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.     

Aluminosilicate and aluminosilicate based polymer composites: Present status,applications and future trends

Aluminosilicates have traditionally been important materials for applications related to adsorbents, water softeners, catalysis and mechanical and thermal reinforcement due to their high surface area, excellent thermal/hydrothermal stability, high shape-selectivity and superior ion-exchange ability. Recently, their use as polymer fillers has allowed to increasingly extending their application range to innovative areas such as medical and biological fields as well as in sensors, filtration membranes, energy storage and novel catalysis routes. Further, the large versatility and tailoring possibilities of both filler and matrix indicates this area as one of the enabling key technologies of the near future.This work summarizes the main developments up to date in this increasingly interesting field, focuses on the main applications already developed as well as on the key challenges for the near future.     

A Convergent Total Synthesis of the Death Cap Toxin α‐Amanitin

The toxic bicyclic octapeptide α‐amanitin is mostly found in different species of the mushroom genus Amanita, with the death cap (Amanita phalloides) as one of the most prominent members. Due to its high selective inhibition of RNA polymerase II, which is directly linked to its high toxicity, particularly to hepatocytes, α‐amanitin received an increased attention as a toxin‐component of antibody‐drug conjugates (ADC) in cancer research. Furthermore, the isolation of α‐amanitin from mushrooms as the sole source severely restricts compound supply as well as further investigations, as structure–activity relationship (SAR) studies. Based on a straightforward access to the non‐proteinogenic amino acid dihydroxyisoleucine, we herein present a robust total synthesis of α‐amanitin providing options for production at larger scale as well as future structural diversifications.     

Reaction of Oximes of α-Diketones with Diphosphorous Tetraiodide for Preparation of Oxadiazoles and Nitriles

The utility of diphosphorous tetraiodide as a new, mild, condensing agent for synthesis of oxadiazole is described. These data indicate the simple dehydration of oximes to 1,2,5-oxadiazole as well as the rearrangements of oximes to normal Beckmann product 1,2,4-oxadiazole. However, mono-oxime of benzil undergoes abnormal Beckman rearrangement to benzaldehyde as major product. The described method is simple and important for the synthesis of the oxadiazoles as well as for nitriles.     

片状纳米CuO用于苯乙烯氧化反应的研究

苯甲醛又称安息香醛,是医药、染料、香料工业的一种重要的中间体,主要用于制造品绿、月桂醛、月桂酸等;也有时用作有机溶剂,测定臭氧及位于羰基旁边的亚甲基及检定酚和生物碱的试剂.传统的工业生产方法是以石油化工中的甲苯为原料,经氯化生成二氯化苄,再经酸性或碱性水解、真空     

Benzothiazoles from Condensation of o-Aminothiophenoles with Carboxylic Acids and Their Derivatives: A Review

Nowadays, organic chemists are interested in the field of heterocyclic chemistry due to its use in the synthesis of a great variety of biologically active compounds. Heterocyclic compounds are widely found in nature and are essential for life. Among these, some natural nitrogen containing heterocyclic compounds have been used as chemotherapeutic agents. Their attachment to sugar molecules either as thioglycosides or as nucleosides analogues plays an important role in vital biological processes as well as in synthetic organic chemistry. Molecules containing benzothiazole (BT) nuclei are of this interesting class of compounds because some of them have been found to have a wide variety of biological activities. In this sense, we selected this topic to review and to then summarize the procedures related to the condensation reactions of o-aminothiophenoles (ATPs) as well as their disulfides with carboxylic acids, esters, orthoesters, acyl chlorides, amides, and nitriles. The condensation reactions with carbon dioxide (CO₂) are included. Conventional methods with the use of acid and metal catalysts as well as recent green techniques, such as microwave irradiation, the use of ionic liquids, and ultrasound (US) chemistry, which have proven to have many advantages, were found in the review.     

Development of a nano-liquid chromatography on chip tandem mass spectrometry method for high-sensitivity hepcidin quantitation

Microfluidic LC systems present undeniable advantages over classical LC in terms of sensitivity. Hepcidin, a peptide marker of clinical disorders linked to iron metabolism, was used as model to demonstrate peptide quantification potentialities of LC-chip coupled to a nanoelectrospray source ion trap mass spectrometer in an aqueous sample. First, stable isotope labelled hepcidin was chosen as internal standard and gradient as well as sample compositions were optimised using design of experiments as development tool. The method was then prevalidated using accuracy profiles in order to select the most appropriate response function and to confirm the ability of the technique to quantify low hepcidin concentration. A reliable and very sensitive quantitation method was finally obtained using this integrated microfluidic technology. Indeed, good results with respect to accuracy, trueness and precision were achieved, as well as a very low limit of quantitation (0.07 ng/ml). Method suitability of nano-LC on chip tandem mass spectrometry for hepcidin quantitation was also demonstrated in complex media such as human plasma.     

Review: Dielectrophoresis in cell characterization

Many cellular functions are affected by and thus can be characterized by a cell's electrophysiology. This has also been found to correspond to other biophysical parameters such as cell morphology and mechanical properties. Dielectrophoresis (DEP) is an electrostatic technique which can be used to examine cellular biophysical parameters through the measuring of single or multiple cell response to electric field induced forces. This label-free method offers many advantages in characterizing a cell population over conventional electrophysiology methods such as patch clamping; however, it has yet to see mainstream pharmacological application. Challenges such as the transdisciplinary nature of the field bridging engineering and the biological sciences, throughput, specificity as well as standardization are being addressed in current literature. This review focuses on the developments of DEP-based cell electrophysiological characterization where determining cellular properties such as membrane conductance and capacitance, and cytoplasmic conductivity are the primary motivation. A brief theoretical review, techniques for obtaining these cell parameters, as well as the resulting cell parameters and their applications are included in this review. This review aims to further support the development of DEP-based cell characterization as an important part of the future of DEP and electrophysiology research.     

Nitraza-/Oxa-Propylene- and Hydrazonemethylene-Bridged 1,2,4-Nitraminotriazoles and Selected Salts

Two new bridged nitraminotriazoles with bridging oxapropylene and nitrazapropylene moieties were synthesized, and converted into several salts, as well as from the hydrazonemethylene bridged nitraminotriazole. All compounds were fully characterized by NMR and IR spectroscopy, elemental analysis as well as differential thermal analysis. The sensitivity towards friction and impact were determined according to BAM standard technics and the energetic properties were calculated by using the EXPLO5 computer code. The neutral compounds as well as the various salts were examined in terms of their physicochemical properties and detonation performance to each other and compared to the commonly used secondary explosive RDX.     

Interactions and uses of antisense peptides in affinity technology.

Antisense peptides, amino acid sequences encoded in the antisense strand of DNA, can interact with significant affinity and selectivity with their corresponding sensepeptides. Experimentally, sense-antisense peptide recognition has been observed repeatedly. However, skepticism about the biological relevance of this phenomenon has persisted. This is due in part to the unexpected and somewhat couterintutive nature of the interaction as well as to its non-universality as an empirical observation. Nonetheless, antisense peptides in several cases investigated so far have been used as immobilized ligands for the successful affinity chromatographic separation of native (sense) peptides and proteins. For example, immobilized antisense peptides corresponding to Arg8-vasopressin (AVP) have been used to separate vasopressin from oxytocin chromatographically as well as to affinity capture AVP-receptor complex. These results, together with improved understanding of the general features of amino acid sequence which drive antisense-sense peptide interactions as well as new ideas for making antisense peptides chimeras, are beginning to suggest improved ways to make antisense-related peptides as affinity agents for separation as well as for other biotechnology applications.     

和医学相关有机化合物绿色鉴别实验的设计*

为了将医用化学实验中“有机化合物的鉴别”实验更加密切地与医学相关专业结合,并提高实验操作的安全性,降低化学试剂的毒性与刺激性,甄选出一系列与医学密切相关的有机化合物作为待鉴别试剂,同时设计绿色环保、安全低毒、现象明显、操作简便、成本低廉的鉴别方法,为学生实验方案的设计提供指导。以期提高医学生学习的积极性与主动性,促进学生灵活运用知识分析问题、解决问题,为相关教学工作的改进提供借鉴意义。     

Controlled release of volatiles under mild reaction conditions: from nature to everyday products

Volatile organic compounds serve in nature as semiochemicals for communication between species, and are often used as flavors and fragrances in our everyday life. The quite limited longevity of olfactive perception has led to the development of pro-perfumes or pro-fragrances--ideally nonvolatile and odorless fragrance precursors which release the active volatiles by bond cleavage. Only a limited amount of reaction conditions, such as hydrolysis, temperature changes, as well as the action of light, oxygen, enzymes, or microorganisms, can be used to liberate the many different chemical functionalities. This Review describes the controlled chemical release of fragrances and discusses additional challenges such as precursor stability during product storage as well as some aspects concerning toxicity and biodegradability. As the same systems can be applied in different areas of research, the scope of this Review covers fragrance delivery as well as the controlled release of volatiles in general.     

Towards the 150th Anniversary of the Markovnikov Rule

The Markovnikov rule, known to every student of organic chemistry, was formulated 150 years ago, in 1869. During its long history (almost as long as the history of organic chemistry itself), attitudes towards this famous statement of chemical reactivity have evolved from indifference up to the 1930s, through common acceptance as a useful educational paradigm with marginal use in research up to the 1990s, to its vigorous relaunch as an important designation of regioselectivity in the last few decades. The unexpected new popularity of the classical rule is accounted for by the rapid expansion in catalytic addition reactions and their critical importance as highly effective atom‐economical, regioselective methods in modern organic synthesis. A historical outline of the life and achievements of Vladimir Markovnikov is included to reveal the very wide scope of his interests as well as his prophetic predictions on structure, reactivity, selectivity, stereochemistry, and other key issues of organic chemistry.     

Asymmetric multicomponent reactions (AMCRs): the new frontier

Asymmetric multicomponent reactions involve the preparation of chiral compounds by the reaction of three or more reagents added simultaneously. This kind of addition and reaction has some advantages over classic divergent reaction strategies, such as lower costs, time, and energy, as well as environmentally friendlier aspects. All these advantages, together with the high level of stereoselectivity attained in some of these reactions, will force chemists in industry as in academia to adopt this new strategy of synthesis, or at least to consider it as a viable option. The positive aspects as well as the drawbacks of this strategy are discussed in this Review.     

Toward a suitable structural analysis of gene delivery carrier based on polycationic carbohydrates by electron transfer dissociation tandem mass spectrometry

Polycationic carbohydrates represent an attractive class of biomolecules for several applications and particularly as non viral gene delivery vectors. In this case, the establishment of structure-biological activity relationship requires sensitive and accurate characterization tools to both control and achieve fine structural deciphering. Electrospray-tandem mass spectrometry (ESI-MS/MS) appears as a suitable approach to address these questions. In the study herein, we have investigated the usefulness of electron transfer dissociation (ETD) to get structural data about five polycationic carbohydrates demonstrated as promising gene delivery agents. A particular attention was paid to determine the influence of charge states as well as both fluoranthene reaction time and supplementary activation (SA) on production of charge reduced species, fragmentation yield, varying from 2 to 62%, as well as to obtain the most higher both diversity and intensity of fragments, according to charge states and targeted compounds. ETD fragmentation appeared to be mainly directed toward pending group rather than carbohydrate cyclic scaffold leading to a partial sequencing for building blocks when amino groups are close to carbohydrate core, but allowing to complete structural deciphering of some of them, such as those including dithioureidocysteaminyl group which was not possible with CID only. Such findings clearly highlight the potential to help the rational choice of the suitable analytical conditions, according to the nature of the gene delivery molecules exhibiting polycationic features. Moreover, our ETD-MS/MS approach open the way to a fine sequencing/identification of grafted groups carried on various sets of oligo-/polysaccharides in various fields such as glycobiology or nanomaterials, even with unknown or questionable extraction, synthesis or modification steps.     

Application of Carrageenan extract from red seaweed (Rhodophyta) in cosmetic products: A review

Cosmetic industries have expanded globally and will continue to increase as there are consumers. Nowadays, the interest starts to incline towards cosmetics formulated using plant-based ingredients. Marine plants such as seaweed possess numerous natural polysaccharides. Carrageenan is one of the compounds that can be extracted from red seaweed (Rhodophyta). This natural polysaccharide is widely known to act as a thickener, stabilizer, and water-binding agent as well as have diverse biological activities that make it a suitable active ingredient in cosmetic products. The review paper is organized by starting with discussing the significant aspects related to carrageenan which are the source, structure, as well as general and biological properties of carrageenan that make it appropriate to be applied in cosmetics. This paper also highlighted the applications of carrageenan in cosmetics, followed by the extraction method and instrument used.     

Cyclopropylamines from N,N-dialkylcarboxamides and Grignard reagents in the presence of titanium tetraisopropoxide or methyltitanium triisopropoxide

Thirty-three different N,N-dialkyl- and N-alkyl-N-phosphorylalkyl-substituted carboxamides 9-17 were treated with unsubstituted as well as with 2-alkyl-, 2,2-dialkyl-, and 3-alkenyl-substituted ethylmagnesium bromides 6 in the presence of stoichiometric amounts of titanium tetraisopropoxide or methyltitanium triisopropoxide to furnish substituted cyclopropylamines 20-25 in 20-98% yield, depending on the substituents with no (1:1) to excellent (>25:1) diastereoselectivities. Generally higher yields (up to 98%) of the cyclopropylamines 20-28 without loss of the diastereoselectivity were obtained with methyltitanium triisopropoxide as the titanium mediator. Under these conditions, even dioxolane-protected ketones and halogen-substituted and chiral as well as achiral alkyloxyalkyl-substituted carboxamides could be converted to the correspondingly substituted cyclopropylamines with unsubstituted as well as phenyl- and a variety of alkyl-substituted ethylmagnesium bromides in addition to numerous heteroatom-containing (e.g., halogen-, trityloxy-, tetrahydropyranyloxy-substituted) Grignard reagents (62 examples altogether). The transformation of N,N-diformylalkylamines 54 with ethylmagnesium bromide in the presence of methyltitanium triisopropoxide to N,N-dicyclopropyl-N-alkylamines 55 can be brought about in up to 82% yield (6 examples). An asymmetric variant of the titanium-mediated cyclopropanation of N,N-dialkylcarboxamides has been developed by applying chiral titanium mediators generated from stoichiometric amounts of titanium tetraisopropoxide and chiral diamino or diol ligands, respectively. The most efficient chiral mediators turned out to be titanium bistaddolates that provided the corresponding cyclopropylamines with enantiomeric excesses (ee) of up to 84%. Evaluation of several silyl-based additives revealed that the reaction can also efficiently be carried out with substoichiometric amounts (down to 25 mol%) of the titanium reagent, as long as 2-aryl- or 2-ethenyl-substituted ethylmagnesium halides are used and a concomitant slight decrease in yields is accepted. The newly developed methodology was successfully applied for the preparation of analogues with cyclopropylamine moieties of known drugs and natural products such as the nicotine metabolite (S)-Cotinine as well as the insecticides Dinotefuran and Imidacloprid.     

Nucleophilic difluoromethylation and trifluoromethylation using tetrakis(dimethylamino)ethylene (TDAE) reagent

In an effort to find new methodologies to introduce difluoromethylene and trifluoromethyl moieties into organic molecules of synthetic and biological interest, tetrakis(dimethylamino)ethylene (TDAE) was found to be an effective reductant of a series of good electron-acceptors such as bromodifluoromethyl heterocycles, chlorodifluoromethylated ketones as well as perfluoroalkyl iodides; the corresponding anions thus generated under very mild conditions, were successfully engaged in a number of intra- and intermolecular coupling reactions with a series of electrophiles (aldehydes, ketones, α-keto esters, N-tosyl aldimines, acyl chlorides, diol sulphates, disulfides, and diselenides). The corresponding adducts were usually obtained in moderate to good yields and the present method was found to be as good or even better as other most popular approaches. This paper gives an overview of our research efforts in this area as well as results from other groups.