Microbial hydroxylation of S-(-)-perillyl alcohol by Fusarium heterosporium

S-(-)-Perillyl alcohol (p-mentha-1, 8-diene-7-ol) (1) (500 mg) was converted by Fusarium heterosporium ATCC 15625 over 10 days at 25 degrees C to a new metabolite, 1,2-dihydroxyperillyl alcohol (p-mentha-8-en-1,2,7-triol) (3) in a yield of 13% (70 mg). The structure of 3 was established by IR and NMR spectroscopic, specific rotation, and mass spectral studies.     

A [Pd]-mediated ω-alkynone cycloisomerization approach for the central tetrahydropyran unit and the synthesis of C(31)-C(48) fragment of aflastatin A

A concise assembly of the central tetrahydropyran unit of aflastatin A featuring a Pd-mediated alkynone cycloisomerization to provide a glycal and its subsequent stereoselective hydroboration to deliver the requisite stereochemistry at C(33) and C(34) centers is documented.     

An in vitro and in vivo study of a novel zinc complex, zinc N-(2-hydroxyacetophenone)glycinate to overcome multidrug resistance in cancer

Multiple drug resistance (MDR) remains a major clinical challenge for cancer treatment. P-glycoprotein is the major contributor and they exceed their role in the chemotherapy resistance of most of the malignancies. Attempts in several preclinical and clinical studies to reverse the MDR phenomenon by using MDR modulators have not yet generated promising results. In the present study, a co-ordination complex of zinc viz., Zn N-(2-hydroxyacetophenone)glycinate (ZnNG) has been synthesized, characterized and its antitumour activity was tested in vitro against drug sensitive and resistant human T-lymphoblastic leukemic cell lines (CCRF/CEM and CEM/ADR5000 respectively) and in vivo against Ehrlich ascites carcinoma (EAC) implanted in female Swiss albino mice. To evaluate the cytotoxic potential of ZnNG, we used sensitive CCRF/CEM and drug resistant CEM/ADR 5000 cell lines in vitro. Moreover, ZnNG also has the potential ability to reverse the multidrug resistance phenotype in drug resistant CEM/ADR 5000 cell line and induces apoptosis in combination with vinblastine. ZnNG remarkably increases the life span of Swiss albino mice bearing sensitive and doxorubicin resistant subline of EAC in presence and in absence of doxorubicin. In addition, intraperitoneal application of ZnNG in mice does not show any systemic toxicity in preliminary trials in normal mice. To conclude, a novel metal chelate of zinc viz., ZnNG, may be a promising therapeutic agent against sensitive as well as drug resistant cancers.     

Aza-Nazarov cyclization cascades

Benzamides with tethered acetal groups undergo reactions in CF₃SO₃H to give ring-fused isoindolinones by a cyclization cascade. The reaction initially forms an N-acyliminium ion which then gives the isoindolinone by the aza-Nazarov reaction. An unusual variant also cyclizes at the allylic position.     

New Molybdaborane Clusters with a Bridged Phosphido Ligand

Abstract  

Treatment of [Cp*MoCl₄], 1 (Cp* = η⁵-C₅Me₅), with [LiBH₄.thf] in toluene at −40 °C, followed by thermolysis with [(thf)Li{CH(PPh₂–BH₃)₂}] results in the formation of a new class of phosphido bridged molybdaborane [(Cp*Mo)₂B₄H₇(μ-PPh₂)], 2 which has been characterized crystallographically. In addition, the above reaction also produces known [(Cp*Mo)₂B₅H₉], 3 and an unusual molybdaborane [(Cp*Mo)₂B₅H₈(O ⁱ Pr)], 4 ( ⁱ Pr = –CH(CH₃)₂). All the new compounds have been characterized in solution by ¹H, ¹¹B, ¹³C, ³¹P NMR spectroscopy and the structural types were unambiguously established by X-ray crystallographic analysis of compounds 2 and 4.     

Synthesis and spectroscopic studies of Sb(III) and Bi(III) complexes of semicarbazones

Summary New complexes of Sb(III) and Bi(III) with semicarbazones of the general formulae SbCl₃ L and BiCl₃ L (whereL=semicarbazones) have been prepared and characterized by IR,¹H- and¹³C-NMR spectral measurements. The results of the spectroscopic studies indicate that the semicarbazone ligands act as bidentate in all the complexes. All complexes are non-electrolytes inDMF solution. The molecular weight determinations indicate that the compounds are monomeric.

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Synthese und spektroskopische Untersuchungen von Sb(III)- und Bi(III)-Komplexen mit Semlcarbazonen

Zusammenfassung Es wurden neue Komplexe von Sb(III) und Bi(III) mit Semicarbazonen von der allgemeinen Formel SbCl₃ L und BiCl₃ L (L=verschiedenene Semicarbazone) dargestellt und mittels IR,¹H- und¹³C-NMR charakterisiert. Die spektroskopischen Untersuchungen zeigten, daß die Semicarbazon-Liganden in allen Komplexen zweizähnig agieren. Molekulargewichtsbestimmungen zeigten die monomere Natur der Verbindungen an.

     

New 1,8-naphthyridine-based probes for the selective fluorescence signalling of toxic cadmium: synthesis,photophysical studies and molecular modelling

Newly synthesised 1,8-naphthyridine-based molecular probes, NAP-1 and NAP-2, exhibit highly selective fluorescence responses towards the toxic cadmium over coordinatively competing Zn²⁺ and several other metal ions examined. On the one hand, NAP-1 (MeOH:H₂O, v/v 80:20, pH 7.4) exhibits ca. 1.5 order of magnitude higher stability constant for Cd²⁺ over Zn²⁺; on the other hand, NAP-2 in MeOH offers unique selectivity only towards Cd²⁺, exhibiting both absorbance and emission red shifts as well as fluorescence enhancement. By ¹H NMR analysis, the tetra-coordinated binding is indicated at least for the NAP-1+Cd²⁺ complex and theoretical calculations reveal relatively stronger binding of Cd²⁺ over Zn²⁺.

     

Free surface dynamics of thin second-grade fluid over a heated stretching sheet with variable fluid properties: long-wave modeling and simulation

Meccanica - In this paper, we extend the long-wave theory for the free surface dynamics of the thin non-Newtonian second-grade fluid (ANZIAM J 60(2): 249–268, 2018) over the stretching sheet...     

Asymptotic theory of dependent Bayesian multiple testing procedures under possible model misspecification

We study asymptotic properties of Bayesian multiple testing procedures and provide sufficient conditions for strong consistency under general dependence structure. We also consider a novel Bayesian multiple testing procedure and associated error measures that coherently accounts for the dependence structure present in the model. We advocate posterior versions of FDR and FNR as appropriate error rates and show that their asymptotic convergence rates are directly associated with the Kullback–Leibler divergence from the true model. The theories hold regardless of the class of postulated models being misspecified. We illustrate our results in a variable selection problem with autoregressive response variables and compare our procedure with some existing methods through simulation studies. Superior performance of the new procedure compared to the others indicates that proper exploitation of the dependence structure by multiple testing methods is indeed important. Moreover, we obtain encouraging results in a maize dataset, where we select influential marker variables.

     

Games,Critical Paths and Assignment Problems in Permutation Flow Shops and Cyclic Scheduling Flow Line Environments

In this paper we address the non-pre-emptive flow shop scheduling problem for makespan minimization in a new modelling framework. A lower bound generation scheme is developed by using appropriately defined linear assignment problems and, based on this new approach, a special class of permutation flow shop problems is identified. We present a game theoretic interpretation of our modelling approach which leads to an integer programming formulation of the scheduling problem. A new branch and bound scheme is developed based on these results. The major advantage of our modelling framework and branch-and- bound approach is that it can be easily extended to address a general class of cyclic scheduling problems for production flow lines with blocking. After a discussion of this extension, we report on computational experience that indicates the very satisfactory performance of the new optimal solution procedure for cyclic scheduling problems with finite capacity buffers.