Rh(II) catalysed intramolecular C-H insertion of diazo substrates in water: a simple and efficient approach to catalyst reuse

Water is an efficient solvent for the Rh2(OAc)4 catalysed intramolecular C-H insertion of a range of diazo substrates without competitive water insertion. Due to the high solubility and stability of the catalyst in water, the catalyst can be efficiently reused.     

A Comparative Study of Naproxen – Beta Cyclodextrin Complexes Prepared by Conventional Methods and Using Supercritical Carbon Dioxide

Naproxen is a poorly soluble anti-inflammatorydrug, the solubility of which canbe enhanced by complexation withbeta-cyclodextrin. Besides that, the inclusioncomplex reduces the incidence of gastrointestinal side effects of the drug. The aim of this work was to compare the physicochemical characteristics of the solid complexes prepared by traditional methods (kneading, freeze-drying and spray-drying) and using a supercritical fluid technology. The unusual solvent properties of carbon dioxide above their critical temperature and pressure were exploited in order to prepare inclusion compounds. Complexes prepared using supercritical fluid technology showed similar properties to those of freeze-drying andspray-drying complexes as proved by DSC, FT-IRand UV.     

Influence of the tannin structure on the disruption effect of carbohydrates on protein-tannin aggregates

The disrupting effect of three different ionic carbohydrates (xanthan, pectin and gum arabic) on the formation of tannin-protein insoluble aggregates was assessed by nephelometry using bovine serum albumin (BSA) and several procyanidin fractions previously extracted from grape seeds. The presence in solution of any of the carbohydrates studied was found to restrain the formation of insoluble protein-tannin aggregates for every procyanidin fraction used. Xanthan was the most effective carbohydrate, whereas gum arabic was the least effective. The present work has revealed that the disrupting effect of carbohydrates is quite different depending on the procyanidin structure complexity. In general, the three carbohydrates studied revealed a similar trend in that their disrupting effect on tannin-BSA aggregate formation decreased with increase of the procyanidin degree of polymerization.     

Evaluating and clustering retrosynthesis pathways with learned strategy

With recent advances in the computer-aided synthesis planning (CASP) powered by data science and machine learning, modern CASP programs can rapidly identify thousands of potential pathways for a given target molecule. However, the lack of a holistic pathway evaluation mechanism makes it challenging to systematically prioritize strategic pathways except for using some simple heuristics. Herein, we introduce a data-driven approach to evaluate the relative strategic levels of retrosynthesis pathways using a dynamic tree-structured long short-term memory (tree-LSTM) model. We first curated a retrosynthesis pathway database, containing 238k patent-extracted pathways along with ∼55 M artificial pathways generated from an open-source CASP program, ASKCOS. The tree-LSTM model was trained to differentiate patent-extracted and artificial pathways with the same target molecule in order to learn the strategic relationship among single-step reactions within the patent-extracted pathways. The model achieved a top-1 ranking accuracy of 79.1% to recognize patent-extracted pathways. In addition, the trained tree-LSTM model learned to encode pathway-level information into a representative latent vector, which can facilitate clustering similar pathways to help illustrate strategically diverse pathways generated from CASP programs.

Tree-structured long short-term memory neural model learns to understand the retrosynthesis design strategies from patent-extracted retrosynthetic pathway data.     

Giant Anomalous Hall and Nernst Conductivities in Magnetic All-d Metal Heusler Alloys

All-d Heuslers are a category of novel compounds combining versatile functionalities such as caloric responses and spintronics with enhanced mechanical properties. Despite the promising transport properties (anomalous Hall (AHC) and anomalous Nernst (ANC) conductivities) shown in the conventional Co₂XY Heuslers with p-d hybridization, the all-d Heuslers with only d-d hybridization open a new horizon to search for new candidates with outstanding transport properties. In this work, the AHC and ANC are evaluated for thermodynamically stable ferro/ferri-magnetic all-d-metal regular Heusler compounds based on high-throughput first-principles calculations. It is observed that quite a few materials exhibit giant AHCs and ANCs, such as cubic Re₂TaMn with an AHC of 2011 S cm^-1, and tetragonal Pt₂CrRh with an AHC of 1966 S cm^-1 and an ANC of 7.50 A m^-1K^-1. Comprehensive analysis on the electronic structure reveals that the high AHC can be attributed to the occurrence of the Weyl nodes or gapped nodal lines in the neighborhood of the Fermi level. The correlations between such transport properties and the number of valence electrons are also thoroughly investigated, which provides a practical guidance to tailor AHC and ANC via chemical doping for transverse thermoelectric applications.     

Determination of manganese and zinc in powdered chocolate samples by slurry sampling using sequential multi-element flame atomic absorption spectrometry

In the present work, a slurry sampling flame atomic absorption spectrometric method to determine directly manganese and zinc in powdered chocolate samples is proposed. The optimization step was performed using univariate methodology involving the following factors: nature and concentration of the acid solution, sonication time, and particle size. The established conditions led to the use of a sample mass of 150 mg, 2.0 mol L^− 1 nitric acid solution, sonication time of 15 min, and a slurry volume of 50 mL. This method allows the determination of manganese and zinc with detection limit of 52 and 61 ng g^− 1, respectively, and a precision expressed as relative standard deviation (RSD) of 2.6% and 3.2% (both, n = 10) for contents of manganese and zinc of 52.4 and 100.0 μg g^− 1, respectively. The proposed method was applied for determination of manganese and zinc in five powdered chocolate samples. In these, the manganese content varied from 42.8 to 52.7 and from 88.6 to 102.4 μg g^− 1 of zinc. The analytical results were compared with the results obtained by analysis of these samples after digestion using open vessel and acid bomb digestion procedures and determination using FS-FAAS. The statistical comparison by t-test (95% confidence level) showed no significant difference between these results.     

Recent discoveries on the structure of iodine(iii) reagents and their use in cross-nucleophile coupling

This perspective article discusses structural features of iodine(iii) compounds as a prelude to presenting their use as umpolung reagents, in particular as pertains to their ability to promote the selective coupling of two nucleophilic species via 2e⁻ oxidation.

This perspective article discusses structural features of iodine(iii) compounds as a prelude to presenting their use as umpolung reagents, to promote the selective coupling of two nucleophilic species via 2e⁻ oxidation.     

An insight into the mechanisms of the phototoxic response induced by cyamemazine in cultured fibroblasts and keratinocytes

The phototoxicity of cyamemazine (CMZ, Tercian), a neuroleptic of the phenothiazine family, has recently been reported in humans. CMZ has an absorbance maximum at 267 nm (molar absorptivity, 25,800 M(-1) cm(-1)) but a weaker molar absorptivity in the ultraviolet A (UV-A) region. CMZ exhibits a fluorescence with maximum emission at 535 nm and a quantum yield of 0.11. CMZ is a powerful photosensitizing agent toward HS 68 human skin fibroblasts and NCTC 2544 keratinocytes. At a UV-A radiation dose of 10 J/cm2, innocuous to cells in the absence of CMZ, the LD50 (lethal dose corresponding to 50% killing) are 0.5 and 1 microM for the fibroblasts and the keratinocytes, respectively, after overnight incubation with the drug. Short incubation times do not significantly alter the LD50. The CMZ-induced phototoxicity is accompanied by lipid membrane peroxidation consistent with the amphiphilic character of this photosensitizer. Keratinocytes are an order of magnitude less sensitive to the photosensitized lipid peroxidation than fibroblasts. Microspectrofluorometry reveals that lysosomal membranes are major sites of CMZ incorporation into the two cell lines because a Forster-type resonance energy transfer process occurs from CMZ to LysoTracker Red DND99 (LTR), a specific fluorescent probe of lysosomal membranes. The CMZ-photosensitized destruction of LTR demonstrates that CMZ retains its photosensitizing capacity after its lysosomal uptake.     

On the index of elliptic partial differential operators inR n

Summary Let A= be an elliptic differential operator inR _u, If, for |α|=l, the coefficients a_α are ? nearly constant ? and, for |α|<l, they tend to zero at infinity with a certain swiftness, it is proved that A is a Fredholm operator with index_x(A)=0 between a suitable weighted Sobolev space M contained in W^l,p (R n) and L^p(R ⁿ, (1+|x|)^lp)== . It is shown, by counterexamples, that the above result, holds only if n>l, p>n/(n−l) and that isomorphism results can be obtained, in general only if the coefficients a_α(|α|<l) are assumed to be ? sufficiently small ? also on compact sets. Then a Sturm-Liouville type problem is studied and a class of negative and falling off at infinity potentials V(x) is constructed in such a way that the Schr?dinger operator H=−Δ+V(x), in L²(R ⁿ), has a zero eigenvalue.

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Sunto Sia un operatore differenziale ellittico inR ⁿ. Se, per |α|=l, i coefficienti a_α sono ? quasi costanti ? e, per |α|<l, tendono a zero all'infinito con una certa rapidità, si dimostra che A è un operatore di Fredholm con indice_X(A)=0 tra un opportuno spazio di Sobolev con peso M contenuto in W^l,p(R ⁿ) ed L^p(R ⁿ, (1+|x|)^lp)== . Si prova, mediante controesempi, che tale risultato è valido solo se n>l, p>n/(n−l) e che teoremi di isomorfismo si possono ottenere, in generale, solo se si assume che i coefficienti a_α (|α|<l) sono ? sufficientemente piccoli ? anche su insiemi compatti. Si studia quindi un problema del tipo Sturm-Liouville e si costruisce una classe di potenziali V(x) negativi e convergenti a zero all'infinito, tali che l'operatore di Schr?dinger H=−δ+V(x) in L²(R ⁿ) abbia un autovalore nullo.

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Entrata in Redazione il 10 agosto 1977.

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Work supported by C.N.R. (G.N.A.F.A.).