Accurate evaluation of combustion enthalpy is of high scientific and industrial importance. Although via ab-initio computation of heat of reactions, as one of the promising and well-established approaches in computational chemistry, this goal should in principle be achievable, examples of reliable and precise evaluation of heat of combustion by ab-initio methods has surprisingly not yet been reported

Cholesterol serves as a biomarker in clinical- and life-sciences. The determination of abnormal levels can indicate several types of human diseases. However, the low polarity of free cholesterol makes it hardly accessible by (nano) electrospray ionization mass spectrometry (nESI-MS). As novel approach, the flexible microtube plasma (FμTP) for post-ionization allows the determination of low-polar compounds

Unraveling challenging problems by machine learning has recently become a hot topic in many scientific disciplines. For developing rigorous machine-learning models to study problems of interest in molecular sciences, translating molecular structures to quantitative representations as suitable machine-learning inputs plays a central role. Many different molecular representations and the state-ofthe-

Crystals are among the most challenging materials to design, both at the molecular and macroscopic levels. We show here that metal-organic frameworks, based on tetrahedral pyridyl ligands, can be used as a morpho-logical and structural mold to form a series of other isostructural crystals having different metal ions. The cati-on exchange is versatile, based on the use of diverse first-row metals; it

We have investigated a bioinspired (N2S2)Ni(II) electrocatalyst that produces H2 from CF3CO2H with a turnover frequency (TOF) of ~200,000 s–1 at low acid concentration (<0.043 M) in MeCN. We also propose an electrochemical mechanism for such an electrocatalyst toward H2 production and benchmarked its activity by comparing its TOF and overpotential with those of other reported molecular Ni H2 evolution

Lipid monolayers provide our lungs and eyes their functionality, and serve as proxy systems in biomembrane research. Therefore, lipid monolayers have been studied intensively also using molecular dynamics simulations, which are able to probe their lateral structure and interactions with, e.g., pharmaceuticals or nanoparticles. However, such simulations have struggled in describing the forces at the

Human immunodeficiency virus 1 (HIV-1) protease is a homo-dimeric aspartic protease essential for replication of HIV. The HIV-1 protease is a target protein in drug discovery for antiretroviral therapy, and various inhibitor molecules of transition state analog were developed. However, serious drug-resistant mutants have emerged. For understanding molecular mechanism of the drug-resistance, accurate

The copper mediated β–C(sp2)–H sulfonylation of benzaldehydes with sulfinate salts is accomplished using β-alanine as a catalytic transient directing group. A broad range of sulfonylated benzaldehydes are prepared us-ing copper fluoride as both copper source and oxidant. Both b-(ortho) and g-(peri)-sulfonylation are demon-strated. Mechanistic studies indicate the turnover limiting step to be a concerted

A comprehensive description of the electrochemical processes in the positive electrode of lithium–sulfur batteries is crucial for the enhancement of sulfur utilization. However, the discharge mechanisms are complicated due to the various reactions in multiple phases and the tortuosity of the highly porous carbon matrix. While previous studies have focused on the precipitation of lithium sulfide, the

A series of s-indaceno[1,2,3-cd:5,6,7-c'd']dipyrene-containing small molecule and ladder polymers were prepared using a palladium catalyzed arylation reaction. Precursor polymers and their resulting ladder polymers with molecular weights up to 13 kDa were prepared. The rigid, planar materials possessed highest occupied molecular orbital (HOMO) energies of -5.39 to -5.23 eV, lowest unoccupied molecular

The self-assembly of amphiphiles is often modified by the presence of co-solutes and significant study has examined this behavior in aqueous systems. Much less is known about the role of polar co-solutes upon amphiphile aggregation within non-polar media, however such conditions are relevant to a variety of industrial processes - not the least of which are separations systems like those found in liquid-liquid

Quantum chemical calculations are reported for the thermal dimerizations of 1,3-cyclohexadiene at 1 atm and high pressures up to 6 GPa. Previous experiments [Klärner et al. Angew. Chem. Int. Ed. 1986, 25, 108], based on measured activation energies and activation volumes, suggested concerted mechanisms for the formation of the endo [4+2] cycloadduct and a [6+4]-ene adduct, and stepwise mechanisms for

Two-dimensional phenomena are attracting enormous interest at present and the search for novel 2D materials is very challenging. We propose here the layered material valleriite composed of altering atomic sheets of Cu-Fe sulfide and Mg-based hydroxide synthesized via a simple hydrothermal pathway as particles of 50-200 nm in the lateral size and 10-20 nm thick. The solid products and aqueous colloids

The prototype of a highly versatile and efficient preparative mass spectrometry system used for the deposition of molecules in ultra-high vacuum (UHV) is presented, along with encouraging performance data obtained on four model species which are thermolabile or not sublimable. The test panel comprises two small organic compounds, a protein, and a large DNA species covering a 4-log mass range up to

Condensed phosphates are a critically important class of molecules in biochemistry, with a myriad of derived structures being known. Moreover, non-natural analogues are important for various applications, such as single molecule real time DNA sequencing. Often, such analogues contain more than three phosphate units in their oligophosphate chain. Consequently, investigations into phosphate reactivity

The pandemic of COVID-2019 has urged the development of antiviral agents against its causative pathogen SARS-CoV-2. The main protease (Mpro), a cysteine protease essential for viral replication, is a promising protein target. Here we report an irreversible SARS-CoV-2 Mpro inhibitor possessing chlorofluoroacetamide (CFA) as the warhead for covalent modification of Mpro. Ugi multi-component reaction

The SARS-CoV-2 spike protein uses its receptor-binding domain (RBD) to interact with the angiotensin-converting enzyme 2 (ACE2) receptor on host cells, establishing the first step of SARS-CoV-2 infection. Inhibitors of RBD-ACE2 interaction, therefore, have shown great promise in preventing SARS-CoV-2 infection. Currently known RBD-ACE2 inhibitors are all based on reversible binding and must compete

Narcissistic self-sorting in supramolecular assemblies can help to construct materials with more complex hierarchies. Whereas controlled changes in pH or temperature have been used to this extent for two-component self-sorted gels, here we show that a chemically fueled approach can provide three-component materials with high precision. The latter materials have interesting mechanical properties, such

Triggered coacervate phase (de)stabilisation in complex coacervate core micelles (C3Ms) has traditionally been limited to changes in pH and salt concentration, limiting options in responsive C3M material design. To expand this toolbox, we have developed C3Ms, that, at constant physiological pH, assemble and disassemble by coupling to a chemical reaction network (CRN) driven by the conversion of electron

Deposition of human Serum Amyloid A (SAA) amyloids in blood vessels, causing inflammation, thrombosis and eventually organ damage, are a commonly seen as a consequence of certain cancers and inflammatory diseases. Several attempts have been made to develop peptide-based drugs that inhibit or at least slow down SAA amyloidosis. We use extensive all-atom molecular dynamic simulations to compare three

The electrochemical hydrogen evolution reaction (HER) is considered a sustainable energy approach to advance fuel-cell technologies, and HER electrocatalysts that resembles the [NiFe] hydrogenases are highly desired. Herein, we report a bioinspired Ni(II) complex (NCHS2)Ni(OTf)2, where NCHS2 is 3,7-dithia-1(2,6)-pyridina-5(1,3)-benzenacyclooctaphane, that is an efficient electrocatalyst for HER with

This study describes and demonstrates a carbon-negative process for manufacturing cement from widely abundant seawater-derived magnesium (Mg) feedstocks. In contrast to conventional Portland cement, which starts with carbon-containing limestone as the source material, the proposed process uses membrane-free electrolyzers to facilitate the conversion of carbon-free magnesium ions (Mg2+) in seawater

The lack of publicly available, large, and unbiased datasets is a key bottleneck for the application of machine learning (ML) methods in synthetic chemistry. Data from electronic laboratory notebooks (ELNs) could provide less biased, large datasets, but no such datasets have been made publicly available. The first real-world dataset from the ELNs of a large pharmaceutical company is disclosed and its

Invariant natural killer T cells (iNKT) are responsible for the production of pro-inflammatory cytokines which induce a systemic immune response. They are distinctive in possessing an invariant T-cell receptor that recognizes glycolipid antigens presented by the class I major histocompatibility complex-related protein CD1d, conserved across multiple mammalian species in a class of proteins well-renowned

Geometric analysis shows that the spike (S) protein in the COVID-19 virus (SARS-Cov-2) can fully or partially enter into the channel of a wide biological pore like perforin (PFN) or streptolysin (SLO) when the latter is anchored in a bilayer lipid membrane. The PFN channel is a β barrel formed from multiple monomers, for example a ~14 nm diameter channel is formed from 22 monomers. Coincidentally the

The microstructure of physically assembled gels depends on mechanical loading and environmental stimuli such as temperature. Here, we report the real-time change in the structure of physically assembled triblock copolymer gels that consist of 10 wt% and 20 wt% of poly(styrene)-poly(isoprene)-poly(styrene) [PS-PI-PS] triblock copolymer in mineral oil (i) during the gelation process with decreasing temperature

The future forecasting ability of machine learning (ML) makes ML a promising tool for predicting long-time quantum dissipative dynamics of open systems. In this Article, we employ nonparametric machine learning algorithm (kernel ridge regression as a representative of the kernel methods) to study the quantum dissipative dynamics of the widely-used spin-boson model. Our ML model takes short-time dynamics

A flexible covalent organic polymer (COP) has been successfully synthesized via dynamic covalent gel (DCG) formation through imine condensation reaction between 6-hydrazinonicotinic hydrazide hydrate and benzene-1,3,5-tricarboxaldehyde within 7 min under ambient condition. An emissive organogel mediated protocol has been developed for the construction of amorphous polymer (COP), selectively in N,N-dimethyl

Polypeptide-based nanoparticles offer unique advantages from a nanomedicine perspective such as biocompatibility, biodegradability and stimuli-responsive properties to (patho)physiological conditions. Conventionally, self-assembled polypeptide nanostructures are prepared by first synthesizing their constituent amphiphilic polypeptides followed by post-polymerization self-assembly. Herein, we describe

We demonstrated herein a versatile protocol for visible-light-induced sulphide anion-catalysed decarboxylative cross-couplings. An array of primary, secondary, tertiary and amino acid-derived redox-active esters (RAEs) were all amenable substrates to undergo radical decarboxylation to be coupled with a diverse range of nucleophiles, creating challenging C(sp3)-C(sp3) and C(sp3)-C(sp2) bonds with high

In the past decade, porous boron nitride (BN) has proven promising as a novel class of inorganic materials in the field of separations and particularly adsorption. Owing to its high surface area and thermal stability, porous BN has been researched for CO2 capture and water cleaning, for instance. However, most research remains at laboratory scale due to a lack of understanding of the formation mechanism

The production of value added C1 and C2 compounds within CO2 electrolyzers has reached sufficient catalytic performance that system and process performance – such as CO2 utilization – have come more into consideration. Efforts to assess the limitations of CO2 conversion and crossover within electrochemical systems have been performed, providing valuable information to position CO2 electrolyzers within

Defects in ionic solid are very much common, which is increased with the rise in temperature. It causes the change in the value of many physical properties and varieties of physical parameters and the Lattice Energy is one such parameter to control the physical properties of the crystals. Considering the loss of ions from lattice points as random, the examination of each of the defects individually

Direct analysis in real time mass spectrometry (DART-MS) is an increasingly employed tool for a wide range of forensic applications including seized drug analysis. A significant body of research surrounds DART-MS for the analysis of seized drugs and how it can be used to address many of the challenges caused by the increased presence of emerging drugs and novel psychoactive substances. A lack of available

Resistive pulse sensors have been used to characterise everything from whole cells to small molecules. Their integration into microfluidic devices have simplified sample handling whilst increasing throughput. Typically, these devices measure a limited size range or a specific analyte, making them prone to blockages in complex sample matrixes. To prolong their life and facilitate their use, samples

The development of single-molecule reaction inside nanoconfinement is benefit to study the intrinsic molecular mechanism of a complex chemical reaction. However, the reaction kinetics model of single-molecule reaction inside confinement remains elusive. Herein we engineered the Aerolysin nanopore reactor to elaborate the single-molecule reaction kinetics inside nanoconfinement. By identifying bond

Binding of ligands to macromolecules changes their physicochemical characteristics. Cyclic di-GMP and other cyclic di-nucleotides are second messengers involved in motility/sessility and acute/chronic infection life style transition. Although the GGDEF domain encoding preferentially a diguanylate cyclase represents one of the most abundant bacterial domain superfamilies, the number of cyclic di-GMP

We introduce a practical method for compacting the time evolution of the quantum state of a closed physical system. The density matrix is specified as a function of a few time-independent observables where their coefficients are time-dependent. The key mathematical step is the vectorization of the surprisal, the logarithm of the density matrix, at each time point of interest. The time span used depends

Molecular single stator-double rotor activity of an oxidized resorcinarene (fuchsonarene) macrocycle containing unsaturated hemiquinonoid groups at its meso positions was investigated. Fuchsonarenes containing two hemiquinonoid substituents at diagonally-opposed meso-positions with two electron rich phenol groups at the remaining meso-positions between the hemiquinonoid groups. All meso-substituents

We report a method for mild and atom-efficient synthesis of ketazines via nickel-catalyzed intermolecular hydroamination of internal alkynes with NH2-hydrazones. This alkyne hydrohydrazonation process is promoted by [Ni(cod)2] as a Ni(0) precatalyst and IPr as a N-heterocyclic carbene (NHC) ligand. A stoichiometric reaction between in situ generated [Ni(IPr)2] and benzophenone hydrazone (Ph2C=NNH2)

We report herein the synthesis, characterization, and coordination chemistry of a free N-aluminylene, namely a carbazolylaluminylene 2b. This species is prepared via a reduction reaction of the corresponding carbazolyl aluminium diiodide. The coordination behavior of 2b towards transition metal centers (W, Cr) is shown to afford a series of novel aluminylene complexes 3-6 with diverse coordination

The recent advances in relative protein-ligand binding free energy calculations have shown the value of alchemical methods in drug discovery. Accurately assessing absolute binding free energies, although highly desired, remains a challenging endeavour, mostly limited to small model cases. Here, we demonstrate accurate first principles based absolute binding free energy estimates for 128 pharmaceutically

Buffer solutions are pervasive in chemistry, biochemistry, analytical chemistry, etc. A better understanding of buffer properties and what controls them is susceptible to be of interest in many scientific and technological fields. For instance, linear pH gradients are commonly used in electrophoresis and their optimization rests on numerical optimization of the concentrations of various weak species

The spin-crossover reaction of thiophosgene has drawn broad attention from both experimenters and theoreticians as a prime example of radiationless intramolecular decay via intersystem crossing. Despite multiple attempts over 20 years, theoretical predictions have typically been orders of magnitude in error relative to the experimentally measured triplet lifetime. We address the T1 → S0 transition

AutoDock VINA is one of the most-used docking tools in the early stage of modern drug discovery. It uses a Monte-Carlo based iterated search method and multithreading parallelism scheme on multicore machines to improve docking accuracy and speed. However, virtual screening from huge compound databases is common for modern drug discovery, which puts forward a great demand for higher docking speed of

Polymer-Nanoparticle hydrogels are a unique class of self-assembled, shear-thinning, yield-stress fluids which have demonstrated potential utility in many impactful applications. Here we present a thorough analysis of the gelation and yielding behavior of these materials with respect to the polymer and nanoparticle component stoichiometry. Through comprehensive rheological and diffusion studies, we

This study examined factors influencing student confidence and their perception of learning in the context of undergraduate chemistry and biochemistry courses. Anonymous online surveys were used to measure the extent to which small group work influenced student confidence in solving problems compared to working individually, as well as how various course factors and the amount of effort and pleasure

Controlling excited state properties to achieve fast reverse intersystem crossing rates of over 107 s-1 is still challenging for intramolecular through-space charge transfer (TSCT) based delayed fluorescent materials. To gain further insight into the relationship between through-space and through-bond charge transfer (TSCT/TBCT), herein, three compounds DPS-24Ac, DPS-25Ac and DPS-OAc were prepared

Decentralized bioanalytical testing in resource-poor settings ranges among the prime applications of microfluidic systems. The high operational autonomy in such point-of-care / point-of-use scenarios requires on-board stored liquid reagents, which need to be safely contained during long-term storage, transport and handling, and reliably released prior to activation. Over the recent decades, centrifugal

We study the excited state absorption (ESA) properties of the four DNA bases (thymine, cytosine, adenine, and guanine) by different single reference quantum mechanical methods, i.e. equation of motion coupled cluster singles and doubles (EOM-CCSD), singles, doubles and perturbative triples (EOM-CC3), and time-dependent density functional theory (TD-DFT), with the long-range corrected CAM-B3LYP functional

Aryl phosphonate esters are valuable moieties for the pharmaceutical and agrochemical industries. Accessing such compounds from affordable and abundant phosphite reagents and a wide range of aromatic building blocks under metal-free, visible light-induced reaction conditions would represent a desirable technology. Herein, we present an efficient and mild methodology for the synthesis of aromatic phosphonate

Zeolites are inorganic materials with wide industrial applications due to their topological diversity. Tailoring confinement effects in zeolite pores, for instance by crystallizing intergrown frameworks, can improve their catalytic and transport properties, but controlling zeolite crystallization often relies on heuristics. In this work, we use computational simulations and data mining to design organic

TiO2-based nanosheets materials with core-shell structure are expected to be one of the promising photocatalysts to degradation of organic pollutions. However, it is a challenge to synthesis of TiO2 shell on functional core materials by desired nucleation and growth process. Layered double hydroxides (LDHs) are considered as ideal platforms to in-situ grow TiO2 and further serve as additional components

Structure-based, virtual High Throughput Screening (vHTS) methods for predicting ligand activity in drug discovery are important when there are no or relatively few known compounds that interact with a therapeutic target of interest. State-of-the-art computational vHTS necessarily relies on effective methods for pose sampling and docking to generate an accurate affinity score from the docked poses

Multifunctional supramolecular systems are a central research topic in light-driven solar energy conversion. Here, we report a polyoxometalate (POM)-based supramolecular dyad, where two platinum-complex hydrogen evolution catalysts are covalently anchored to an Anderson polyoxomolybdate anion. Supramolecular electrostatic coupling of the system to an iridium photosensitizer enables visible light-driven

Fourier-transform near-infrared (FT-NIR) spectroscopy was used to determine the geographical origin of 233 hazelnut samples of various varieties from five different countries (Germany, France, Georgia, Italy, Turkey). The experimental determination of the geographical origin of hazelnuts is important, because there are usually large price differences between the producer countries and thus a risk of

Triggered coacervate phase (de)stabilisation in complex coacervate core micelles (C3Ms) has traditionally been limited to changes in pH and salt concentration, limiting options in responsive C3M material design. To expand this toolbox, we have developed C3Ms, that, at constant physiological pH, assemble and disassemble by coupling to a chemical reaction network (CRN) driven by the conversion of electron

The first asymmetric total synthesis of fungal secondary metabolites, (R)-nodulone C (4) and trans-nodulone D (5) has been reported through the chemoenzymatic approach. The strategy utilizes NADPH-dependent naphthol reductases of Magnaporthe grisea for the reduction of putative biosynthetic substrates, synthesized non-enzymatically in multiple steps. A dihydronaphthalenone 32 and cis-nodulone D (30)

Data-driven computer-aided synthesis planning utilizing organic or biocatalyzed reactions from large databases has gained increasing interest in the last decade, sparking the development of numerous tools to extract, apply and score general reaction templates. The generation of reaction rules for enzymatic reactions is especially challenging, since substrate promiscuity varies between enzymes, causing

The importance of epigenetic drug and probe discovery is on the rise. This is not only paramount to identify and develop therapeutic treatments associated with epigenetic processes but also to understand the underlying epigenetic mechanisms involved in biological processes. To this end, chemical vendors have been developing synthetic compound libraries focused on epigenetic targets to increase the