Synthesis Of Biomolecules Research Articles

The effect of sterilization treatment on the synthesis of key biomolecules and microbial communities in fruit wine fermentation

Sterilization treatments impact microbial communities and key biomolecule synthesis, influencing the aroma and quality of fruit wine fermentation. However, the roles of microorganisms in various fermentation techniques and the impact of sterilization treatments on aroma formation and key biomolecule synthesis are not well understood. This study aims to elucidate the effects of sterilization treatments on the synthesis of key biomolecules and microbial community dynamics in fruit wine fermentation, focusing on their relation to aroma compounds. Using purple fruit as the primary subject, we analyzed the starting and final microbe populations in controlled test fermentation (CTF) and natural test fermentation (NTF) under different sterilizing treatments employing advanced sequencing strategies. We utilized multivariate analysis and regression analyses, via the SPSS tool to examine relationships between microbial fungal and bacterial genus-level communities, microbiological diversity, permanent substances aromatic substances, and physiological indexes. In NTF, we identified a total of 150 fungal genera, and 140 bacterial genera, with dominant genera including Candida, Burkholderia, Streptococcus, and Oenococcus. In CTF, 400 fungal genera, and 120 bacterial genera were identified, with the dominant genera being Geotrichum, Pichia, Aspergilus, and Saccharomyces, alongside Streptococcus, Paucibacter, Pantoea, Akkermansia, Lactobacillus, and Bifidobacterium. Positive correlations were observed between specific microbial genera and flavor compounds in both fermentation methods. This study provides insights into how sterilization treatments affect microbial dynamics and key biomolecule synthesis, offering valuable resources for enhancing the aromatic profile of fruit wine.

Enhanced CRC Growth in Iron-Rich Environment, Facts and Speculations.

The contribution of nutritional factors to disease development has been demonstrated for several chronic conditions including obesity, type 2 diabetes, metabolic syndrome, and about 30 percent of cancers. Nutrients include macronutrients and micronutrients, which are required in large and trace quantities, respectively. Macronutrients, which include protein, carbohydrates, and lipids, are mainly involved in energy production and biomolecule synthesis; micronutrients include vitamins and minerals, which are mainly involved in immune functions, enzymatic reactions, blood clotting, and gene transcription. Among the numerous micronutrients potentially involved in disease development, the present review will focus on iron and its relation to tumor development. Recent advances in the understanding of iron-related proteins accumulating in the tumor microenvironment shed light on the pivotal role of iron availability in sustaining pathological tumor hallmarks, including cell cycle regulation, angiogenesis, and metastasis.

Synthesis and Stability of Biomolecules in C-H-O-N Fluids under Earth's Upper Mantle Conditions.

How life started on Earth is an unsolved mystery. There are various hypotheses for the location ranging from outer space to the seafloor, subseafloor, or potentially deeper. Here, we applied extensive ab initio molecular dynamics simulations to study chemical reactions between NH3, H2O, H2, and CO at pressures (P) and temperatures (T) approximating the conditions of Earth's upper mantle (i.e., 10-13 GPa, 1000-1400 K). Contrary to the previous assumptions that large organic molecules might readily disintegrate in aqueous solutions at extreme P-T conditions, we found that many organic compounds formed without any catalysts and persisted in C-H-O-N fluids under these extreme conditions, including glycine, ribose, urea, and uracil-like molecules. Particularly, our free-energy calculations showed that the C-N bond is thermodynamically stable at 10 GPa and 1400 K. Moreover, while the pyranose (six-membered ring) form of ribose is more stable than the furanose (five-membered ring) form at ambient conditions, we found that the formation of the five-membered-ring form of ribose is thermodynamically more favored at extreme conditions, which is consistent with the exclusive incorporation of β-d-ribofuranose in RNA. We have uncovered a previously unexplored pathway through which the crucial biomolecules could be abiotically synthesized from geofluids in the deep interior of Earth and other planets, and these formed biomolecules could potentially contribute to the early stage of the emergence of life.

Bioprocess strategies for enhanced performance in single‐use bioreactors for biomolecule synthesis: A biokinetic approach

AbstractSingle‐use bioreactors (SUB) have made a significant impact on the field of bioprocessing, becoming increasingly popular for biomolecule synthesis due to their many advantages, such as minimizing contamination risks and streamlining processes. Extensive research has been conducted on the hydrodynamic conditions within single‐use bioreactors, with a focus on parameters like mixing time, oxygen transfer rate, and stress levels to improve cell cultivation procedures. Several studies have demonstrated that SUB can effectively nurture various cell types, including those that generate monoclonal antibodies, yielding outcomes similar to conventional bioreactor systems, thus highlighting their adaptability and effectiveness in biomolecule processing. SUB equipped with wave mechanisms have shown to display comparable metabolic behaviors and fermentation consistency to conventional bioreactors, confirming their dependability in supporting fungal growth and metabolite generation. Mechanical stirring for agitation leads to high shear forces alongside enhanced monitoring and control, influencing microbial physiology and macro‐morphologies. This underscores the importance of operational factors such as rocking speed, rocking angle, and gas flow rate. Overall, the integration of single‐use bioreactors in biomolecule synthesis is expected to expand, driven by the need for increased yields and cost‐effective manufacturing solutions.

Genetic requirements for uropathogenic E. coli proliferation in the bladder cell infection cycle.

Urinary tract infections (UTIs) are one of the most frequent infections worldwide. Uropathogenic Escherichia coli (UPEC), which accounts for ~80% of UTIs, must rapidly adapt to highly variable host environments, such as the gut, bladder sub-surface, and urine. In this study, we searched for UPEC genes required for bacterial growth and survival throughout the cellular infection cycle. Genes required for de novo synthesis of biomolecules and cell envelope integrity appeared to be important, and other genes were also implicated in bacterial dispersal and recovery from infection of cultured bladder cells. With further studies of individual gene function, their potential as therapeutic targets may be realized. This study expands knowledge of the UTI cycle and establishes an approach to genome-wide functional analyses of stage-resolved microbial infections.

Synthesis of carboxamide sensors for neurotoxic Cu2+ ions in safer green solvents and reaction conditions

Green amidation is simple and efficient for the synthesis of drugs and biomolecules. Green chemistry synthesis is always directed at achieving sustainability. Neurotoxins are critical targets for metabolic medicines to capture and eliminate from the body. Copper is a fatal brain neurotoxin. The C1-C4 probes were synthesized by reacting 3-coumarin carboxylic acid with 4-phenyl butyl amine, N-ethyl benzylamine, 4-dodecylaniline, and 3,3 - diphenyl propylamine in polar green solvent ethanol. These were tested for their metal-binding ability in environmentally safe aqueous acetonitrile with hyphenated techniques. The probes show significant binding with Cu2+ ions in the aqueous acetonitrile. The ascending order of anti-neurotoxin action is C3>C4>C2>C1 seen in the Limit of detection (Lod) values. Also, molecular mechanics (MM2) descriptors firmly point towards their use as drugs.

Copper-catalyzed three-component reaction to construct thietane ring using elemental sulfur

Thietanes are vital aliphatic four-membered rings associated with various pharmaceuticals, building blocks and synthons of intermediates used in the total synthesis of natural products and biomolecules. Also, 4-thiazolidinone is a core pharmacophore of many drug molecules. Based on their various applications in medicinal chemistry and organic synthesis, an effort has been made to achieve a thietane ring on 4-thiazolidinone nucleus via quasi-benzylic acid-type intramolecular rearrangement using elemental sulfur, benzyl bromide and Cu(I). The designed methodology is environmentally benign, cheap, and easily accessible, with a broad range of substrate scopes and carried out by the employment of earth-abundant metal catalysts like copper.

Computational Methodologies in Synthesis, Preparation and Application of Antimicrobial Polymers, Biomolecules, and Nanocomposites.

The design and optimization of antimicrobial materials (polymers, biomolecules, or nanocomposites) can be significantly advanced by computational methodologies like molecular dynamics (MD), which provide insights into the interactions and stability of the antimicrobial agents within the polymer matrix, and machine learning (ML) or design of experiment (DOE), which predicts and optimizes antimicrobial efficacy and material properties. These innovations not only enhance the efficiency of developing antimicrobial polymers but also enable the creation of materials with tailored properties to meet specific application needs, ensuring safety and longevity in their usage. Therefore, this paper will present the computational methodologies employed in the synthesis and application of antimicrobial polymers, biomolecules, and nanocomposites. By leveraging advanced computational techniques such as MD, ML, or DOE, significant advancements in the design and optimization of antimicrobial materials are achieved. A comprehensive review on recent progress, together with highlights of the most relevant methodologies' contributions to state-of-the-art materials science will be discussed, as well as future directions in the field will be foreseen. Finally, future possibilities and opportunities will be derived from the current state-of-the-art methodologies, providing perspectives on the potential evolution of polymer science and engineering of novel materials.

Carbonic anhydrase encapsulation using bamboo cellulose scaffolds for efficient CO2 capture and conversion

Utilizing carbonic anhydrase (CA) to catalyze CO2 hydration offers a sustainable and potent approach for carbon capture and utilization. To enhance CA's reusability and stability for successful industrial applications, enzyme immobilization is essential. In this study, delignified bamboo cellulose served as a renewable porous scaffold for immobilizing CA through oxidation-induced cellulose aldehydation followed by Schiff base linkage. The catalytic performance of the resulting immobilized CA was evaluated using both p-NPA hydrolysis and CO2 hydration models. Compared to free CA, immobilization onto the bamboo scaffold increased CA's optimal temperature and pH to approximately 45 °C and 9.0, respectively. Post-immobilization, CA activity demonstrated effective retention (>60 %), with larger scaffold sizes (i.e., 8 mm diameter and 5 mm height) positively impacting this aspect, even surpassing the activity of free CA. Furthermore, immobilized CA exhibited sustained reusability and high stability under thermal treatment and pH fluctuation, retaining >80 % activity even after 5 catalytic cycles. When introduced to microalgae culture, the immobilized CA improved biomass production by ∼16 %, accompanied by enhanced synthesis of essential biomolecules in microalgae. Collectively, the facile and green construction of immobilized CA onto bamboo cellulose block demonstrates great potential for the development of various CA-catalyzed CO2 conversion and utilization technologies.

Interactions of Clay Minerals with Biomolecules and Protocells Complex Structures in the Origin of Life: A Review

AbstractThe origin of life (OoL) has always been a mysterious and challenging topic that puzzles human beings. Clay minerals have unique properties and wide distribution in early Earth environments. They can not only adsorb biological small molecules to catalyze their polymerization, but play an active role in the formation and evolution of protocells. In this review, the research progress on the interactions of clay minerals with biomolecules and protocells complex structures in the field of the OoL based on chemical evolution theory is summarized. The types, structures and properties of clay minerals, biological molecules and protocell models related to the OoL are introduced in detail. The mechanism of interaction between clay minerals and biological molecules, the construction of protocells and the role of clay minerals in the formation, structure and stability of protocells are systematically described. Finally, the future research priorities and challenges in the field of OoL based on clay minerals, biomolecules and protocells are discussed. It is aspired that this review can further advance the exploration of the OoL from a new perspective, and can also bring some interesting findings and ideas to the interdisciplinary research of materials, biology, chemistry and other related disciplines.Clay minerals have a variety of interactions with small biomolecules, which can be used as structural and functional templates to promote the organic synthesis of biomolecules and the formation and evolution of protocells, playing a non‐negligible role in the field of the OoL.

Exploring the bioactive potential of Enterococcus mundtii TW278: Synthesis and utilization of biomolecules in yogurt production

Currently, there is a high demand for fresh, minimally processed foods. Therefore, the search for natural compounds that can be used to increase the quality and shelf life of food, as well as to control or eliminate the development of pathogens has been increasing. The general objective was to determine the simultaneous production, at a controlled pH 6, of bacteriocin and bioemulsifier by the Enterococcus mundtii Tw278 strain and evaluate the conservation capacity in a food model. The pH control did not affect the production of the compounds when the optimal production media were used (LAPTg for bacteriocin and LAPLW for bioemulsifier), respectively. The values obtained for bacteriocin were 819,200 AU/mL at 9 h in the batch, while this value was obtained at 12 h in the reactor. The highest emulsification index (E24) was 60.97 at 24 h in the batch, while in the reactor, it was 54.3 at 12 h. The bioemulsifier produced would be a glyprotein, according to FTIR analysis, with the capacity to form polydisperse oil-in-water emulsions with particles with an average diameter of 50 μm. Finally, it was found that E. mundtii Tw278 strain, as well as its antilisteria extract, were able to control and reduce the initial population of 3.4 log CFU/mL of Listeria monocytogenes Scott A to undetectable values in a yogurt model, with production at 42 °C for 8 h and storage at 4 °C for 15 days and bacteriocinogenic strain and its extract did not alter the physicochemical properties inherent to yogurt.

Reactions Driven by Primitive Nonbiological Polyesters.

ConspectusAll life on Earth is composed of cells, which are built from and run by biological reactions and structures. These reactions and structures are generally the result of action by cellular biomolecules, which are indispensable for the function and survival of all living organisms. Specifically, biological catalysis, namely by protein enzymes, but also by other biomolecules including nucleic acids, is an essential component of life. How the biomolecules themselves that perform biological catalysis came to exist in the first place is a major unanswered question that plagues researchers to this day, which is generally the focus of the origins of life (OoL) research field. Based on current knowledge, it is generally postulated that early Earth was full of a myriad of different chemicals, and that these chemicals reacted in specific ways that led to the emergence of biochemistry, cells, and later, life. In particular, a significant part of OoL research focuses on the synthesis, evolution, and function of biomolecules potentially present under early Earth conditions, as a way to understand their eventual transition into modern life. However, this narrative overlooks possibilities that other molecules contributed to the OoL, as while biomolecules that led to life were certainly present on early Earth, at the same time, other molecules that may not have strict, direct biological lineage were also widely and abundantly present. For example, hydroxy acids, although playing a role in metabolism or as parts of certain biological structures, are not generally considered to be as essential to modern biology as amino acids (a chemically similar monomer), and thus research in the OoL field tends to perhaps focus more on amino acids than hydroxy acids. However, their likely abundance on early Earth coupled with their ability to spontaneously condense into polymers (i.e., polyesters) make hydroxy acids, and their subsequent products, functions, and reactions, a reasonable target of investigation for prebiotic chemists. Whether "non-biological" hydroxy acids or polyesters can contribute to the emergence of life on early Earth is an inquiry that deserves attention within the OoL community, as this knowledge can also contribute to our understanding of the plausibility of extraterrestrial life that does not exactly use the biochemical set found in terrestrial organisms. While some demonstrations have been made with respect to compartment assembly, compartmentalization, and growth of primitive polyester-based systems, whether these "non-biological" polymers can contribute any catalytic function and/or drive primitive reactions is still an important step toward the development of early life. Here, we review research both from the OoL field as well as from industry and applied sciences regarding potential catalysis or reaction driven by "non-biological" polyesters in various forms: as linear polymers, as hyperbranched polyesters, and as membraneless microdroplets.

The inorganic pyrophosphatases of microorganisms: a structural and functional review

Pyrophosphatases (PPases) are enzymes that catalyze the hydrolysis of pyrophosphate (PPi), a byproduct of the synthesis and degradation of diverse biomolecules. The accumulation of PPi in the cell can result in cell death. Although the substrate is the same, there are variations in the catalysis and features of these enzymes. Two enzyme forms have been identified in bacteria: cytoplasmic or soluble pyrophosphatases and membrane-bound pyrophosphatases, which play major roles in cell bioenergetics. In eukaryotic cells, cytoplasmic enzymes are the predominant form of PPases (c-PPases), while membrane enzymes (m-PPases) are found only in protists and plants. The study of bacterial cytoplasmic and membrane-bound pyrophosphatases has slowed in recent years. These enzymes are central to cell metabolism and physiology since phospholipid and nucleic acid synthesis release important amounts of PPi that must be removed to allow biosynthesis to continue. In this review, two aims were pursued: first, to provide insight into the structural features of PPases known to date and that are well characterized, and to provide examples of enzymes with novel features. Second, the scientific community should continue studying these enzymes because they have many biotechnological applications. Additionally, in this review, we provide evidence that there are m-PPases present in fungi; to date, no examples have been characterized. Therefore, the diversity of PPase enzymes is still a fruitful field of research. Additionally, we focused on the roles of H+/Na+ pumps and m-PPases in cell bioenergetics. Finally, we provide some examples of the applications of these enzymes in molecular biology and biotechnology, especially in plants. This review is valuable for professionals in the biochemistry field of protein structure–function relationships and experts in other fields, such as chemistry, nanotechnology, and plant sciences.

Single-tissue proteomics in Caenorhabditis elegans reveals proteins resident in intestinal lysosome-related organelles

The nematode intestine is the primary site for nutrient uptake and storage as well as the synthesis of biomolecules; lysosome-related organelles known as gut granules are important for many of these functions. Aspects of intestine biology are not well understood, including the export of the nutrients it imports and the molecules it synthesizes, as well as the complete functions and protein content of the gut granules. Here, we report a mass spectrometry (MS)-based proteomic analysis of the intestine of the Caenorhabditis elegans and of its gut granules. Overall, we identified approximately 5,000 proteins each in the intestine and the gonad and showed that most of these proteins can be detected in samples extracted from a single worm, suggesting the feasibility of individual-level genetic analysis using proteomes. Comparing proteomes and published transcriptomes of the intestine and the gonad, we identified proteins that appear to be synthesized in the intestine and then transferred to the gonad. To identify gut granule proteins, we compared the proteome of individual intestines deficient in gut granules to the wild type. The identified gut granule proteome includes proteins known to be exclusively localized to the granules and additional putative gut granule proteins. We selected two of these putative gut granule proteins for validation via immunohistochemistry, and our successful confirmation of both suggests that our strategy was effective in identifying the gut granule proteome. Our results demonstrate the practicability of single-tissue MS-based proteomic analysis in small organisms and in its future utility.

Cadmium content, metabolite profile, biological properties of Eclipta alba (L.) Hassk plant exposed to elevated cadmium in soil

Cadmium (Cd), a highly mobile and hazardous toxic heavy metal negatively affects plant’s yield by regulating synthesis of biomolecules, involved in both physiological and biochemical activities. The present study investigated the Cd content, metabolite profile, antioxidant and antibacterial activities of methanolic leaf extracts (MLEs) of Eclipta alba L., plant exposed to elevated soil Cd (eCdS). The tested plants were grown in earthen pot and were weekly treated with Cd as CdCl2. H20 (20 mg/L) till 70 days after the plant transplantation. The results showed that eCdS significantly elevated Cd content in root and shoot tissue of E. alba plant (91 % and 94 %, respectively) as compared to the control. UHPLC-HRMS profile of MLEs revealed a significant decrease in the amino acids and its derivatives with an increased level of phenolic contents, fatty acids, and lipids. Metabolites in MLEs were also upregulated and downregulated (31 and 98, respectively) by an eCdS. An eCdS further increased both total phenolics and total flavonoids content in MLEs of E. alba by 71 % and 31 %, respectively over the control. In-vitro antioxidant activities in MLEs were also found to be significantly increased due to eCdS as DPPH > ABTS > FRAP (30 %, 26 % and 21 %, respectively) as compared to the control. Cd treated plant’s MLEs also revealed maximum reduction in an inhibition zone of Pseudomonas aeruginosa (ATCC 27853), among the tested bacterial strains. The present study concludes that eCdS led to the significant changes in the metabolite profile, phenolics content and biological activities of E. alba’s MLEs suggesting its ameliorating role in improving the medicinal value of E. alba plant. However, direct consumption of raw material of E. alba plant is not recommended due to high accumulation of Cd in its different parts.

Design, optimization, characterization, and in vitro evaluation of metformin-loaded liposomes for triple negative breast cancer treatment

Recently, metformin (Met) has shown to have antineoplastic properties in cancer treatment by improving hypoxic tumor conditions, and causing reduction in the synthesis of biomolecules, which are vital for cancer growth. However, as an orally administered drug, Met has low bioavailability and rapid renal clearance. Thus, the goal of this study was to vectorize Met inside liposomes in the context of triple negative breast cancer (TNBC), which currently lacks treatment options when compared to other types of breast cancer. Vectorization of Met inside liposomes was done using Bangham method by implementing double design of experiment methodology to increase Met drug loading (minimum-run resolution V characterization design and Box-Behnken design), as it is generally extremely low for hydrophilic molecules. Optimization of Met-loaded liposome synthesis was successfully achieved with drug loading of 190 mg/g (19% w/w). The optimal Met-liposomes were 170 nm in diameter with low PdI (< 0.1) and negative surface charge (-20 mV), exhibiting sustained Met release at pH 7.4. The liposomal Met delivery system was stable over several months, and successfully reduced TNBC cell proliferation due to the encapsulated drug. This study is one the first reports addressing liposome formulation through thin-film hydration using two design of experiment methods aiming to increase drug loading of Met.

Enhancing Teaching and Learning of Glycolysis in Biochemistry: A PCK-based Approach for Biochemistry Educators

The Pedagogical Content Knowledge (PCK)-based approach is a teaching framework that integrates both subject matter knowledge (content knowledge) and effective teaching strategies (pedagogical knowledge). In biochemistry education, the PCK-based approach aims to enhance the teaching and learning of glycolysis by providing educators with the necessary tools and strategies to effectively convey complex concepts to students. Glycolysis is a fundamental metabolic pathway in biochemistry that plays a crucial role in energy production and the synthesis of important biomolecules. As biochemistry educators, it is essential to effectively teach and facilitate the learning of glycolysis concepts and principles to ensure students' comprehensive understanding and application of this pathway. To achieve this, adopting a pedagogical content knowledge (PCK)-based approach can provide biochemistry educators with a framework to enhance their teaching strategies and improve student learning outcomes..

Controlled Modification of Triaminoguanidine-Based μ3 Ligands in Multinuclear [VIVO]/[VVO2] Complexes and Their Catalytic Potential in the Synthesis of 2-Amino-3-cyano-4H-pyrans/4H-chromenes.

Reaction of tris(2-hydroxybenzylidene)-triaminoguanidinium chloride (I·HCl) and tris(5-bromo-2-hydroxybenzylidene)-triaminoguanidinium chloride (II·HCl) with [VIVO(acac)2] (1:1 molar ratio) in refluxing methanol resulted in mononuclear [VIVO] complexes, [VIVO(H2L1')(MeOH)] (1) and [VIVO(H2L2')(MeOH)] (2), respectively, where I and II undergo intramolecular triazole ring formation. Aerial oxidation of 1 and 2 in MeOH in the presence of Cs2CO3 gave corresponding cis-[VVO2] complexes Cs[(VO2)(H2L1')] (3) and Cs[(VO2)(H2L2')] (4). However, reaction of an aerially oxidized methanolic solution of [VIVO(acac)2] with I·HCl and II·HCl in the presence of Cs2CO3 (in 1:1:1 molar ratio) gave mononuclear complexes Cs[(VO2)(H3L1)] (5) and Cs[(VO2)(H3L2)] (6) without intramolecular triazole ring formation. Similar anionic trinuclear complexes Cs2[(VO2)3(L1)] (7) and Cs2[(VO2)3(L2)] (8) were isolable upon increasing the amounts of the vanadium precursor and Cs2CO3 to 3 equiv to the reaction applied for 5 and 6. Keeping the reaction mixture of 1 in MeOH under air gave [VVO(H2L1')(OMe)] (9). Structures of 3, 7, 8, and 9 were confirmed by X-ray crystal structure study. A permanent porosity in the crystalline metal-organic framework of 7 confirmed by single-crystal X-ray investigation was further verified by the BET study. Along with a suitable reaction mechanism, these synthesized compounds were explored as effective catalysts for the synthesis of biomolecules 4H-pyran/4H-chromenes.

Cellular metabolism: A key player in cancer ferroptosis.

Cellular metabolism is the fundamental process by which cells maintain growth and self-renewal. It produces energy, furnishes raw materials, and intermediates for biomolecule synthesis, and modulates enzyme activity to sustain normal cellular functions. Cellular metabolism is the foundation of cellular life processes and plays a regulatory role in various biological functions, including programmed cell death. Ferroptosis is a recently discovered form of iron-dependent programmed cell death. The inhibition of ferroptosis plays a crucial role in tumorigenesis and tumor progression. However, the role of cellular metabolism, particularly glucose and amino acid metabolism, in cancer ferroptosis is not well understood. Here, we reviewed glucose, lipid, amino acid, iron and selenium metabolism involvement in cancer cell ferroptosis to elucidate the impact of different metabolic pathways on this process. Additionally, we provided a detailed overview of agents used to induce cancer ferroptosis. We explained that the metabolism of tumor cells plays a crucial role in maintaining intracellular redox homeostasis and that disrupting the normal metabolic processes in these cells renders them more susceptible to iron-induced cell death, resulting in enhanced tumor cell killing. The combination of ferroptosis inducers and cellular metabolism inhibitors may be a novel approach to future cancer therapy and an important strategy to advance the development of treatments.

The impact of chemical properties of the solid-liquid-adsorbate interfaces on the entropy-enthalpy compensation involved in adsorption.

Despite extensive studies on the thermodynamic mechanism governing molecular adsorption at the solid-water interface, a comprehensive understanding of the crucial role of interface properties in mediating the entropy-enthalpy compensation during adsorption is lacking, particularly at a quantitative level. Herein, we employed two types of surface models (hydroxyapatite and graphene) along with a series of amino acids to successfully elucidate how distinct interfacial features dictate the delicate balance between entropy and enthalpy variations. The adsorption of all amino acids on the hydroxyapatite surface is an enthalpy-dominated process, where the water-induced enthalpic component of the free energy and the surface-adsorbate electrostatic interaction term alternatively act as the driving force for adsorption in different regions of the surface. Although favorable interactions are observed between amino acids and the graphene surface, the entropy-enthalpy compensation exhibits dependence on the molecular size of the adsorbates. For small amino acids, favorable enthalpy changes predominantly determine their adsorption behavior; however, larger amino acids tend to bind more tightly with the graphene surface, which is thermodynamically dominated by the entropy variations despite the structural characteristics of amino acids. This study reveals specific entropy-enthalpy mechanisms underlying amino acid adsorption at the solid-liquid interface, providing guidance for surface design and synthesis of new biomolecules.