High Temperature Continuous Flow Syntheses of Iron Oxide Nanoflowers Using the Polyol Route in a Multi-Parametric Millifluidic Device

One of the most versatile routes for the elaboration of nanomaterials in materials science, including the synthesis of magnetic iron oxide nanoclusters, is the high-temperature polyol process. However, despite its versatility, this process still lacks reproducibility and scale-up, in addition to the low yield obtained in final materials. In this work, we demonstrate a home-made multiparametric continuous flow millifluidic system that can operate at high temperatures (up to 400 °C). After optimization, we validate its potential for the production of nanomaterials using the polyol route at 220 °C by elaborating ferrite iron oxide nanoclusters called nanoflowers (CoFe2O4, Fe3O4, MnFe2O4) with well-controlled nanostructure and composition, which are highly demanded due to their physical properties. Moreover, we demonstrate that by using such a continuous process, the chemical yield and reproducibility of the nanoflower synthesis are strongly improved as well as the possibility to produce these nanomaterials on a large scale with quantities up to 45 g per day.

Exploiting the Chiral Ligands of Bis(imidazolinyl)- and Bis(oxazolinyl)thiophenes—Synthesis and Application in Cu-Catalyzed Friedel–Crafts Asymmetric Alkylation

Five new C2-symmetric chiral ligands of 2,5-bis(imidazolinyl)thiophene (L1–L3) and 2,5-bis(oxazolinyl)thiophene (L4 and L5) were synthesized from thiophene-2,5-dicarboxylic acid (1) with enantiopure amino alcohols (4a–c) in excellent optical purity and chemical yield. The utility of these new chiral ligands for Friedel–Crafts asymmetric alkylation was explored. Subsequently, the optimized tridentate ligand L5 and Cu(OTf)2 catalyst (15 mol%) in toluene for 48 h promoted Friedel–Crafts asymmetric alkylation in moderate to good yields (up to 76%) and with good enantioselectivity (up to 81% ee). The bis(oxazolinyl)thiophene ligands were more potent than bis(imidazolinyl)thiophene analogues for the asymmetric induction of the Friedel–Crafts asymmetric alkylation.

The Cosmic Carbon Footprint of Massive Stars Stripped in Binary Systems

The cosmic origin of carbon, a fundamental building block of life, is still uncertain. Yield predictions for massive stars are almost exclusively based on single-star models, even though a large fraction interact with a binary companion. Using the MESA stellar evolution code, we predict the amount of carbon ejected in the winds and supernovae of single and binary-stripped stars at solar metallicity. We find that binary-stripped stars are twice as efficient at producing carbon (1.5–2.6 times, depending on choices regarding the slope of the initial mass function and black hole formation). We confirm that this is because the convective helium core recedes in stars that have lost their hydrogen envelope, as noted previously. The shrinking of the core disconnects the outermost carbon-rich layers created during the early phase of helium burning from the more central burning regions. The same effect prevents carbon destruction, even when the supernova shock wave passes. The yields are sensitive to the treatment of mixing at convective boundaries, specifically during carbon-shell burning (variations up to 40%), and improving upon this should be a central priority for more reliable yield predictions. The yields are robust (variations less than 0.5%) across our range of explosion assumptions. Black hole formation assumptions are also important, implying that the stellar graveyard now explored by gravitational-wave detections may yield clues to better understand the cosmic carbon production. Our findings also highlight the importance of accounting for binary-stripped stars in chemical yield predictions and motivates further studies of other products of binary interactions.

Straightforward Regio- and Diastereoselective Synthesis, Molecular Structure, Intermolecular Interactions and Mechanistic Study of Spirooxindole-Engrafted Rhodanine Analogs

Straightforward regio- and diastereoselective synthesis of bi-spirooxindole-engrafted rhodanine analogs 5a–d were achieved by one-pot multicomponent [3 + 2] cycloaddition (32CA) reaction of stabilized azomethine ylide (AYs 3a–d) generated in situ by condensation of L-thioproline and 6-chloro-isatin with (E)-2-(5-(4-chlorobenzylidene)-2,4-dioxothiazolidin-3-yl)-N-(2-morpholinoethyl)acetamide. The bi-spirooxindole-engrafted rhodanine analogs were constructed with excellent diastereo- and regioselectivity along with high chemical yield. X-ray crystallographic investigations for hybrid 5a revealed the presence of four contiguous stereocenters related to C11, C12, C19 and C22 of the spiro structure. Hirshfeld calculations indicated the presence of many short intermolecular contacts such as Cl...C, S...S, S...H, O...H, N...H, H...C, C...C and H...H interactions. These contacts played a very important role in the crystal stability. The polar nature of the 32CA reaction was studied by analysis of the conceptual DFT reactivity indices. Theoretical study of this 32CA reaction indicated that it takes place through a non-concerted two-stage one-step mechanism associated with the nucleophilic attack of AY 3a to the electrophilic ethylene derivative.

Active pyridinium based ionic liquid anchored quinuclidine organocatalyst for Morita-Baylis-Hillman reaction

: In the present manuscript, we easily synthesized three different types of ionic liquid supported 3-quinuclidinone organocatalysts such as [PyAmEQ][BF4] (Py-CATALYST-1), [PyAmEQ][PF6] (Py-CATALYST-2), and [PyAmEQ][NTf2] (Py-CATALYST-3). After performing the careful characterization of the above catalysts with sophisticated analytical techniques, we utilized them as a catalyst to study the passive Morita-Baylis-Hillman reaction. The corresponding Morita-Baylis-Hillman adducts were easily isolated, followed by the simple ether extraction method. Moreover, the above protocol also promoted low catalyst loading, short reaction time, wide substrate scope, easy product, and catalyst recycling. We easily recycled the catalytic system for 5 runs with no noticeable loss in the chemical yield. Additionally, Py-CATALYST-3 was also used to prepare biologically active materials, i.e., N-((E,3S,4R)-5-benzylidene-tetrahydro-4-hydroxy-6-oxo-2H-pyran-3-yl) palmitamide derivatives.

On the Use of Real-World Datasets for Reaction Yield Prediction

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 relationship to high-throughput experimentation (HTE) datasets is described. For chemical yield predictions, a key task in chemical synthesis, an attributed graph neural network (AGNN) performs as good or better than the best previous models on two HTE datasets for the Suzuki and Buchwald-Hartwig reactions. However, training of the AGNN on the ELN dataset does not lead to a predictive model. The implications of using ELN data for training ML-based models are discussed in the context of yield predictions.

Use of the chemical Fricke dosimeter and its modifications for dosimetry of gamma neutron radiation of a pulsed reactor

The paper investigates the characteristics of the chemical Fricke dosimeter (with the standard composition (D1), without NaCl addition to the solution (D2), without NaCl but with a tenfold increased concentration of Fe2+ (D3)) under continuous and pulsed irradiation with an ultra-high dose rate of the BARS-6 reactor with unshielded metallic cores. The dosimeter radiosensitivity had a linear dependence on the gamma neutron radiation dose in a range of 25 to 750 Gy and was respectively 1.96 ± 0.05 μGy–1 (D1), 2.04 ± 0.05 μGy–1 (D2), and 2.08 ± 0.5 μGy–1 (D3) in the continuous irradiation mode, and 1.24 ± 0.05 μGy–1, 2.00 ± 0.05 μGy–1, and 1.94 ± 0.05 μGy–1 in the pulsed irradiation mode. This makes ≈ 60% of their sensitivity to the 60Со gamma radiation (3.40 ± 0.02 μGy–1), and 36%, 1.6 times as less, for a standard Fricke dosimeter irradiated in the pulsed mode. The experimental value of the radiation chemical yield, Gn(Fe3+), for all solution modifications and both irradiation modes varied slightly and was 0.84 ± 0.11 μM/J on the average, except for the standard solution in the pulsed mode (0.66 ± 0.07 μM/J). The neutron doses determined by chemical and activation dosimeters coincided within the error limits, but the chemical dosimeter readings were systematically higher, by about 20%. Therefore, in the fission spectrum neutron dose rate range of 0.4 to 7×108 Gy/min, there is no dose rate effect both in the standard Fricke dosimeter version (without NaCl) and in the modified version, which makes it possible to use modified Fricke dosimeters to assess the physical and dosimetry characteristics of mixed gamma neutron radiation beams.

Organocatalytic Asymmetric Michael Addition in Aqueous Media by a Hydrogen-Bonding Catalyst and Application for Inhibitors of GABAB Receptor

Catalysts based on (R, R)-1,2-diphenylethylenediamine are, as chiral organic catalysts, applied to the asymmetric Michael addition to α, β-unsaturated nitroalkenes under neutral conditions. The role of an aqueous medium for organic catalytic activity can be reversed concerning hydrophilic-hydrophobic function depending on the reaction conditions. In this study, to provide an environmentally friendly system, the thiourea-based catalyst substituted with 3,5-(CF3)2-Ph was used in water solvents. The hydrophobic effect of the substituent provided fast reaction, high chemical yield, and mirror-image selectivity. This reaction allowed the preparation of GABAB agonists in an optically pure manner. Additionally, GABA (γ-aminobutyric acid) analogs such as baclofen and phenibut were synthesized as R-type S-type with high optical purity.

Radiochemical separation and purification of non-carrier-added silicon-32

32Si (T 1/2 = 153(19) y) is an extremely rare, naturally-occurring isotope that has been considered as a geochronometer suitable for radiometric dating over the time span from 100 to 1000 years ago – a time span that has proved rather difficult to explore in this manner. Past attempts to determine the 32Si half-life have resulted in a wide range of values possessing significant uncertainties because only low-activity samples could be made available for such measurements. Utilizing the 590 MeV ring cyclotron at PSI, megabecquerel quantities of 32Si have been produced by exposing metallic vanadium discs to high-energy protons in order to induce spallation. A radiochemical separation procedure has been successfully developed and applied to the irradiated discs as part of the SINCHRON project, based on a combination of ion-exchange and extraction resins. The process was shown to be reliable and robust with a high chemical yield. Radiochemically pure 32Si solutions with activity concentrations of up to several kBq/g can be produced to perform individual measurements (AMS, ICP-MS, LSC) for various studies. Thus, a careful redetermination of the 32Si half-life has become feasible to begin the first steps toward the confident implementation of this radionuclide for geochronological purposes.

Synthesis and X-ray Crystal Structure of New Substituted 3-4’-Bipyrazole Derivatives. Hirshfeld Analysis, DFT and NBO Studies

A new compounds named 3-4’-bipyrazoles 2 and 3 were synthesized in high chemical yield from a reaction of pyran-2,4-diketone 1 with aryl hydrazines under thermal conditions in MeOH. Compound 2 was unambiguously confirmed by single-crystal X-ray analysis. It crystalizes in a triclinic crystal system and space group P-1. Its crystal structure was found to be in good agreement with the spectral characterizations. With the aid of Hirshfeld calculations, the H...H (54.8–55.3%) and H...C (28.3–29.2%) intermolecular contacts are the most dominant, while the O...H (5.8–6.5%), N...H (3.8–4.6%) and C...C (3.0–4.9%) are less dominant. The compound has a polar nature with a net dipole moment of 6.388 Debye. The BD(2)C31-C32→BD*(2)N4-C34 (27.10 kcal/mol), LP(1)N5→BD*(2)C31-C32 (36.90 kcal/mol), BD(1)C32-C34→BD*(1)C18-C31 (6.78 kcal/mol) and LP(1)N4→BD*(1)N5-C31 (7.25 kcal/mol) are the strongest π→π*, n→π*, σ-σ* and n→σ* intramolecular charge transfer processes, respectively.