vesicles was measured. The distributions reveal that the cholesterol iso-octyl chain tends to align with saturated PL chains and shifts to a thermal distribution for unsaturated PL chains. The results agree with the templating effect of cholesterol on PL membranes and show that the top of the iso-octyl chain is rigid like the rings. It is also shown that the inclusion of water molecules hydrogen bonded to the cholesterol hydroxy group in the DFT calculations may improve the spectral fitting for future studies.

Graphene-Templated Achiral Hybrid Perovskite for Circularly Polarized Light Sensing.

This study points out the importance of the templating effect in hybrid organic-inorganic perovskite semiconductors grown on graphene. By combining two achiral materials, we report the formation of a chiral composite heterostructure with electronic band splitting. The effect is observed through circularly polarized light emission and detection in a graphene/α-CH(NH2)2PbI3 perovskite composite, at ambient temperature and without a magnetic field. We exploit the spin-charge conversion by introducing an unbalanced spin population through polarized light that gives rise to a spin photoconductive effect rationalized by Rashba-type coupling. The prepared composite heterostructure exhibits a circularly polarized photoluminescence anisotropy gCPL of ∼0.35 at ∼2.54 × 103 W cm-2 confocal power density of 532 nm excitation. A carefully engineered interface between the graphene and the perovskite thin film enhances the Rashba field and generates the built-in electric field responsible for photocurrent, yielding a photoresponsivity of ∼105 A W-1 under ∼0.08 μW cm-2 fluence of visible light photons. The maximum photocurrent anisotropy factor gph is ∼0.51 under ∼0.16 μW cm-2 irradiance. The work sheds light on the photophysical properties of graphene/perovskite composite heterostructures, finding them to be a promising candidate for developing miniaturized spin-photonic devices.

Structure and optical properties of ZnxCd1-xS and Cu:ZnxCd1-xS templated on DNA molecules

One-dimensional ZnxCd1−xS and Cu: Zn x Cd1−x S nanostructures were prepared using DNA as a template to promote growth along the molecular axis. The formation of homogeneously alloyed nanocrystals with cubic zinc blende-type structures was verified using x-ray diffraction and Raman spectroscopy. X-ray photoemission spectra revealed the presence of Cu(I) in the doped Cu: Zn x Cd1−x S nanocrystals. The effectiveness of the DNA template to direct the semiconductor growth in one dimension was demonstrated by AFM and TEM. The nanostructures displayed a granular morphology comprising nanoparticles with an average diameter of 14 nm composed of assemblies of smaller crystallites of 2.0 nm in size. Rope-like assemblies with an average diameter of 48 nm and extending in length to several hundred micrometres were obtained by evaporation-induced self-assembly. UV-Vis absorption and emission spectra indicated that the optical bandgaps (2.89–4.00eV) and photoluminescence peaks (608–819 nm) of the DNA-templated nanocrystals could be precisely controlled by modifying the molar ratios of their Zn/Cd precursors. Doping with Cu(I) gave an increase in photoluminescence intensity and a composition-independent red-shift of 0.23 eV. The preparation of DNA-templated Zn x Cd1−x S and Cu: Zn x Cd1−x S provides a simple, low-temperature route to aqueous dispersions of inorganic materials with controlled optical gap.

In-situ assembly of polypyrrole onto heterocyclic aramid for high-strength, ultratough, durable, and multifunctional films

High-strength, ultratough, multifunctional polymer-based electromagnetic interference (EMI) shielding nanocomposite films have colossal application potential in artificial intelligence, 5G communications, and flexible electronics. In this work, a large-scale, high-strength, and ultratough heterocyclic aramid@polypyrrole (HA@PPy) composite film is developed via the in-situ loading of PPy onto the HA template. The synthesized films achieve remarkable mechanical properties and high electronic conductivity by using the template effect of HA to guide the assembly of conductive polymers. When the content of PPy is 45 wt%, the HA@PPy (HP45) film possesses excellent tensile strength (240.3 MPa), significant elongation at break (25.9 %), outstanding toughness (53.1 MJ m−3), and exceptional folding durability owing to strong hydrogen bond interaction between PPy and HA. Furthermore, thanks to the highly connected conductive paths formed by PPy, the HP45 film exhibits satisfactory EMI shielding effectiveness (EMI SE) of 45.5 dB and specific EMI SE of 14691.6 dB cm2 g−1 at an ultra-thin thickness (26.3 μm). The HP45 film also demonstrates excellent electromagnetic protection, electro-/photothermal deicing, thermal therapy, and flame retardancy applications. Therefore, high-performance and multifunctional HA@PPy films have substantial potential for widespread application in EMI shielding and thermal management.

The crystal engineering of 3d-metal with two tetrazole-phenyl-carboxylate linkers and multiple post-synthetic metal exchange

Ligand with mixed-groups contributes to the construction of special structure motif with novel properties, yet it is challenging to understand and regulate the competitive coordination of different functional groups toward metal ions. Herein, the crystal engineering for MOF construction from two linear di-topic linkers of 4-(1H-tetrazol-5-yl)benzoic acid (H2tzba) and the longer 4′-(1H-tetrazol-5-yl)-[1,1′-biphenyl]-4-carboxylic acid (H2tzbba) featuring dual groups of phenyl-carboxylate and tetrazole, with three typical 3d metal ions (Mn2+, Fe2+ and Zn2+) were investigated. A series of five new MOFs, that are [Mn3(tzba)3(dmf)4]·11dmf (1, dmf = N,N-Dimethylformamide), [Mn(tzba)(H2O)] (2), [Zn2(tzba)2(dmf)]·0.5dmf (3), [Fe2(tzba)2(dmf)]·0.5dmf (4) and [Zn2(tzbbz)(gac)(dmf)2]·1.5dmf (5), were synthesized under solvothermal reactions. The modified solvent template and temperature effects lead to 3D framework of 1 (dmf solution under 433 K) with [Mn3(tz)3(COO)3] nodes and 1D hexagonal channels, while the 2 (water solution under 373 K) posssesses compact pillared-layer motif from [Mn2(tz)2] nodes. Under changed metal salt reactents but same solvent of dmf, the generated 3 and 4 have isoreticular and porous pillared-layer structure constituted of [M2(COO)2] nodes. The use of tzbba coupled with a crucial auxiliary ligand of glycollic acid, leads to 5 as porous pillared-layer MOFs with 1D rounded channels. The porous flexible skeleton of 1 constructed from [Mn3] node with four coordinated dmf facilitates post-synthetic metal exchange of the Mn2+ by radius similar metal ions following priority of Cu2+ < Zn2+ < Ni2+< Co2+, with maximum exchange percentage ranging from 17 % to 69 %. Time dependent ICP-AES analysis revealed the quite wide feasible solvents for post-synthetic metal exchange, as well as the fine control on substituting degree based on soaking temperature and time. Particularly, the compatible introduce of four different metal ions support the potential of preparing bi-, tri-, tetra- and penta- metal MOF crystals, that can not be obtained by traditional solvothermal reactions.

Templated Nucleation of Clotrimazole and Ketoprofen on Polymer Substrates.

The use of different template surfaces in crystallization experiments can directly influence the nucleation kinetics, crystal growth, and morphology of active pharmaceutical ingredients (APIs). Consequently, templated nucleation is an attractive approach to enhance crystal nucleation kinetics and preferentially nucleate desired crystal polymorphs for solid-form drug molecules, particularly large and flexible molecules that are difficult to crystallize. Herein, we investigate the effect of polymer templates on the crystal nucleation of clotrimazole and ketoprofen with both experiments and computational methods. Crystallization was carried out in toluene solvent for both APIs with a template library consisting of 12 different polymers. In complement to the experimental studies, we developed a computational workflow based on molecular dynamics (MD) and derived descriptors from the simulations to score and rank API-polymer interactions. The descriptors were used to measure the energy of interaction (EOI), hydrogen bonding, and rugosity (surface roughness) similarity between the APIs and polymer templates. We used a variety of machine learning models (14 in total) along with these descriptors to predict the crystallization outcome of the polymer templates. We found that simply rank-ordering the polymers by their API-polymer interaction energy descriptors yielded 92% accuracy in predicting the experimental outcome for clotrimazole and ketoprofen. The most accurate machine learning model for both APIs was found to be a random forest model. Using these models, we were able to predict the crystallization outcomes for all polymers. Additionally, we have performed a feature importance analysis using the trained models and found that the most predictive features are the energy descriptors. These results demonstrate that API-polymer interaction energies are correlated with heterogeneous crystallization outcomes.

On-Surface Synthesis of Macrocycles, Non-Planar Carbon Ribbons and Heteroatom-Doped Nanographenes

On-surface synthesis via covalent coupling of adsorbed molecules on metal surfaces has attracted significant attention recently due to its potential to fabricate low-dimensional carbon materials with atomic precision. The bottom-up, atomically precise synthesis of carbon nanostructures enables the tailoring of their electronic properties at a molecular level. To understand and control the surface-chemistry-driven synthesis, many efforts have been made to design innovative precursors, explore novel reaction schemes, and utilize templating effects from the substrate.My presentation focuses on high-resolution scanning probe microscopy experiments combined with density functional theory to demonstrate recent highlights on the assembly of surface-supported low-dimensional carbon structures on metal surfaces. First, the assembly and electronic structure of planar π-extended cycloparaphenylene macrocycles, representing the first nanographene with an all-armchair edge topology, will be presented [1]. The second part will discuss the bottom-up synthesis of covalently-linked non-planar carbon ribbons and their electronic properties depending on their adsorption geometry. Finally, I will conclude with the on-surface cyclomerization of oxygen heterocycles to understand the on-surface synthesis of furan and pyran derivatives from ketone-functionalized precursors on metal surfaces.[1] Xiang, et al. Nature Chem., 2022 14, 871–876.