Recent Advances in DMSO-Based Direct Synthesis of Heterocycles

Besides serving as a low-toxicity, inexpensive and easily accessible solvent, dimethyl sulfoxide (DMSO) has also been extensively used as a versatile reagent for the synthesis of functionalized molecules. Dimethyl sulfoxide can not only be utilized as a carbon source, a sulfur source and an oxygen source, but also be employed as a crucial oxidant enabling various transformations. The past decade has witnessed a large number of impressive achievements on the direct synthesis of heterocycles as well as modifications of heterocyclic compounds by applying DMSO as a reagent. This review summarized the DMSO-based direct heterocycle constructions from 2012 to 2022.     

Synthesis of a bicyclic analogue of AZT restricted in an unusual O4'-endo conformation.

The [3.2.0]bicyclic beta-nucleoside analogue 5 has been designed as a conformationally restricted analogue of the anti-HIV drug AZT. The synthesis of 5 as well as its alpha-anomer 29 is hereby described. The synthesis was accomplished from D-arabinose via a modified Corey-Link procedure stereoselectively incorporating the azide moiety as well as a methyl ester function. When the tert-butyldiphenylsilyl group was used as a permanent protecting group, a selective formation of an oxetane ring failed. When using the p-methoxyphenyl group as a permanent protecting group, 5 and 29 were efficiently obtained via a selective reduction of the ester, a nucleobase coupling followed by separation of the anomers and ring-closing procedures. The nucleoside 5 is conformationally restricted in an unusual O4'-endo (East) conformation, which is an intermediate between the North- and South-type conformations. Nevertheless, neither 5 nor 29 displayed any anti-HIV activity.     

Low-field NMR for quality control on oils

Oil is a prominent, but multifaceted material class with a wide variety of applications. Technical oils, crude oils as well as edibles are main subclasses. In this review, the question is addressed how low-field NMR can contribute in oil characterization as an analytical tool, mainly with respect to quality control. Prerequisite in the development of a quality control application, however, is a detailed understanding of the oils and of the measurement. Low-field NMR is known as a rich methodical toolbox that was and is explored and further developed to address questions about oils, their quality, and usability as raw materials, during production and formulation as well as in use.     

Lipid II: total synthesis of the bacterial cell wall precursor and utilization as a substrate for glycosyltransfer and transpeptidation by penicillin binding protein (PBP) 1b of Escherichia coli.

An essential feature in the life cycle of both gram positive and gram negative bacteria is the production of new cell wall. Also known as murein, the cell wall is a two-dimensional polymer, consisting of a linear, repeating N-acetylmuramic acid (MurNAc) and N-acetylglucosamine (GlcNAc) motif, cross-linked via peptides appended to MurNAc. The final steps in the maturation of murein are catalyzed by a single, bifunctional enzyme, known as a high MW, class A penicillin binding protein (PBP). PBPs catalyze polymerization of the sugar units (glycosyltransfer), as well as peptide cross-linking (transpeptidation) utilizing Lipid II as substrate. Detailed enzymology on this enzyme has been limited, due to difficulties in obtaining sufficient amounts of Lipid II, as well as the availability of a convenient and informative assay. We report the total chemical synthesis of Lipid II, as well as the development of an appropriate assay system and the observation of both catalytic transformations.     

Proficiency testing programmes as a tool in food quality assurance: Overview of Italian experiences

Proficiency testing involves the performance of test procedures on routine samples by a number of laboratories. Interlaboratory proficiency testings provide multiple benefits to participants since they play a key-role in the total quality control of laboratory activities. They serve as a means of self-improving, as a mechanism of continuing education and as a source of information for accreditation agencies. This review highlights basic principles, benefits, criteria and capabilities of a proficiency testing programme for food analysis laboratories as well as their role in the implementation of rapidly developing food control legislation.     

Effect of butterfly-shaped sulfur-bridged ligand and counter anions on the catalytic activity and diastereoselectivity of organobismuth complexes

In the direct Mannich reaction and synthesis of α,β-unsaturated ketones, the use of organobismuth complexes as catalysts leads to high diastereoselectivity and products of single trans conformation. In this paper, we illustrate the relationship between structure and catalytic activity as well as diastereoselectivity of organobismuth complexes having a 5,6,7,12-tetrahydrodibenz [c,f][1,5]thiobismocine framework as well as bearing a butterfly-shaped sulfur-bridged ligand and tunable anions. With the exposed bismuth center acting as a Lewis acid site and the uncoordinated lone pair electrons of sulfur as a Lewis base site, the cationic organobismuth complexes work as bifunctional Lewis acid/base catalysts. Due to the steric influence of the butterfly-shaped structure and synergistic effect of Lewis acid and Lewis base centers, the complexes can direct substrate attack in organic synthesis. By adjusting the electron-withdrawing ability of the counter anions, the S-Bi bond strength can be regulated, leading to a significant change in Lewis acidity and Lewis basicity as well as catalytic activity. Through synergistic modulation of the above effects, one can control the diastereoselectivity of the organobismuth complexes for the generation of a single diastereoisomer.     

Polylactic acid (PLA) synthesis and modifications: a review

This article reviews various methods of synthesizing polycondensation and ring-opening polymerization and modifying properties of polylactic acid (PLA), which may be used as biomaterials, such as a drug carrier in a drug delivery system, as a cell scaffold and suture in tissue engineering, and as packaging materials in packaging engineering field. Copolymerization of lactide with other monomers or polymers such as malic acid, polyethylene glycol (PEG), polyglycolic acid (PGA), or dextran, as well as blending polylactide with natural derivatives and other methods of modification are discussed. Surface modifications of PLA-type copolymers, such as surface coating, chemical modification, and plasma treatment are described.     

N,N-dimethylformamide: a multipurpose building block

Often used as a common solvent for chemical reations and utilized widely in industry as a reagent, N,N-dimethylformamide (DMF) has played an important role in organic synthesis for a long time. Numerous highly useful articles and reviews discussing its utilizations have been published. With a focus on the performance of DMF as a multipurpose precursor for various units in numerous reactions, this Minireview summarizes recent developments in the employment of DMF in the fields of formylation, aminocarbonylation, amination, amidation, and cyanation, as well as its reaction with arynes.     

Direct fluorescence monitoring of the delivery and cellular uptake of a cancer-targeted RGD peptide-appended naphthalimide theragnostic prodrug

Presented here is a multicomponent synthetic strategy that allows for the direct, fluorescence-based monitoring of the targeted cellular uptake and release of a conjugated therapeutic agent. Specifically, we report here the design, synthesis, spectroscopic characterization, and preliminary in vitro biological evaluation of a RGD peptide-appended naphthalimide pro-CPT (compound 1). Compound 1 is a multifunctional molecule composed of a disulfide bond as a cleavable linker, a naphthalimide moiety as a fluorescent reporter, an RGD cyclic peptide as a cancer-targeting unit, and camptothecin (CPT) as a model active agent. Upon reaction with free thiols in aqueous media at pH 7.4, disulfide cleavage occurs. This leads to release of the free CPT active agent, as well as the production of a red-shifted fluorescence emission (λ(max) = 535 nm). Confocal microscopic experiments reveal that 1 is preferentially taken up by U87 cells over C6 cells. On the basis of competition experiments involving okadaic acid, an inhibitor of endocytosis, it is concluded that uptake takes place via RGD-dependent endocytosis mechanisms. In U87 cells, the active CPT payload is released within the endoplasmic reticulum, as inferred from fluorescence-based colocalization studies using a known endoplasmic reticulum-selective dye. The present drug delivery system (DDS) could represent a new approach to so-called theragnostic agent development, wherein both a therapeutic effect and drug uptake-related imaging information are produced and can be readily monitored at the subcellular level. In due course, the strategy embodied in conjugate 1 could allow for more precise monitoring of dosage levels, as well as an improved understanding of cellular uptake and release mechanisms.     

Review and Perspectives of the Use of Alginate as a Polymer Matrix for Microorganisms Applied in Agro-Industry

Alginate is a polysaccharide with the property of forming hydrogels, which is economic production, zero toxicity, and biocompatibility. In the agro-industry, alginate is used as a super absorbent polymer, coating seeds, fruits, and vegetables and as a carrier of bacteria and fungi as plant-growth promoters and biocontrol. The latter has a high impact on agriculture since the implementation of microorganisms in a polymer matrix improves soil quality; plant nutrition, and is functional as a preventive measure for the appearance of phytopathogenic. Additionally, it minimizes losses of foods due to wrong post-harvest handling. In this review, we provide an overview of physicochemical properties of alginate, some methods for preparation and modification of capsules and coatings, to finally describe its application in agro-industry as a matrix of plant-growth-promoting microorganisms, its effectiveness in cultivation and post-harvest, and its effect on the environment, as well as the prospects for future agro-industrial applications.     

Mapping electric fields generated by microelectrodes using optically trapped charged microspheres

In this work, we show a new technique to measure the direction and amplitude of the electric field generated by microelectrodes in a liquid environment, as often used in microfluidic devices. The method is based on the use of optical tweezers as a force transducer. A trapped, charged particle behaves as a probe. With this technique, it is possible to obtain a detailed map of the electric field, even for very complex electrode structures with a resolution below a micrometre and with a sensitivity as low as a few hundreds of V m(-1).     

Synthesis of 9-geranylterpinolene as a mixture of isomers,and synthesis of α- and β-springene,possible kairomones of the beech leaf-mining weevil,Orchestes fagi (L.)

The beech leaf-mining weevil, Orchestes fagi (L.), also known as the beech flea weevil, is a common and widespread pest of beech, Fagus sylvatica L., in its native Europe. It now appears to be well established in Nova Scotia, Canada. We have previously reported the synthesis of 9-geranyl-p-cymene and 9-geranyl-α-terpinene, as they are both found in eclosing beech buds, and have researched the synthesis of other diterpenes that are isomers of 9-geranyl-α-terpinene. We now wish to report a synthesis of the diterpene 9-geranylterpinolene as a mixture of isomers, as a novel diterpene, and as a possible kairomone of O. fagi. Also, all trans-α-springene, its 3Z-isomer, and β-springene were synthesized as a mixture, as well as pure β-springene, utilizing known methods.     

Usage of Date Stones as Adsorbents: A Review

In this article, the use of date stones (thrown as a waste material) as adsorbent for the removal of a variety of adsorbates in aqueous and gaseous streams have been reviewed. Adsorption plays a role in the wastewater treatment as a polishing process, especially on activated carbon at tertiary treatments. In this review, the preparation and characterization technique along with the applications of the date stones as adsorbent has been presented in detail. A comprehensive study and the comparison of the available data in literature reveal that the date stones can be used as a potential adsorbent for a wide variety of toxic contaminants such as dyes, heavy metals, insecticides, etc.     

掺氮介孔炭作为双功能材料用于氧还原与超级电容器

以壳聚糖为含氮碳源,正硅酸乙酯为软模板,硝酸镍为催化剂,通过简单的低温水热法及后续炭化,成功合成出掺氮介孔炭材料（NMC-1）.NMC-1含有多孔结构以及氮氧等杂原子,能提高其电催化性能、双电层电容与赝电容.由于NMC-1在碱液中表现出显著的催化氧还原反应活性和具有较高的超级电容器比电容（在0.2A/g时为252F/g）及好的循环稳定性,因此,它有可能作为一种可再生、环保的双功能材料同时应用于燃料电池与超级电容器领域.     

Spektrochemische schnellbestimmung einiger spurenelemente in der kohlenasche mit alumininmelektroden und verwendung des sichtbaren spektralgebietes

Using an a.c. arc and visible spectral lines a spectrographic method for the rapid determination of traces of Co, Cr, Ga.In, Pb and V in synthetic coal ashes has been worked out, in which the samples are burned in Al electrodes thus avoiding perturbation by cyanogen bands. With the help of intensity-time studies an exposure time of 10 sec was found giving optimum power of detection as well as optimum reproducibility. By a suitable choice of experimental conditions the background density was adjusted to a value which permitted making accurate background corrections and using the background as reference radiation at the same time. Variation of the method included the application of intermediate diaphragms and the use of Fe-lines as well as of the background as reference signals with and without background correction. The standard deviations as well as the tested concentration ranges are reported.     

Enzyme-based biocatalysis for the treatment of organic pollutants and bioenergy production

Enzyme-based biocatalysis is emerging as an advanced technique to develop green processes that help to maintain the sustainability of the environment. The bioremediation of toxic organic pollutants and waste to bioenergy production using enzymes as biocatalysts is rapidly growing due to its eco-friendly and sustainable nature. Additionally, a range of microbial species that typically grow on organic wastes can be used to produce these enzymes in an efficient manner. This is seen as a potential strategy for the development of cost-effective manufacturing for a number of biotechnological applications. The present study discusses biocatalysis as a promising and sustainable method toward the bioremediation of hazardous organic pollutants as well as for bioenergy production, based on the immense potential of enzymes as biocatalysts. Emphasis has been placed on evaluating the critical elements that can enhance the production of enzymes used as biocatalysts, as well as their functional effectiveness and stability.     

圆柱形纳米孔道内受限溶液I2/Ar的分子动力学模拟研究

利用分子动力学模拟方法, 考察了受限于圆柱形纳米孔道内I2/Ar溶液的振动传能及扩散动力学. 计算得到了溶质振动弛豫时间T1、溶剂轴向扩散系数Dz随孔道半径变化的规律. 结果表明: T1随着孔道半径的增大而减小; 而Dz随着孔道半径的增大而增大; 与预期的一致, 随着孔道半径的增大, 孔道的限制作用逐渐减小, T1与Dz趋近于相应的非受限溶液体相值. 此外, 通过考察溶质、溶剂与孔道的相互作用, 在原子、分子层次上揭示了限制作用对传能与传质影响的机制.     

GC-MS Determination of an Unknown Pesticide. II. An Experiment Investigating Quality of Analysis Using Random Sampling and Estimation of Variance

Newly devised components are described which significantly enhance both the scientific and pedagogical components of a previously published, qualitatively oriented experiment for students in an undergraduate instrumental analysis course. To provide a laboratory exercise containing as much real-world experience as possible, the earlier experiment was modified in such a way as to allow its use as a quantitative experiment illustrating such principles as sampling, experimental design, analysis of variance, and the use of internal standards.