Uncharged Compounds Research Articles

ConfRank: Improving GFN-FF Conformer Ranking with Pairwise Training.

Conformer ranking is a crucial task for drug discovery, with methods for generating conformers often based on molecular (meta)dynamics or sophisticated sampling techniques. These methods are constrained by the underlying force computation regarding runtime and energy ranking accuracy, limiting their effectiveness for large-scale screening applications. To address these ranking limitations, we introduce ConfRank, a machine learning-based approach that enhances conformer ranking using pairwise training. We demonstrate its performance using GFN-FF-generated conformer ensembles, leveraging the DimeNet++ architecture trained on pairs of 159 760 uncharged organic compounds from the GEOM data set with r2SCAN-3c reference level. Instead of predicting only on single molecules, this approach captures relative energy differences between conformers, leading to a significant improvement of the overall conformational ranking, outperforming GFN-FF and GFN2-xTB. Thereby, the pairwise RMSD of the relative energy difference of two conformers can be reduced from 5.65 to 0.71 kcal mol-1 on the test data set, allowing to correctly identify up to 81% of all lowest lying conformers correctly (GFN-FF: 10%, GFN2-xTB: 47%). The ConfRank approach is cost-effective, allowing for scalable deployment on both CPU and GPU, achieving runtime accelerations by up to 2 orders of magnitude compared to GFN2-xTB. Out-of-sample investigations on CREST-generated conformer ensembles from the QM9 data set and conformers taken from an extended GMTKN55 data set show promising results for the robustness of this approach. Thereby, ranking correlation coefficient such as Spearman can be improved to 0.90 (GFN-FF: 0.39, GFN2-xTB: 0.84) reducing the probability of an incorrect sign flip in pairwise energy comparison from 32 to 7%. On the extended GMTKN55 subsets the pairwise MAD (RMSD) could be reduced on almost all subsets by up to 62% (58%) with an average improvement of 30% (29%). Moreover, an exemplary case study on vancomycin shows similar performance, indicating applicability to larger (bio)molecular structures. Furthermore, we motivate the usage of the pairwise training approach from a theoretical perspective, highlighting that while pairwise training can lead to a decline in single sample prediction of absolute energies for ML models, it significantly enhances conformer ranking performance. The data and models used in this study are available at https://github.com/grimme-lab/confrank.

Pharmacokinetics of nano- and microcrystal formulations of low solubility compounds after intramuscular injection to mice.

The aim of this study was to investigate the pharmacokinetics (PK) of poorly soluble compounds when administered intramuscularly (i.m.) as crystalline particles of different sizes. Three uncharged compounds (griseofulvin, AZ'72, and AZ'07) with varying aqueous solubility were dosed to mice at 10 and 50mg/kg as nano- and microparticle formulations. The PK of the compounds was evaluated. The smaller particles of the drugs resulted in higher maximum plasma concentration (Cmax) and area under the plasma concentration-time profile (AUC) at 50mg/kg. There was a dose-proportional increase in AUC but less than dose dose-proportional increase in Cmax. The evaluation at 10mg/kg was more complex as increased exposure for nanoparticles was only observed for griseofulvin which has the highest solubility. In addition, there was an increase in half-life with an increase in dose. This study highlights that general expectations based on in vitro dissolution (i.e. that smaller particles dissolve faster than larger particles when surrounded by liquid) do not always translate to in vivo and demonstrates the importance of understanding the physicochemical properties of the drug, the characteristics of the formulations and the microphysiology at the delivery site.

A basic study of pretreatment method using antibody modified with glucose oxidase for pungent‐taste measurement of taste sensor

AbstractA polyclonal antibody against the analog of piperine, which is a typical pungent taste substance, was produced, and its binding ability to piperine was evaluated using a surface plasmon resonance sensor. The antibody was labeled with glucose oxidase (GOx), and the hydrogen ions produced by the enzymatic reaction were measured at a lipid polymer membrane electrode for sourness in a taste sensor. The results showed that piperine could be detected by that polyclonal antibody; the response of the sourness sensor increased in dependence on the GOx‐labeled antibody concentration when the GOx of GOx‐labeled antibody was reacted with glucose. Thus, it was shown that uncharged pungent compounds can be converted into hydrogen ions. Pungent taste can be measured by the taste sensor using GOx‐labeled antibodies, and GOx‐labeled antibodies can be used as a pretreatment.

味覚センサの辛味測定のためのグルコース酸化酵素標識抗体を用いた前処理法の基礎検討

A polyclonal antibody against the analog of piperine, which is a typical pungent taste substance, was produced, and its binding ability to piperine was evaluated using a surface plasmon resonance sensor. The antibody was labeled with glucose oxidase (GOx), and the hydrogen ions produced by the enzymatic reaction were measured at a lipid polymer membrane electrode for sourness in a taste sensor. The results showed that piperine could be detected by that polyclonal antibody; the response of the sourness sensor increased in dependence on the GOx-labeled antibody concentration when the GOx of GOx-labeled antibody was reacted with glucose. Thus, it was shown that uncharged pungent compounds can be converted into hydrogen ions. Pungent taste can be measured by the taste sensor using GOx-labeled antibodies, and GOx-labeled antibodies can be used as a pretreatment.

Mesoionic compounds: the role of intermolecular interactions in their crystalline design

The quest for understanding crystal structures using supramolecular cluster demarcation has been applied to various uncharged compounds, and, more recently, to charged compounds. So, what would be the supramolecular behavior of mesoionic compounds?

Molecular simulation of lignin-related aromatic compound permeation through gram-negative bacterial outer membranes

Lignin, an abundant aromatic heteropolymer in secondary plant cell walls, is the single largest source of renewable aromatics in the biosphere. Leveraging this resource for renewable bioproducts through targeted microbial action depends on lignin fragment uptake by microbial hosts and subsequent enzymatic action to obtain the desired product. Recent computational work has emphasized that bacterial inner membranes are permeable to many aromatic compounds expected from lignin depolymerization processes. In this study, we expand on these findings through simulations for 42 lignin-related compounds across a gram-negative bacterial outer membrane model. Unbiased simulation trajectories indicate that spontaneous crossing for the full outer membrane is relatively rare at molecular simulation timescales, primarily due to preferential membrane partitioning and slow diffusion within the lipopolysaccharide layer within the outer membrane. Membrane partitioning and permeability coefficients were determined through replica exchange umbrella sampling simulations to overcome sampling limitations. We find that the glycosylated lipopolysaccharides found in the outer membrane increase the permeation barrier to many lignin-related compounds, particularly the most hydrophobic compounds. However, the effect is relatively modest; at industrially relevant concentrations, uncharged lignin-related compounds will readily diffuse across the outer membrane without the need for specific porins. Together, our results provide insight into the permeability of the bacterial outer membrane for assessing lignin fragment uptake and the future production of renewable bioproducts.

QSAR and molecular docking study for uncharged acetylcholinesterase reactivators inhibited by organophosphate

Organophosphate can be toxic to humans by inhibiting the acetylcholinesterase which plays an important role in the nerve impulse transmission system. Poisoning of this compound can be treated by uncharged compounds as acetylcholinesterase reactivators which work in the central nervous system. The purpose of this study is to create a QSAR modeling, designing new reactivators and perform molecular docking to find reactivators with better activity. Two QSAR equation models were obtained as follows: Model 1: logIC50 = 0.1943 (±0.0475) [RDF115u] - 0.0910 (±0.0668) [RDF155e] - 0.1115 (±0.0142) [RDF25i] - 17.7959 (±4.8605) [E1e] + 16.0383 (±2.6845). Model 2: logIC50 = 0.1992 (± 0.0464) [RDF115u] – 0.2658 (± 0.1751) [RDF155p] - 0.1126 (± 0.0136) [RDF25i] - 18.1643 (± 4.7041) [E1e] + 16.2485 (± 2.5996). Three design compounds with the best activity prediction of QSAR modeling were used for molecular docking. logIC50 prediction values of reactivators U1, U2 and U3 from model 1 were respectively 1.19, 0.103 and 0.142. The result of logIC50 prediction from model 2 is 1.33, 0.203 and 0.179 respectively. Molecular docking showed that the design compound interacted with the same enzyme residues as the native ligand with docking scores of U1, U2, U3 reactivator respectively -9.5, -9.7 and -9.1 kcal/mol. These results indicate that the design compounds have better activity than previous studies and the potential to be used as an organophosphate-inhibited acetylcholines-terase reactivator.

Downscaling reverse osmosis for single-household wastewater reuse: towards low-cost decentralised sanitation through a batch open-loop configuration

Abstract There is a significant demand for water recycling in low-income countries. However, wastewater infrastructure is primarily decentralised, necessitating the development of affordable household-scale reclamation technology. In this study, a batch open-loop reverse osmosis (RO) system is therefore investigated as a low-cost clean water reclamation route from highly saline concentrated blackwater. In a single-stage configuration, increasing feed pressure from 10 to 30 bars improved selective separation at water recovery exceeding 85%, whereas lower cross-flow velocity improved product recovery, reducing specific permeate energy demand from 21 to 4.8 kWh m−3. Rejection achieved for total phosphorous (99%), chemical oxygen demand (COD, 96%), and final pH (8.7) of the RO permeate was compliant with the ISO30500 reuse standard for discharge. However, the rejection of total nitrogen in the RO permeate was non-compliant with the reuse standard due to the transmission of low-molecular weight (MW) uncharged organic compounds. It is suggested that rejection may be improved by increasing feed pressure to rebalance selectivity but may also be controlled by reducing fluid residence time (storage) to constrain the hydrolysis of urea. The economic analysis identified that a high-pressure 1812 element cost of ∼US$30 meets the sanitation affordability index of US$0.05 capita−1 day−1. However, the unit cost of a high-pressure feed pump must be reduced to ∼US$500 to obtain an affordable system cost. These unit costs can be achieved by manufacturing 1812 elements at economies of scale, and by adopting pumping solutions that have been developed for other applications requiring high pressures and low flows. Overall, our findings suggest that RO in the batch open-loop configuration has the potential to deliver affordable and safe water production from blackwater in a decentralised (single-household) context.

Molecular and Electronic Structures of Neutral Polynitrogens: Review on the Theory and Experiment in 21st Century.

The data on the existence and physicochemical characteristics of uncharged single element chemical compounds formed by nitrogen atoms and containing more than two nuclides of this element (from N4 to N120, oligomeric and polymeric polynitrogens) have been systematized and generalized. It has been noticed that these data have a predominantly predictive character and were obtained mainly using quantum chemical calculations of various levels (HF, DFT, MP, CCSD etc.). The possibility of the practical application of these single element compounds has been considered. The review mainly covers articles published in the last 25 years. The bibliography contains 128 references.

Transport mechanisms behind enhanced solute rejection in forward osmosis compared to reverse osmosis mode

Forward osmosis (FO) as emerging technology for water treatment was reported to exhibit higher solute rejections compared to reverse osmosis (RO). In this work, the rejection of two uncharged organic compounds (nicotinamide, caffeine) were investigated the first time in low-pressure reverse osmosis (LPRO) mode and FO under similar process conditions utilizing the same hollow fiber forward osmosis membrane modules. FO consistently showed higher rejection than LPRO mode for both nicotinamide (FO: 94.8%, LPRO: 85.5%) and caffeine (FO: 99.9%, LPRO: 99.2%). To elucidate the influence of draw solute on the rejection, different salts (NaCl, MgCl2, MgSO4), concentrations, and draw flow rates were investigated. A rise in draw concentration increased rejection in FO for all salts (RNaCl:94.1→97.2%,RMgCl2:94.5→97.5%,RMgSO4:90.0→94.7%) indicating an enhancement of rejection due to the presence of salt on the permeate side of the membrane. Two theories are proposed: While the resistance for feed solute transport could be increased due to the counter-directed reverse solute flux and the presence of salt in the support layer, the driving force for feed solute diffusion might be lowered due the presence of an ionic compound on the permeate side of the membrane.

Sorption of urea hydrogen peroxide by co-pyrolysed bone meal and cow dung slowed-down phosphorus and nitrogen releases but boosted agronomic efficiency

Co-pyrolysis of animal manure biomass with bone meal (BM) and soaking of the resultant biochar in urea containing solutions may offer a sustainable and cheap way of formulating slow-release nitrogen (N) and phosphorus (P) fertilisers. This method can lead to optimisation of the carbon sequestration capacity of the biochar, abatement of environmental pollution by P and N and alleviation of the severity of the projected future scarcity of P. A few studies have indicated that sorption can create efficient slow-release fertilisers although all of them utilised charged moieties such as ammonium ions to formulate them and as a result, there is a paucity of data concerning the efficiency of fertilisers formulated using uncharged compounds like urea. It’s against that background that we examined the possibility of leveraging co-pyrolysis and sorption with urea containing solutions to formulate slow-release N and P fertilisers along with assessing the agronomic efficiency of the formulated fertilisers through cultivating lettuce in pots for two seasons. Both urea-hydrogen peroxide (UHP) and urea were utilised as N sources. UHP (CDBM-UHP) and urea (CDBM-Urea) containing biochars averagely released 64.40% and 87.00% of the added N, respectively over the 28-day incubation period with the amount of N released decreasing with increasing concentrations of BM in the biochar. Lettuce yields and nutrient use efficiencies of N and P were higher in the CDBM-UHP than in the CDBM-Urea treatments. It’s therefore clear that sorption of UHP by BM containing biochar concomitantly slows-down releases of N and P and boosts the agronomic efficiency of the fertilisers.

Treatment of non-ideality in the SPACCIM multiphase model – Part 2: Impacts on the multiphase chemical processing in deliquesced aerosol particles

Abstract. Tropospheric deliquesced particles are characterised by concentrated non-ideal solutions (“aerosol liquid water” or ALW) that can affect the occurring multiphase chemistry. However, such non-ideal solution effects have generally not yet been considered in and investigated by current complex multiphase chemistry models in an adequate way. Therefore, the present study aims at accessing the impact of non-ideality on multiphase chemical processing in concentrated aqueous aerosols. Simulations with the multiphase chemistry model (SPACCIM-SpactMod) are performed under different environmental and microphysical conditions with and without a treatment of non-ideal solutions in order to assess its impact on aqueous-phase chemical processing. The present study shows that activity coefficients of inorganic ions are often below unity under 90 % RH-deliquesced aerosol conditions and that most uncharged organic compounds exhibit activity coefficient values of around or even above unity. Due to this behaviour, model studies have revealed that the inclusion of non-ideality considerably affects the multiphase chemical processing of transition metal ions (TMIs), oxidants, and related chemical subsystems such as organic chemistry. In detail, both the chemical formation and oxidation rates of Fe(II) are substantially lowered by a factor of 2.8 in the non-ideal base case compared to the ideal case. The reduced Fe(II) processing in the non-ideal base case, including lowered chemical rates of the Fenton reaction (−70 %), leads to a reduced processing of HOx∕HOy under deliquesced aerosol conditions. Consequently, higher multiphase H2O2 concentrations (larger by a factor of 3.1) and lower aqueous-phase OH concentrations (lower by a factor of ≈4) are modelled during non-cloud periods. For H2O2, a comparison of the chemical reaction rates reveals that the most important sink, the reaction with HSO3-, contributes with a 40 % higher rate in the non-ideal base case than in the ideal case, leading to more efficient sulfate formation. On the other hand, the chemical formation rates of the OH radical are about 50 % lower in the non-ideal base case than in the ideal case, leading to lower degradation rates of organic aerosol components. Thus, considering non-ideality influences the chemical processing and the concentrations of organic compounds under deliquesced particle conditions in a compound-specific manner. For example, the reduced oxidation budget under deliquesced particle conditions leads to both increased and decreased concentration levels, e.g. of important C2∕C3 carboxylic acids. For oxalic acid, the present study demonstrates that the non-ideality treatment enables more realistic predictions of high oxalate concentrations than observed under ambient highly polluted conditions. Furthermore, the simulations imply that lower humidity conditions, i.e. more concentrated solutions, might promote higher oxalic acid concentration levels in aqueous aerosols due to differently affected formation and degradation processes.

Formation and Fate of Carbonyls in Potable Water Reuse Systems.

Low molecular weight, uncharged compounds have been the subject of considerable study at advanced treatment plants employed for potable water reuse. However, previously identified compounds only account for a small fraction of the total dissolved organic carbon remaining after reverse osmosis treatment. Uncharged carbonyl compounds (e.g., aldehydes and ketones) formed during oxidation have rarely been monitored in potable water reuse systems. To determine the relative importance of these compounds to final product water quality, samples were collected from six potable water reuse facilities and one conventional drinking water treatment plant. Saturated carbonyl compounds (e.g., formaldehyde, acetone) and α,β-unsaturated aldehydes (e.g., acrolein, crotonaldehyde) were quantified with a sensitive new analytical method. Relatively high concentrations of carbonyls (i.e., above 7 μM) were observed after ozonation of wastewater effluent. Biological filtration reduced concentrations of carbonyls by over 90%. Rejection of the carbonyls during reverse osmosis was correlated with molecular weight, with concentrations decreasing by 33% to 58%. Transformation of carbonyls resulted in decreases in concentration of 10% to 90% during advanced oxidation, with observed decreases consistent with rate constants for reactions of the compounds with hydroxyl radicals. Overall, carbonyl compounds accounted for 19% to 38% of the dissolved organic carbon in reverse osmosis-treated water.

Organic Cation Transporters in Health and Disease.

The organic cation transporters (OCTs) OCT1, OCT2, OCT3, novel OCT (OCTN)1, OCTN2, multidrug and toxin exclusion (MATE)1, and MATE kidney-specific 2 are polyspecific transporters exhibiting broadly overlapping substrate selectivities. They transport organic cations, zwitterions, and some uncharged compounds and operate as facilitated diffusion systems and/or antiporters. OCTs are critically involved in intestinal absorption, hepatic uptake, and renal excretion of hydrophilic drugs. They modulate the distribution of endogenous compounds such as thiamine, L-carnitine, and neurotransmitters. Sites of expression and functions of OCTs have important impact on energy metabolism, pharmacokinetics, and toxicity of drugs, and on drug-drug interactions. In this work, an overview about the human OCTs is presented. Functional properties of human OCTs, including identified substrates and inhibitors of the individual transporters, are described. Sites of expression are compiled, and data on regulation of OCTs are presented. In addition, genetic variations of OCTs are listed, and data on their impact on transport, drug treatment, and diseases are reported. Moreover, recent data are summarized that indicate complex drug-drug interaction at OCTs, such as allosteric high-affinity inhibition of transport and substrate dependence of inhibitor efficacies. A hypothesis about the molecular mechanism of polyspecific substrate recognition by OCTs is presented that is based on functional studies and mutagenesis experiments in OCT1 and OCT2. This hypothesis provides a framework to imagine how observed complex drug-drug interactions at OCTs arise. Finally, preclinical in vitro tests that are performed by pharmaceutical companies to identify interaction of novel drugs with OCTs are discussed. Optimized experimental procedures are proposed that allow a gapless detection of inhibitory and transported drugs.

A Tale of Two Treatments: The Multiple Barrier Approach to Removing Chemical Contaminants During Potable Water Reuse.

In response to water scarcity and an increased recognition of the risks associated with the presence of chemical contaminants, environmental engineers have developed advanced water treatment systems that are capable of converting municipal wastewater effluent into drinking water. This practice, which is referred to as potable water reuse, typically relies upon reverse osmosis (RO) treatment followed by exposure to ultraviolet (UV) light and addition of hydrogen peroxide (H2O2). These two treatment processes individually are capable of controlling many of the chemical and microbial contaminants in wastewater; however, a few chemicals may still be present after treatment at concentrations that affect water quality. Low-molecular weight (<200 Da), uncharged compounds represent the greatest challenge for RO treatment. For potable water reuse systems, compounds of greatest concern include oxidation products formed during treatment (e.g., N-nitrosodimethylamine, halogenated disinfection byproducts) and compounds present in wastewater effluent (e.g., odorous compounds, organic solvents). Although the concentrations of most of these compounds decrease to levels where they no longer compromise water quality after they encounter the second treatment barrier (i.e., UV/H2O2), low-molecular weight compounds that are resistant to direct photolysis and exhibit low reactivity with hydroxyl radical (·OH) may persist. While attempts to identify the compounds that pass through both barriers have accounted for approximately half of the dissolved organic carbon remaining after treatment, it is unlikely that a significant fraction of the remaining unknowns will ever be identified with current analytical techniques. Nonetheless, the toxicity-weighted concentration of certain known compounds (e.g., disinfection byproducts) is typically lower in RO-UV/H2O2 treated water than conventional drinking water. To avoid the expense associated with managing the concentrate produced by RO, environmental engineers have begun to employ alternative treatment barriers. The use of alternatives such as nanofiltration, ozonation followed by biological filtration, or activated carbon filtration avoids the problems associated with the production and disposal of RO concentrate, but they may allow a larger number of chemical contaminants to pass through the treatment process. In addition to the transformation products and solvents that pose risks in the RO-UV/H2O2 system, these alternative barriers are challenged by larger, polar compounds that are not amenable to oxidation, such as perfluoroalkyl acids and phosphate-containing flame retardants. To fully protect consumers who rely upon potable water reuse systems, new policies are needed to prevent chemicals that are difficult to remove during advanced treatment from entering the sewer system. By using knowledge about the composition of municipal wastewater and the mechanisms through which contaminants are removed during treatment, it should be possible to safely reuse municipal wastewater effluent as a drinking water source.

Continuous micellar electrokinetic focusing of neutral species driven by ion concentration polarization.

Ion concentration polarization (ICP) has been broadly applied to accomplish electrokinetic focusing of charged species. However, ICP-based extraction and enrichment of uncharged (neutral) compounds, important for pharmaceutical, biological, and environmental applications, has not yet been reported. Here, we report the ICP-based continuous extraction of two neutral compounds from aqueous solution, by their partition into an ionic micellar phase. Our initial results show that the efficiency of the extraction increases with the concentration of the surfactant comprising the micellar phase, reaching 98 ± 2%, and drops precipitously when the concentration of the target compound exceeds the capacity of the micelles. As a key feature relevant to the practical application of this method, we show that focusing occurs even an order of magnitude below the critical micelle concentration through the local enrichment and assembly of surfactants into micelles, thus minimizing their consumption. To underscore the relevance of this approach to water purification, this method is applied to the extraction of pyrene, a model for polyaromatic hydrocarbons. This approach provides access to a broad range of strategies for selective separation that have been developed in micellar electrokinetic chromatography.

Fast blood plasma separation device for point-of-care applications

In this work, a simple device for extremely fast separation of blood plasma from diluted whole blood was developed. The device accommodates an asymmetric polysulfone membrane/supporting membrane sandwich that allows collection of 10 µL blood plasma into a narrow glass capillary in less than 10 s. The composition of diluent solution was optimized in order to achieve maximum recoveries for selected metabolites of alcohol intoxication. 5% solution of [tris(hydroxymethyl)methylamino] propanesulfonic acid provided recoveries of formate, oxalate and glycolate close to 100% and only moderate erythrocyte lysis. Both charged and uncharged compounds from the whole blood samples can be analyzed in the separated blood plasma by capillary electrophoresis with contactless conductometric detection and spectrophotometry, respectively. The developed device might find wide application in on-site testing and point-of-care analysis, when only microliter volumes of whole blood are available.

UC2 search: using unique connectivity of uncharged compounds for metabolite annotation by database searching in mass spectrometry-based metabolomics.

SummaryFor metabolite annotation in metabolomics, variations in the registered states of compounds (charged molecules and multiple components, such as salts) and their redundancy among compound databases could be the cause of misannotations and hamper immediate recognition of the uniqueness of metabolites while searching by mass values measured using mass spectrometry. We developed a search system named UC2 (Unique Connectivity of Uncharged Compounds), where compounds are tentatively neutralized into uncharged states and stored on the basis of their unique connectivity of atoms after removing their stereochemical information using the first block in the hash of the IUPAC International Chemical Identifier, by which false-positive hits are remarkably reduced, both charged and uncharged compounds are properly searched in a single query and records having a unique connectivity are compiled in a single search result.Availability and implementationThe UC2 search tool is available free of charge as a REST web service (http://webs2.kazusa.or.jp/mfsearcher) and a Java-based GUI tool.Supplementary information Supplementary data are available at Bioinformatics online.

Chiral-at-Metal Phosphorescent Square-Planar Pt(II)-Complexes from an Achiral Organometallic Ligand.

The synthesis and characterization of a new kind of cis- and trans-cyclometalated square-planar platinum(II) complexes is reported. Uncharged organometallic compounds carrying one or two of the C∧N-donor ligand LCN were prepared. Due to the heterobidentate coordination of the achiral chelate ligand, the formed [PtLCNCl(SEt2)], cis- and trans-[PtLCN2] complexes are chiral with the metal serving as the stereo center. The enantiomers of complex trans-[PtLCN2] could be separated and their absolute configuration was determined by anomalous X-ray diffraction, in accordance with CD spectroscopic results and TD-DFT calculations. All compounds were fully characterized by NMR spectroscopy, mass spectrometry and X-ray structure determination. The photophysical properties of trans-[PtLCN2] have been investigated showing phosphorescence in solution and in the solid state with a moderate quantum yield. For the enantiomers, strong circular dichroism (CD) and circularly polarized luminescence (CPL) effects were observed, rendering this new structural motif suitable for application in chiroptical and luminescent materials.

Salting-out and salting-in effects of organic compounds and applications of the salting-out effect of Pentasodium phytate in different extraction processes

The influence of different uncharged and charged organic compounds on the Lowest Solution Temperature (LST) of a water/dipropylene glycol propyl ether (DPnP) mixture is investigated. Depending on the nature of the additive, a salting-out or salting-in behavior could be observed. For the binary mixture, a salting-out effect is associated with a decrease of the LST with increasing additive concentrations. The reverse effects are observed with increasing salting-in additive concentrations. Typical sugars, short carboxylate sodium salts, ammonium organic salts and amino-acids were found to be salting-out, whereas all studied sweeteners and organic acids showed a salting-in behavior. The Pentasodium phytate ((Phy5−, 5Na+)) was found being the most efficient organic salting-out compound. Three possible applications were investigated in order to compare the salting-out effect of (Phy5−, 5Na+) to classical inorganic salts. First, the liquid-liquid extraction of 5-hydroxymethylfurfural (HMF) was investigated and compared to former results obtained using lithium, sodium and aluminium sulfate salts. Secondly, we considered a liquid-liquid, ethanol-water separation and compared the results to the one obtained using ammonium sulfate and potassium pyrophosphate. Finally, the salting-out effect of (Phy5−, 5Na+) on glycerol was investigated and also compared to the inorganic salts, sodium chloride and lithium sulfate as well as potassium and sodium phosphates.Due to higher water solubility, (Phy5−, 5Na+) allowed a more pronounced separation of HMF than the tested sulfate salts. This high water solubility drives also to a more pronounced separation of ethanol in comparison to ammonium sulfate; potassium pyrophosphate being the most water soluble and most efficient salt to separate ethanol and water. The use of (Phy5−, 5Na+) and potassium pyrophosphate showed a salting-out effect on glycerol in contrast to the inorganic salts sodium chloride and lithium sulfate for which a salting-in effect on glycerol was observed. The salting-out effect of sodium triphosphate was limited by its water solubility.