C12-Helix development in ()n sequences - spectroscopic characterization of Boc-Aib-4(R)Val]-OMe oligomers

The solution conformations of the -hybrid oligopeptides Boc-Aib-4(R)Val]n-OMe (n = 1-8) in organic solvents have been probed by NMR, IR, and CD spectroscopic methods. In the solid state, this peptide series favors C12-helical conformations, which are backbone-expanded analogues of 310 helices in -peptide sequences. NMR studies of the six- (n = 3) and 16-residue (n = 8) peptides reveal that only two NH protons attached the N-terminus residues Aib(1) and 4(R)Val(2) are solvent-exposed. Sequential NiH-Ni+1H NOEs characteristic of local helical conformations are also observed at the residues. IR studies establish that chain extension leads to a large enhancement in the intensities of the hydrogen-bonded NH stretching bands (3343-3280 cm-1), which suggest elongation of intramolecularly hydrogen-bonded structures. The development of C12-helical structures upon lengthening of the sequence is supported by the NMR and IR observations. The CD spectra of the ()n peptides reveal a negative maximum at ca. 206 nm and a positive maximum at ca. 192 nm, spectral feature that are distinct from those of 310 helices in -peptides.

低碳烯烃合成C12-C18的ZrZSM-5分子筛催化剂及制备方法

本发明公开了一种低碳烯烃合成Ｃ↓［１２］－Ｃ↓［１８］的ＺｒＺＳＭ－５分子筛催化剂及制备方法，催化剂的重量百分比组成为：Ｚｒ：２．０～７．０％，ＺＳＭ－５分子筛９３．０～９８．０％，所述的ＺＳＭ分子筛是Ｓｉ／Ａｌ摩尔比为２４～７８的氢型ＺＳＭ－５分子筛，采用在酸性溶液中进行离子交换而将Ｚｒ离子引入沸石中对其物性进行调整，使分子筛的强酸活性中心向中强酸的弱酸中心调变。在相同的反应条件下改质后齐聚反应的活性和Ｃ↓［１２］～Ｃ↓［１８］的选择性均有增加，Ｃ↓［１２］～Ｃ↓［１８］的择性由４０％增加至７８％左右，使低碳烯烃合成柴油成为可能。

Biofilm Eradication Kinetics of the Ultrashort Lipopeptide C12-OOWW-NH2 Utilizing a Modified MBEC Assay™

In this study, we report the antimicrobial planktonic and biofilm kill kinetics of ultrashort cationic lipopeptides previously demonstrated by our group to have a minimum biofilm eradication concentration (MBEC) in the microgram per mL (μg/mL) range against clinically relevant biofilm-forming micro-organisms. We compare the rate of kill for the most potent of these lipopeptides, dodecanoic (lauric) acid-conjugated C₁₂-Orn-Orn-Trp-Trp-NH₂ against the tetrapeptide amide H-Orn-Orn-Trp-Trp-NH₂ motif and the amphibian peptide Maximin-4 via a modification of the MBEC Assay™ for Physiology & Genetics (P&G). Improved antimicrobial activity is achieved upon N-terminal lipidation of the tetrapeptide amide. Increased antimicrobial potency was demonstrated against both planktonic and biofilm forms of Gram-positive micro-organisms. We hypothesize rapid kill to be achieved by targeting of microbial membranes. Complete kill against established 24-h Gram-positive biofilms occurred within 4 h of exposure to C₁₂-OOWW-NH₂ at MBEC values [methicillin-resistant Staphylococcus epidermidis (ATCC 35984): 15.63 μg/mL] close to the values for the planktonic minimum inhibitory concentration (MIC) [methicillin-resistant Staphylococcus epidermidis (ATCC 35984): 1.95 μg/mL]. Such rapid kill, especially against sessile biofilm forms, is indicative of a reduction in the likelihood of resistant strains developing with the potential for quicker resolution of pathogenic infection. Ultrashort antimicrobial lipopeptides have high potential as antimicrobial therapy.

Energieberatungsbericht zum Gebäude C12, Hochschule Darmstadt

Im Rahmen des vom Hessischen Ministerium der Finanzen geförderten Forschungsprojektes „Bausteine für die CO2-Neutralität im Liegenschaftsbestand hessischer Hochschulen“ wird die neu entwickelte Teilenergiekennwertmethode, kurz TEK - an dem Gebäude C12 der Hochschule Darmstadt in der Schöfferstraße 3, 64295 Darmstadt, angewandt. Das Gebäude von 1989 wird von den Fachbereichen Maschinenbau und Kunststofftechnik genutzt. Der Grundriss des Objektes beschreibt eine symmetrische U-Form. Es ist nicht unterkellert und mit einem Flachdach versehen. Bisher haben keine Sanierungsmaßnahmen stattgefunden. Die aus den Analysen gewonnenen Gebäude- und Anlagendaten dienen als Datengrundlage für eine Querschnittsanalyse zum Nichtwohngebäudebestand. Der folgende Kurzbericht umfasst: • Eine kurze Beschreibung des Projektes und des Gebäudes, • die Bewertung des Ist-Zustands des Gebäudes, • die Angabe von Modernisierungsmaßnahmen unter Nennung der Energieeinsparung, der Grobkosten und der sich hieraus ergebenden Wirtschaftlichkeit, • einen Anhang mit ausführlichen Informationen zur Gebäudeanalyse. Der Primärenergiebedarf des Objektes wurde mit 476 kWh/(m²a) unter Berücksichtigung der vorhandenen Nutzung als „hoch“ eingestuft. Die in den Laboren eingesetzte RLT-Anlage weist einen wesentlichen Anteil am Gesamtenergieverbrauch des Gebäudes auf. Hier werden Sanierungs- bzw. Modernisierungsmaßnahmen mit Anpassung der Betriebsweise empfohlenen. Ebenfalls sollte in Erwägung gezogen werden, beim Austausch vorhandener Fenster diese durch 3-fach Wärmeschutzglas zu ersetzten. Zusätzlich kann eine Senkung des Stromverbrauchs durch den Einsatz moderner Beleuchtungstechnik mit Präsenzmeldern geschaffen werden.

Desenvolvimento de emulsão contendo C12 - 25 acid PEG 8 éster e avaliação da estabilidade com diferentes concentrações de óleo essencial de Achillea millefolium

Emulsões são utilizadas especialmente na área de cosméticos. São sistemas dispersos constituídos de duas fases líquidas imiscíveis (oleosa e aquosa), onde a fase dispersa ou interna é finamente dividida e distribuída em outra fase contínua ou externa. A estabilidade da emulsão é garantida com o uso de agentes emulsificantes, podendo ser melhorada com a ajuda de agentes espessantes, que aumentam a viscosidade. Os agentes espessantes podem ser: polímeros, álcoois, ácidos ou ésteres graxos e ceras naturais. O objetivo deste estudo foi avaliar a estabilidade de um sistema emulsionado não-iônico, apresentando como tensoativo emulsificante uma base auto emulsionável não-iônica e incorporado de óleo essencial em diferentes concentrações, para posterior avaliação da atividade antiirritante em cosméticos pós-barba e pós depilação. Para isto, foi necessário realizar os teste de estabilidade, que fornecem informações sobre a confiabilidade e a segurança das preparações, além da caracterização reológica completa, como auxiliar do desenvolvimento da preparação e do estudo de estabilidade. Foram realizados testes de estabilidade preliminar, que auxiliam na triagem das formulações e também realizou-se testes de estabilidade acelerada, com o objetivo de estimar o prazo de validade do produto. Com o objetivo de analisar o comportamento do produto durante o armazenamento e no momento do uso, estudou-se o comportamento reológico das preparações, onde avaliou-se as curvas de fluxo, a tixotropia e os testes oscilatórios. Os resultados obtidos mostraram que a emulsão proposta é estável frente aos testes de estabilidade, não apresentando alterações significativas quanto aos parâmetros analisados. Foi verificado que ela pode receber um ativo e liberá-lo, no entanto, as concentrações de óleo essencial de Achillea millefolium incorporadas... (Resumo completo, clicar acesso eletrônico abaixo)

Synthesis and SAR of C12-C13-oxazoline derivatives of epothilone A

The SAR of a series of new epothilone A derivatives with a 2-substituted-1,3-oxazoline moiety trans-fused to the C12-C13 bond of the deoxy macrocycle have been investigated with regard to tubulin polymerization induction and cancer cell growth inhibition. Significant differences in antiproliferative activity were observed between different analogs, depending on the nature of the substituent at the 2-position of the oxazoline ring. The most potent compounds showed comparable activity with the natural product epothilone A. Modeling studies provide a preliminary rationale for the observed SAR.

Modeling conditional correlations of asset returns : a smooth transition approach

In this paper we propose a new multivariate GARCH model with time-varying conditional correlation structure. The time-varying conditional correlations change smoothly between two extreme states of constant correlations according to a predetermined or exogenous transition variable. An LM–test is derived to test the constancy of correlations and LM- and Wald tests to test the hypothesis of partially constant correlations. Analytical expressions for the test statistics and the required derivatives are provided to make computations feasible. An empirical example based on daily return series of five frequently traded stocks in the S&P 500 stock index completes the paper.

Elastic Constants of Sodium Nitrate from 77 to 300 K

The six independent elastic constants of sodium nitrate are determined using 10 MHz ultrasonic pulse echo superposition technique over the temperature interval 77 to 300 K. The values obtained at 300 K are C11 = 5.71, C12 = 2.16, C33 = 3.3, C13 = 1.66, C44 = 1.24, C14 = 0.82, and at 77 K C11 = 6.63, C12 = 2.07, C33 = 3.99, C13 = 1.67, C44 = 1.69, C14 = 1.16 all expressed in units of 1011 dyn/cm2.

Elastic constants of galena down to liquid helium temperatures

The elastic constants of single crystal galena have been determined from the measured ultrasonic velocities down to liquid helium temperature. A cryostat incorporating an arrangement to inject the liquid bonding material at low temperature is described. At 5 K, the values of elastic constants are C11=14.90, C12=3.51 and C44=2.92×1010 N/m2.

The elastic constants of isomorphous sodium bromate and sodium chlorate from 77 to 350 K

The elastic constants of NaBrO3 and NaClO3 are evaluated from ultrasonic velocity measurements using pulse superposition techniques. The values of C11, C12 and C44 for NaBrO3 at 298°K are 5.578, 1.705, 1.510 (x 1010 N/m2) and for NaClO3 the values are 4.897, 1.389, 1.174. The values at 77°K are respectively 6.35, 1.98 and 1.65 for NaBrO3 and 6.15, 2.16 and 1.32 for NaClO3.

Backbone chemical shift assignments of the acyl-acyl carrier protein intermediates of the fatty acid biosynthesis pathway of Plasmodium falciparum

We report the backbone chemical shift assignments of the acyl-acyl carrier protein (ACP) intermediates of the fatty acid biosynthesis pathway of Plasmodium falciparum. The acyl-ACP intermediates butyryl (C4), -octanoyl (C8), -decanoyl (C10), -dodecanoyl (C12) and -tetradecanoyl (C14)-ACPs display marked changes in backbone HN, Cα and Cβ chemical shifts as a result of acyl chain insertion into the hydrophobic core. Chemical shift changes cast light on the mechanism of expansion of the acyl carrier protein core.

Elastic constants of triclinic copper sulphate pentahydrate crystals

Using an iterative technique to obtain the exact solutions of the cubic Christoffel equation, the 21 elastic constants of copper sulphate pentahydrate have been determined at 25°C by the ultrasonic pulse echo method. The elastic constants, referred to the IRE recommended system of axes, are c11=5·65, c12=2·65, c13=3·21, c14=−0·33, c15=−0·08, c16=−0·39, c22=4·33, c23=3·47, c24=−0·07, c25=−0·21, c26=0·02, c33=5·69, c34=−0·44, c35=−0·21, c36=−0·16, c44=1·73, c45=0·09, c46=0·03, c55=1·22, c56=−0·26 and c66=1·00 in units of 1010 N m−2.

Synthesis of 1,3-dimethyl-1,3-dicarboxycyclohexane-2-acetic acid. An isomer of the degradation product of abietic acid

A synthesis of 1,3-dimethyl-1,3-dicarboxycyclohexane-2-acetic acid has been described, and proved to be an isomer of the C12-acid-an oxidative degradation product of abietic acid.