Intersection Of Chemistry Research Articles

Ionic Liquid‐Mediated Dynamic Polymerization for Facile Aqueous‐Phase Synthesis of Enzyme‐Covalent Organic Framework Biocatalysts

AbstractUtilizing covalent organic framework (COF) as a hypotoxic and porous scaffold to encapsulate enzyme (enzyme@COF) has inspired numerous interests at the intersection of chemistry, materials, and biological science. In this study, we report a convenient scheme for one‐step, aqueous‐phase synthesis of highly crystalline enzyme@COF biocatalysts. This facile approach relies on an ionic liquid (2 μL of imidazolium ionic liquid)‐mediated dynamic polymerization mechanism, which can facilitate the in situ assembly of enzyme@COF under mild conditions. This green strategy is adaptive to synthesize different biocatalysts with highly crystalline COF “exoskeleton”, as well evidenced by the low‐dose cryo‐EM and other characterizations. Attributing to the rigorous sieving effect of crystalline COF pore, the hosted lipase shows non‐native selectivity for aliphatic acid hydrolysis. In addition, the highly crystalline linkage affords COF “exoskeleton” with higher photocatalytic activity for in situ production of H2O2, enabling us to construct a self‐cascading photo‐enzyme coupled reactor for pollutants degradation, with a 2.63‐fold degradation rate as the poorly crystalline photo‐enzyme reactor. This work showcases the great potentials of employing green and trace amounts of ionic liquid for one‐step synthesis of crystalline enzyme@COF biocatalysts, and emphasizes the feasibility of diversifying enzyme functions by integrating the reticular chemistry of a COF.

Ionic Liquid-Mediated Dynamic Polymerization for Facile Aqueous-Phase Synthesis of Enzyme-Covalent Organic Framework Biocatalysts.

Utilizing covalent organic framework (COF) as a hypotoxic and porous scaffold to encapsulate enzyme (enzyme@COF) has inspired numerous interests at the intersection of chemistry, materials, and biological science. In this study, we report a convenient scheme for one-step, aqueous-phase synthesis of highly crystalline enzyme@COF biocatalysts. This facile approach relies on an ionic liquid (2 μL of imidazolium ionic liquid)-mediated dynamic polymerization mechanism, which can facilitate the in situ assembly of enzyme@COF under mild conditions. This green strategy is adaptive to synthesize different biocatalysts with highly crystalline COF "exoskeleton", as well evidenced by the low-dose cryo-EM and other characterizations. Attributing to the rigorous sieving effect of crystalline COF pore, the hosted lipase shows non-native selectivity for aliphatic acid hydrolysis. In addition, the highly crystalline linkage affords COF "exoskeleton" with higher photocatalytic activity for in situ production of H2 O2 , enabling us to construct a self-cascading photo-enzyme coupled reactor for pollutants degradation, with a 2.63-fold degradation rate as the poorly crystalline photo-enzyme reactor. This work showcases the great potentials of employing green and trace amounts of ionic liquid for one-step synthesis of crystalline enzyme@COF biocatalysts, and emphasizes the feasibility of diversifying enzyme functions by integrating the reticular chemistry of a COF.

Edge-based metric resolvability of anti-depression molecular structures and its application

Chemical graph theory represents an interdisciplinary field at the intersection of chemistry and mathematics, focusing on the analysis of various chemical structures through graph-theoretical frameworks. This area facilitates the examination of complex and extensive chemical configurations by leveraging graph theory principles. In chemical structure graphs, atoms are depicted as vertices, with edges representing the bonds between them. By employing chemical graph theory, the exploration of diverse drug compounds and intricate molecular structures becomes more manageable. A key concept in this field is the resolvability parameter, a metric derived from graph theory. It stipulates that each vertex in a structure must possess a distinct representation via elected vertices, known as a metric basis, resolving set, or locating set in different scientific contexts. The metric dimension, defined as the minimum number of vertices in the resolving set, plays a crucial role in characterizing the structural properties of chemical graphs. In this study, we discussed the edge metric dimension of structures of benzodiazepines, alprazolam, chlordiazepoxide, clobazam, clonazepam, diazepam, nitrazepam, lolendazam, alferez, which are types of drug that used for the treatment of depression. We also put to use the edge metric dimension in anti-depression chemical structures, which are different types of Benzodiazepine. For application of this topic, we select the hospitals and health centers in any emergency situation. In any chronic disease situation, these chosen health centers provide all medical facilities to other hospitals efficiently only because we assigned each hospital and health center a unique code.

Re-evaluating retrosynthesis algorithms with Syntheseus.

Automated synthesis planning has recently re-emerged as a research area at the intersection of chemistry and machine learning. Despite the appearance of steady progress, we argue that imperfect benchmarks and inconsistent comparisons mask systematic shortcomings of existing techniques, and unnecessarily hamper progress. To remedy this, we present a synthesis planning library with an extensive benchmarking framework, called SYNTHESEUS, which promotes best practice by default, enabling consistent meaningful evaluation of single-step and multi-step synthesis planning algorithms. We demonstrate the capabilities of SYNTHESEUS by re-evaluating several previous retrosynthesis algorithms, and find that the ranking of state-of-the-art models changes in controlled evaluation experiments. We end with guidance for future works in this area, and call on the community to engage in the discussion on how to improve benchmarks for synthesis planning.

Low throughput screening in neuroscience: using light to study central synapses one at a time.

Neurophotonic approaches have fostered substantial progress in our understanding of the brain by providing an assortment of means to either monitor or manipulate neural processes. Among these approaches, the development of two-photon uncaging provides a useful and flexible approach to manipulate the activity of individual synapses. In this short piece, we explore how this technique has emerged at the intersection of chemistry, optics, and electrophysiology to enable spatially and temporally precise photoactivation for studying functional aspects of synaptic transmission and dendritic integration. We discuss advantages and limitations of this approach, focusing on our efforts to study several functional aspects of glutamate receptors using uncaging of glutamate. Among other advancements, this approach has contributed to further our understanding of the subcellular regulation, trafficking, and biophysical features of glutamate receptors (e.g., desensitization and silent synapse regulation), the dynamics of spine calcium, and the integrative features of dendrites, and how these functions are altered by several forms of plasticity.

Molecular modeling in the radiation therapy. The algebraic approach

The rapid development of the chemical industry and science, and new challenges in the healthcare sector, put forward increased demands for the development of the theory of organic and inorganic chemistry, for the search and implementation of new modeling and analysis methods, and for the improvement of technological processes. One of the main challenges at the intersection of chemistry, physics, biol- ogy, medicine, and genetics is the search for new methods and approaches to the diagnosis and treatment of cancer. A deeper understanding of cancer’s genetics and molecular biology has led to the identification of an increasing number of potential molecular targets that can be used for the discovery and development of anticancer drugs, radiation therapy, etc. One of the main places in this is occupied by molecular modeling. Despite the availability of more and more data on existing proteins and nucleic acids and the availability of modeling methods and tools, the development and use of a wide variety of combined methods and tools for modeling and computing large molecular systems remain an open issue. One of the possible solutions for this problem is the application of the algebraic approach and the corresponding formal methods, which have proven effective in many other fields today. The main idea of the research is the application of algebraic modeling technology and quantum chemical apparatus for modeling and verification of organic chemistry problems, in particular, modeling and analysis of radiation therapy problems. The paper presents the first steps of the research. The example of the formalization of the synchrotron operation principle and the example of the interaction of protons with substance in the example of the determination/calculation of the physically absorbed dose are given in the paper.

Design, Synthesis and Actual Applications of the Polymers Containing Acidic P-OH Fragments: Part 1. Polyphosphodiesters.

Among natural and synthetic polymers, main-chain phosphorus-containing polyacids (PCPAs) (polyphosphodiesters), stand in a unique position at the intersection of chemistry, physics, biology and medicine. The structural similarity of polyphosphodiesters PCPAs to natural nucleic and teichoic acids, their biocompatibility, mimicking to biomolecules providing the 'stealth effect', high bone mineral affinity of polyphosphodiesters resulting in biomineralization at physiological conditions, and adjustable hydrolytic stability of polyphosphodiesters are the basis for various biomedical, industrial and household applications of this type of polymers. In the present review, we discuss the synthesis, properties and actual applications of polyphosphodiesters.

CHEMICAL AND PHARMACOLOGICAL EVOLUTION OF SOME SYNTHESIZED CHALCONES AND HETROCYCLIC COMPOUNDS

Pharmaceutical chemistry is focused on quality aspects of medicines and aims to assure fitness for the purpose of medicinal products. With centuries medicinal chemistry had emerged as a magnanimous field of science getting a facelift from the available natural compounds for synthesis of newer and complex molecules possessing medicinal activity while the transit from the earth to a synthetically furnished laboratory. Medicinal chemistry or pharmaceutical chemistry is a discipline at the intersection of chemistry and pharmacology involved with designing, synthesizing and developing pharmaceutical drugs. Chalconesis a generic term given to compounds bearing the 1,3-diarylprop2-en-1-one, which can be functionlized in the propane chain by the presence of olefinic, keto and/or hydroxyl group. Chalcones belongs to the flavonoid family. Chemically chalcones consisted of open chain flavonoids in which the two aromaticrings are joined by a three carbon a,ß-unsaturated carbonyl system (Dhar, 1981). Microorganisms are a heterogeneous group of several distinct classes of living beings. They were classified under third kingdom, theProstita. Based on differences in cellular organization and biochemistry, the kingdom prostita has been divided into two groups, Prokaryotes and Eukaryotes. Bacteria and blue green algae are prokaryotes while fungi, other algae, slime moulds and protozoa are eukaryotes. Anti-fungal drugs are among the most frequently prescribed preparations because of their fungal activity. They are widely used for the treatment of the fungal diseases such as Candidiasis and Apergillosis. These agents prevent from fungal infection. Anti-oxidant drugs are among the most frequently prescribed preparations prevent Oxidation.

CHEMICAL AND PHARMACOLOGICAL EVOLUTION OF SOME SYNTHESIZED CHALCONES AND HETROCYCLIC COMPOUNDS

Pharmaceutical chemistry is focused on quality aspects of medicines and aims to assure fitness for the purpose of medicinal products. With centuries medicinal chemistry had emerged as a magnanimous field of science getting a facelift from the available natural compounds for synthesis of newer and complex molecules possessing medicinal activity while the transit from the earth to a synthetically furnished laboratory. Medicinal chemistry or pharmaceutical chemistry is a discipline at the intersection of chemistry and pharmacology involved with designing, synthesizing and developing pharmaceutical drugs. Chalconesis a generic term given to compounds bearing the 1,3-diarylprop2-en-1-one, which can be functionlized in the propane chain by the presence of olefinic, keto and/or hydroxyl group. Chalcones belongs to the flavonoid family. Chemically chalcones consisted of open chain flavonoids in which the two aromaticrings are joined by a three carbon a,ß-unsaturated carbonyl system (Dhar, 1981). Microorganisms are a heterogeneous group of several distinct classes of living beings. They were classified under third kingdom, theProstita. Based on differences in cellular organization and biochemistry, the kingdom prostita has been divided into two groups, Prokaryotes and Eukaryotes. Bacteria and blue green algae are prokaryotes while fungi, other algae, slime moulds and protozoa are eukaryotes. Anti-fungal drugs are among the most frequently prescribed preparations because of their fungal activity. They are widely used for the treatment of the fungal diseases such as Candidiasis and Apergillosis. These agents prevent from fungal infection. Anti-oxidant drugs are among the most frequently prescribed preparations prevent Oxidation.

Primo Levi: A frustrated stereochemist?-Insight in hindsight.

Primo Levi (1919-1987) has become an iconic figure at the intersection of chemistry and culture. Levi has long been praised for his autobiographical account as survivor in Auschwitz and by his literary masterpiece "The Periodic Table." Little is however known beyond such facts, especially his academic period and early research on stereochemistry at the University of Turin, which were abruptly truncated by the racial laws and WWII. Even if, later on, Primo Levi succeeded as industrial chemist, he had a vivid interest in molecular asymmetry that lasted through his entire life. This concise paper highlights a little known academic period in the midst of social and political upheaval. Levi left us his humanity in an otherwise tortuous life, and his literature took inspiration from chemistry; perhaps as a metaphor connecting the physical world and people's life.

Construction of Supramolecular Polymers Based on Host‐Guest Recognition†

What is the most favorite and original chemistry developed in your research group?The establishment of two new types of host‐guest recognition building blocks (21‐crown‐7/secondary ammonium salt and pillar[5]arene/alkyl chain) for supramolecular polymers.How do you get into this specific field? Could you please share some experiences with our readers?I got my introduction to supramolecular chemistry during the postgraduate period. There are many phenomena closely related to the weak non‐covalent interactions in nature, such as the storage and transmission of genetic information through the DNA double helix structure. Inspired by these fascinating natural phenomena, scientists try to use non‐covalent interactions to prepare many very complex self‐assembled systems including supramolecular polymers from natural and artificially designed structural units. In 1987, Lehn, Cram, and Pederson won the Nobel Prize for their contribution to supramolecular chemistry. At present, supra‐molecular chemistry has developed into an emerging discipline formed by the intersection of chemistry, physics, life sciences, materials science, and electronic engineering.How do you supervise your students?Lead by example, teach students according to their aptitude, strive for excellence, and be a teacher and a friend.What is the most important personality for scientific research?Curiosity, thinking, hard work, and concentration.What's your hobbies? What's your favorite book(s)?Hiking and reading. Swordmen novels.How do you keep balance between research and family?Reasonable arrangement and choice.Who influences you mostly in your life?My grandmother. She taught me: “No pains, no gains”.Self‐assembly is a topic of intense scientific interest. Supramolecular polymers are one of the most important research directions in the field of chemical self‐assembly. As a novel kind of polymeric systems, supramolecular polymers are still in the early stage of their development. There are three fundamental scientific problems: How to expand host‐guest recognition building blocks? How to realize the control of the structures of supramolecular polymers at multiple levels? And how to realize multi‐stimuli responsivenesses of supramolecular polymers? To address these scientific problems, we constructed a series of novel supramolecular polymers based on host‐guest recognition.

Mass transport properties and applications of nanochannels

With the development of materials science, micro/nano processing technologies, and mass transport theories at the micro/nano scale, nanochannel-based technology has been receiving increasing attention. Nanochannels can be classified as biological and artificial. The size of a nanochannel is typically 1-100 nm, which greatly enhances the interaction between the channel surface and substances inside the channel, inducing several special mass transport properties such as ion selectivity, ionic current rectification, and resistive current pulse. Ion selectivity is caused by the electrostatic interaction between ions and the surface charge of the nanochannel, ionic current rectification arises from the asymmetric distribution of the electrochemical potential inside the nanochannel, and a resistive current pulse is generated by the blocking of the nanochannel during the transport of ions/molecules. By taking advantage of these mass transport properties, nanochannels can be applied to various fields. For example, gated ion transport can be realized by modifying the surface of the nanochannel with functional groups; single-molecule sensing can be realized using sub-nanoscale channels; the separation of ions, molecules, or nanoparticles can be realized by regulating the interaction between the nanochannel and transport substances; and various forms of energy, such as light, heat, and salt gradient, can drive charge separation within the nanochannel and be converted into electricity by harnessing the ion selectivity of the nanochannel. However, despite the achievements in nanochannel-based technology, in-depth exploration of the mass transport properties at the nanoscale and further expansion of its application remain to be realized. For the development of this technology, four major issues need to be addressed: fabrication of a single-atom-thick nanochannel/nanopore membrane, precise control of the nanochannel structure, effective regulation of the surface properties of the nanochannel, and enrichment and development of mass transport theories. Nanochannel-based technology requires interdisciplinary efforts at the intersection of chemistry, materials science, and nanotechnology, and shows good promise for solving basic problems in biology, environment, and energy. Herein, we briefly describe the mass transport properties of nanochannels and some emerging developments and applications, and finally provide a brief outlook on this field.

Synthetic investigation of competing magnetic interactions in 2D metal-chloranilate radical frameworks.

The discovery of emergent materials lies at the intersection of chemistry and condensed matter physics. Synthetic chemistry offers a pathway to create materials with the desired physical and electronic structures that support fundamentally new properties. Metal–organic frameworks are a promising platform for bottom-up chemical design of new materials, owing to their inherent chemical predictability and tunability relative to traditional solid-state materials. Herein, we describe the synthesis and magnetic characterization of a new 2,5-dihydroxy-1,4-benzoquinone based material, (NMe2H2)3.5Ga2(C6O4Cl2)3 (1), which features radical-based electronic spins on the sites of a kagomé lattice, a geometric lattice known to engender exotic electronic properties. Vibrational and electronic spectroscopies, in combination with magnetic susceptibility measurements, revealed 1 exhibits mixed valency between the radical-bearing trianionic and diamagnetic tetraanionic oxidation states of the ligand. This unpaired electron density on the ligand forms a partially occupied kagomé lattice where approximately 85% of the lattice sites are occupied with an S = ½ spin. We found that gallium mediates ferromagnetic coupling between ligand spins, creating a ferromagnetic kagomé lattice. By modulation of the interlayer spacing via post-synthetic cation metathesis of 1 to (NMe4)3.5Ga2(C6O4Cl2)3 (2) and (NEt4)2(NMe4)1.5Ga2(C6O4Cl2)3 (3), we determined the nature of the magnetic coupling between neighboring planes is antiferromagnetic. Additionally, we determined the role of the metal in mediating this magnetic coupling by comparison of 2 with the In3+ analogue, (NMe4)3.5In2(C6O4Cl2)3 (4), and we found that Ga3+ supports stronger superexchange coupling between ligand-based spins than In3+. The combination of intraplanar ferromagnetic coupling and interplanar antiferromagnetic coupling exchange interactions suggests these are promising materials to host topological phenomena.

Recent Progress in Ferroptosis Inducers for Cancer Therapy.

Ferroptosis is a newly discovered form of regulated cell death that is the nexus between metabolism, redox biology, and human health. Emerging evidence shows the potential of triggering ferroptosis for cancer therapy, particularly for eradicating aggressive malignancies that are resistant to traditional therapies. Recently, there has been a great deal of effort to design and develop anticancer drugs based on ferroptosis induction. Recent advances of ferroptosis-inducing agents at the intersection of chemistry, materials science, and cancer biology are presented. The basis of ferroptosis is summarized first to highlight the feasibility and characteristics of triggering ferroptosis for cancer therapy. A literature review of ferroptosis inducers (including small molecules and nanomaterials) is then presented to delineate their design, action mechanisms, and anticancer applications. Finally, some considerations for research on ferroptosis inducers are spotlighted, followed by a discussion on the challenges and future development directions of this burgeoning field.

Solid-Phase Chemical Synthesis of Stable Isotope-Labeled RNA to Aid Structure and Dynamics Studies by NMR Spectroscopy

RNA structure and dynamic studies by NMR spectroscopy suffer from chemical shift overlap and line broadening, both of which become worse as RNA size increases. Incorporation of stable isotope labels into RNA has provided several solutions to these limitations. Nevertheless, the only method to circumvent the problem of spectral overlap completely is the solid-phase chemical synthesis of RNA with labeled RNA phosphoramidites. In this review, we summarize the practical aspects of this methodology for NMR spectroscopy studies of RNA. These types of investigations lie at the intersection of chemistry and biophysics and highlight the need for collaborative efforts to tackle the integrative structural biology problems that exist in the RNA world. Finally, examples of RNA structure and dynamic studies using labeled phosphoramidites are highlighted.

Designing and transforming yield-stress fluids

We review progress in designing and transforming multi-functional yield-stress fluids and give a perspective on the current state of knowledge that supports each step in the design process. We focus mainly on the rheological properties that make yield-stress fluids so useful and the trade-offs which need to be considered when working with these materials. Thinking in terms of “design with” and “design of” yield-stress fluids motivates how we can organize our scientific understanding of this field. “Design with” involves identification of rheological property requirements independent of the chemical formulation, e.g. for 3D direct-write printing which needs to accommodate a wide range of chemistry and material structures. “Design of” includes microstructural considerations: conceptual models relating formulation to properties, quantitative models of formulation-structure-property relations, and chemical transformation strategies for converting effective yield-stress fluids to be more useful solid engineering materials. Future research directions are suggested at the intersection of chemistry, soft-matter physics, and material science in the context of our desire to design useful rheologically-complex functional materials.

Targeting RNA with Small Molecules To Capture Opportunities at the Intersection of Chemistry, Biology, and Medicine.

The biology of healthy and disease-affected cells is often mediated by RNA structures, desirable targets for small molecule chemical probes and lead medicines. Although structured regions are found throughout the transcriptome, some even with demonstrated functionality, human RNAs are considered recalcitrant to small molecule targeting. However, targeting structured regions with small molecules provides an important alternative to oligonucleotides that target sequence. In this Perspective, we describe challenges and progress in developing small molecules interacting with RNA (SMIRNAs) to capture their significant opportunities at the intersection of chemistry, biology, and medicine. Key to establishing a new paradigm in chemical biology and medicine is the development of methods to obtain, preferably by design, bioactive compounds that modulate RNA targets and companion methods that validate their direct effects in cells and pre-clinical models. While difficult, demonstration of direct target engagement in the complex cellular milieu, along with methods to establish modes of action, is required to push this field forward. We also describe frameworks for accelerated advancements in this burgeoning area, their implications, key new technologies for development of SMIRNAs, and milestones that have led to broader acceptance of RNA as a small molecule druggable target.

Precisely Defined Conjugated Oligoelectrolytes for Biosensing and Therapeutics.

Conjugated oligoelectrolytes (COEs) are a relatively new class of synthetic organic molecules with, as of yet, untapped potential for use in organic optoelectronic devices and bioelectronic systems. COEs also offer a novel molecular approach to biosensing, bioimaging, and disease therapy. Substantial progress has been made in the past decade at the intersection of chemistry, materials science, and the biological sciences developing COEs and their polymer analogues, namely, conjugated polyelectrolytes (CPEs), into synthetic systems with biological and biomedical utility. CPEs have traditionally attracted more attention in arenas of sensing, imaging, and therapy. However, the precisely defined molecular structures and interactions of COEs offer potential key advantages over CPEs, including higher reliability and fluorescence quantum efficiency, larger diversity of subcellular targeting strategies, and improved selectivity to biomolecules. Here, the unique-and sometimes overlooked-properties of COEs are discussed and the noticeable progress in their use for biological sensing, imaging, and therapy is reviewed.

Association and differences between on-surface chemistry and solution chemistry

As an emerging discipline in the intersection of chemistry and physics, on-surface chemistry has been at the forefront of surface science since its inception. On-surface chemistry has obvious differences from classical solution chemistry although they are closely related. Many reactions in solution become applicable in on-surface reactions under ultra-high vacuum conditions without the involvement of solvents. Furthermore, with the aid of surface confinement effects, a series of highly accurate, highly selective chemical reactions that are difficult to achieve in traditional solution reactions can be accomplished, which shows attractive potential for functional macromolecule design, synthetic chemistry, and new material fabrication. In this review, we present some representative on-surface reactions. By comparing the differences in reaction paths and products with traditional solution reactions, the characteristics of on-surface chemistry are epitomized. In addtion, we make a brief outlook for the opportunities and challenges of this novel synthetic tool facing in the future.

Perspectives: The intertwined histories of chemistry, fashion, and advertising

When thinking about the intersection of chemistry and design, many chemists might first envision the design of molecules or industrial processes. Stepping back to view the bigger picture, however, reveals that the interplay of innovations in chemistry and the design of physical objects are more deeply ingrained in our daily lives than it might seem. Exploring the chemistry-design intersection of fibers in our clothing, fiber treatments such as dyeing, and fashion, for example, not only illustrates the history, technology development, and impacts of innovation, but also hints at how studying interesting (and perhaps underexamined) stories could lead to thinking ahead about social responsibility and about innovations in both the chemistry and design fields. Deciphering the intertwined histories of chemistry and fashion design requires an interdisciplinary approach. This includes studying the archival records of synthetic fibers and their design applications, discussions between fiber producers and the fashi...