Determination of traces of fluorine or sulfur by x-ray analysis

New X-ray methods have been developed for the determination of as little as 1 μg of fluorine or as little as 0.1 μg of sulfur. Fluorine as fluoride is precipitated as lanthanum fluoride in 75% ethanol-water mixture and determined by measuring the amount of lanthanum present in the precipitate. Sulfur as sulfate is precipitated as barium sulfate from a barium sulfate saturated 50% ethanol-buffer mixture, using selenate as a coprecipitant, and determined by measuring the amount of sulfur present. Sulfur as sulfide is precipitated as cadmium sulfide and determined by measuring the amount of sulfur or cadmium in the precipitate.     

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.     

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.     

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.     

Extraordinary atomic mobility of Au{111} at 80 Kelvin: effect of styrene adsorption

We describe how the presence of styrene, a weakly adsorbed molecule, dramatically restructures the Au{111} surface at temperatures as low as 80 K. The restructuring manifests itself both in mobility of step-edge atoms, as well as changes in the position of the herringbone reconstruction over time. These effects are explained in terms of the preferential adsorption sites of styrene allowing it to assist in atom detachment from step edges, as well as lowering of the energetic barrier for movement of the herringbone reconstruction. This work has important consequences for studies in which Au is used as a support for or as an electrical contact to molecules.     

咪草烟分子印迹聚合物的制备及其选择性吸附性能的研究

以丙烯酸为聚合单体,TMPTA为交联剂,AIBN为引发剂,咪草烟为模板分子,采用在低温光聚合的方法,制备了对咪草烟分子具有选择性识别能力的分子印迹聚合物．通过IR和HPLC表征,咪草烟分子印迹聚合物对咪草烟分子具有良好的识别作用．     

三明治式双极膜的制备及其光催化性能

以Cr3+交联羧甲基纤维素钠(CMC)作为阳膜层,戊二醛改性壳聚糖(CS)作为阴膜层,纳米TiO2光催化剂作为双极膜的中间层,在TiO2上涂布光敏剂八羟基喹啉（Oxine）以增强其光催化解离水的性能,制备了三明治式的双极膜（mCMC/TiO2-Oxine/mCS BPM)。 该双极膜在紫外光照射下,具有高的水解离效率,优良的亲水性能,双极膜阻抗小,工作电压低,当工作电流密度达0.12 A/cm2时,电槽工作电压小于5.0 V。     

Chemical reaction and Soret effects on MHD convective flow of second grade fluid through an absorbent medium with ramped wall temperature as well as ramped surface concentration

In the present paper, the heat generating and/or absorption as well as thermo-diffusion on the unsteady free convection MHD gyrating flow of radiation and chemical reactive second grade fluid past an unbounded perpendicular plate during absorbent medium have been discussed. Here, it is assumed that, the confining plate has the ramped wall temperature with ramped surface concentration and isothermal temperature with ramped surface concentration. The analytical solutions for the governing equations are found by utilization of Laplace transformation methodology. The velocity, temperature and concentration profiles are analyzed with quite few figures. It is determined that, velocity, temperature and concentration distribution sketches in case of ramped temperature as well as ramped surface concentration are not as much of as those of isothermal temperature as well as ramped surface concentration. In addition to the idioms of skin friction, Nusselt number as well as Sherwood number are achieved and characterized numerically with tabular format.     

Analytical devices based on light-emitting diodes – a review of the state-of-the-art

A general overview of the development of the uses of light-emitting diodes in analytical instrumentation is given. Fundamental aspects of light-emitting diodes, as far as relevant for this usage, are covered in the first part. The measurement of light intensity is also discussed, as this is an essential part of any device based on light-emitting diodes as well. In the second part, applications are discussed, which cover liquid and gas-phase absorbance measurements, flow-through detectors for chromatography and capillary electrophoresis, sensors, as well as some less often reported methods such as photoacoustic spectroscopy.     

双氧水氧化环己烯催化合成己二酸研究进展

评述了近年来以环己烯为底物,双氧水为氧源,分别采用钨酸盐、钨酸、杂多酸及杂多酸盐、功能化分子筛和负载离子液体等为催化剂催化合成己二酸的研究进展.     

Combining enabling techniques in organic synthesis: continuous flow processes with heterogenized catalysts

The concepts article describes enabling techniques (solid-phase assisted synthesis, new reactor design, microwave irradiation and new solvents) in organic chemistry and emphasizes the combination of several of them for creating new synthetic technology platforms. Particular focus is put on the combination of immobilized catalysts as well as biocatalysts with continuous flow processes. In this context, the PASSflow continuous flow technique fulfils both chemical as well as chemical engineering requirements. It combines reactor design with optimized, monolithic solid phases as well as reversible immobilization techniques for performing small as well as large scale synthesis with heterogenized catalysts under continuous flow conditions.     

Solid-phase synthesis of lipidated peptides

Characteristic partial structures of lipidated proteins embodying different lipid groups as well as additional fluorescent tags or a maleimide for coupling to proteins can be synthesized readily by means of a new solid-phase technique employing the oxidative cleavage of the hydrazide linker as well as on-resin farnesylation and palmitoylation after appropriate deprotection of cysteine thiol groups as the key steps.     

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.     

Microwave spectrum of ethylamine-gauche

The gauche rotamer of the ethylamine molecule was successfully assigned making ample use of MW-MW-DR-techniques. The transitions of the gauche form appear as quartets due to two large amplitude motions: the CN torsion and inversion. The rotational as well as interaction constants for all four states were fitted as well as their relative energies.     

PSORALEN-OLEFIN PHOTOPRODUCI'S: FIRST OBSERVATION OF A PHOTO-ENE REACTION

Abstract Methyl-substituted psoralens (4'-(hydroxymethyl)-4,5',8-trimethylpsoralen and 4,5',8-trimethylpsoralen) are found to yield an ene product as well as the expected [2+2] cycloaddition product from photochemical reaction with simple olefins. As determined by absorbance, liquid chromatography-mass spectrometry and nuclear magnetic resonance, both products are formed at the pyrone side of the respective psoralen. The product distribution is dependent on olefin concentration as well as the nature of the olefin. In deoxygenated solutions, cyclic olefins form as much as 50% ene product, while unsubstituted straight-chain olefins form as little as 3%. In oxygenated solutions, the product distribution is strongly affected by singlet oxygen.     

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.     

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.     

Eka-elements as chemical pure possibilities

From Mendeleev’s time on, the Periodic Table has been an attempt to exhaust all the chemical possibilities of the elements and their interactions, whether these elements are known as actual or are not known yet as such. These latter elements are called “eka-elements” and there are still some of them in the current state of the Table. There is no guarantee that they will be eventually discovered, synthesized, or isolated as actual. As long as the actual existence of eka-elements is predicted, they cannot be considered as actual but only as purely possible. Given that eka-elements are chemical pure possibilities, a possibilist approach, entitled “panenmentalism,” can gain support as well as an important implication.     

Spectroscopy and photophysics of methylphenylsiloxaneand diphenylsiloxane-based molecules and polymers

Spectroscopy and photophysics of various types of methylphenylsiloxane- and diphenylsiloxane-based oligomers and polymers are reviewed. The molecules treated here include homopolymers such as poly(methylphenylsiloxane) and copolymers such as poly(dimethylsiloxane-codiphenylsiloxane) as well as related oligomers or molecules such as diphenyltetramethyldisiloxane. These polymers and oligomers normally exhibit monomer fluorescence in fluid solution at temperatures near room temperature, and the monomer fluorescence and phosphorescence in rigid matrices at 77 K. In addition to these emissions, the excimer fluorescence is often observed depending on the molecular structure of the siloxanes. These emission properties are rationalized based on the molecular structure and kinetics of the excimer formation processes as well as on the flexibility of the Si-O-Si bonds.