Enantioselective copper-catalysed propargylic substitution: synthetic scope study and application in formal total syntheses of (+)-anisomycin and (-)-cytoxazone

A copper catalyst with a chiral pyridine-2,6-bisoxazoline (pybox) ligand was used to convert a variety of propargylic esters with different side chains (R=Ar, Bn, alkyl) into their amine counterparts in very high yields and with good enantioselectivities (up to 90% enantiomeric excess (ee)). Different amine nucleophiles were applied in the reactions and the highest enantioselectivities were obtained for aniline and its analogues. Interestingly, some carbon nucleophiles could also be used and with indoles excellent ee values were obtained (up to 98% ee). The versatility of the propargylic amines obtained was demonstrated by their further elaboration to formal total syntheses of the antibiotic (+)-anisomycin and the cytokine modulator (-)-cytoxazone.     

Coordination and Activation of AlH and GaH Bonds

The modes of interaction of donor‐stabilized Group 13 hydrides (E=Al, Ga) were investigated towards 14‐ and 16‐electron transition‐metal fragments. More electron‐rich N‐heterocyclic carbene‐stabilized alanes/gallanes of the type NHC?EH₃ (E=Al or Ga) exclusively generate κ² complexes of the type [M(CO)₄(κ²‐H₃E?NHC)] with [M(CO)₄(COD)] (M=Cr, Mo), including the first κ² σ‐gallane complexes. β‐Diketiminato (′nacnac′)‐stabilized systems, {HC(MeCNDipp)₂}EH₂, show more diverse reactivity towards Group 6 carbonyl reagents. For {HC(MeCNDipp)₂}AlH₂, both κ¹ and κ² complexes were isolated, while [Cr(CO)₄(κ²‐H₂Ga{(NDippCMe)₂CH})] is the only simple κ² adduct of the nacnac‐stabilized gallane which can be trapped, albeit as a co‐crystallite with the (dehydrogenated) gallylene system [Cr(CO)₅(Ga{(NDippCMe)₂CH})]. Reaction of [Co₂(CO)₈] with {HC(MeCDippN)₂}AlH₂ generates [(OC)₃Co(μ‐H)₂Al{(NdippCme)₂CH}][Co(CO)₄] ( 12 ), which while retaining direct Al?H interactions, features a hitherto unprecedented degree of bond activation in a σ‐alane complex.     

Quantification of morphine and its major metabolites M3G and M6G in antemortem and postmortem samples

Morphine is one of the most effective agents for the control of significant pain, primarily metabolized to morphine‐3‐glucuronide (M3G) and morphine‐6‐glucuronide (M6G). While M6G is a potent opioid agonist, M3G has no opioid action and seems to have a role in side‐effects caused by morphine. In this study, a reversed‐phase high‐performance liquid chromatographic method with diode‐array and electrochemical detection was developed for the simultaneous determination of morphine, M3G and M6G in antemortem and postmortem samples (plasma, whole blood, urine, liver, kidney and brain). Morphine, glucuronides and internal standard were extracted by double solid‐phase extraction and the separation was carried out with a Waters Spherisorb® ODS2 reversed‐phase column and potassium phosphate buffer (pH = 2.2)–acetonitrile containing sodium dodecyl sulfate as the mobile phase. The method proved to be specific with good linearity for all analytes in a calibration range from 1 to 600 ng/mL and proved to be accurate and have adequate precision and recovery. Limits of detection in the studied matrices were 0.4–4.5 ng/mL for morphine, 2.7–6.1 ng/mL for M3G and 0.8–4.4 ng/mL for M6G. The proposed method can be successfully applied to quantify morphine and its metabolites in several biological samples, covering the major routes of distribution, metabolism and elimination of morphine. Copyright © 2014 John Wiley & Sons, Ltd.     

Analysing and exploiting the Mantin biases in RC4

We explore the use of the Mantin biases (Mantin, Eurocrypt 2005) to recover plaintexts from RC4-encrypted traffic. We provide a more fine-grained analysis of these biases than in Mantin’s original work. We show that, in fact, the original analysis was incorrect in certain cases: the Mantin biases are sometimes non-existent, and sometimes stronger than originally predicted. We then show how to use these biases in a plaintext recovery attack. Our attack targets two unknown bytes of plaintext that are located close to sequences of known plaintext bytes, a situation that arises in practice when RC4 is used in, for example, TLS. We provide a statistical framework that enables us to make predictions about the performance of this attack and its variants. We then extend the attack using standard dynamic programming techniques to tackle the problem of recovering longer plaintexts, a setting of practical interest in recovering HTTP session cookies and user passwords that are protected by RC4 in TLS. We perform experiments showing that we can successfully recover 16-byte plaintexts with 80% success rate using \(2^{31}\) ciphertexts, an improvement over previous attacks.     

Cryopreservation of Arabidopsis thaliana shoot tips

Development of a successful shoot tip cryopreservation method for Arabidopsis thaliana L. will enable researchers to use molecular tools to study processes important for successful cryopreservation in this model organism. We demonstrate that Arabidopsis can be successfully cryopreserved using either plant vitrification solution 2 (PVS2) or plant vitrification solution 3 (PVS3) as cryoprotectants prior to rapidly cooling shoot tips in liquid nitrogen (LN). Shoot tip regrowth after PVS2 cryoprotectant treatment was improved after cold acclimation treatments of 8 or 18 days. All of the shoots tips regrew after LN exposure when cryoprotected with PVS3 for 60 min at 22 degree C. In addition, shoot tips could be cryopreserved using a two-step cooling procedure with PGD (polyethylene glycol-glucose-dimethyl sulfoxide) as a cryoprotectant. The high levels of shoot formation after LN exposure of Arabidopsis shoot tips makes this a desirable system in which molecular tools can be used to examine how alterations in biochemical, metabolic and developmental processes affect regrowth after cryoprotective treatments.     

Electrospun Polyacrylonitrile Nanofibrous Membranes for Point-of-Use Water and Air Cleaning

Novel electrospun polyacrylonitrile (PAN) nanofibrous membranes were prepared by using heat-press lamination under various conditions. The air permeability and the burst-pressure tests were run to select the membranes for point-of-use air and water cleaning. Membrane characterization was performed by using scanning electron microscopy, contact angle, and average pore size measurements. Selected membranes were used for both air dust filtration and cross-flow water filtration tests. Air dust filter results indicated that electrospun PAN nanofibrous membranes showed very high air-dust filtration efficiency of more than 99.99 % in between PM_0.3 and PM_2.5, whereas cross-flow filtration test showed very high water permeability over 600 L/(m²hbar) after 6 h of operation. Combining their excellent efficiency and water permeability, these membranes offer an ideal solution to filter both air and water pollutants.     

Mobius Instability of Sampling for Small Weighted Spaces of Analytic Functions

In this paper, the space A (D)is considered, consisting of thoseholomorphic functions f on the unit disk D such that || f ||= sup_{z D} | f(z)|(|z|) < +, with (1) = 0. The sampling problemis studied for weights satisfying ln (r)/ln(1 – r) 0.Möbius stability of sampling is shown to fail in this space.2000 Mathematics Subject Classification 30H05 (primary), 30D60(secondary).     

Cracking in a vitrification solution during cooling or warming does not effect growth of cryopreserved mint shoot tips

No obvious decrease in viability or in the ability of mint shoot tips to develop into a shoot occurred during vitrification when the external glass cracked upon either cooling or warming. Samples within semen straws did not show a decrease in survival over three cycles of cooling and warming either in the presence or absence of cracking. No physical defects were visible in treated shoot tips. Cracking of the external glass formed from PVS2 did not obviously influence shoot tip survival in mint species.     

Carbo‐biphenyls and Carbo‐terphenyls: Oligo(phenylene ethynylene) Ring Carbo‐mers

Ring carbo‐mers of oligo(phenylene ethynylene)s (OPEn, n=0–2), made of C₂‐catenated C₁₈ carbo‐benzene rings, have been synthesized and characterized by NMR and UV‐vis spectroscopy, crystallography and voltammetry. Analyses of crystal and DFT‐optimized structures show that the C₁₈ rings preserve their individual aromatic character according to structural and magnetic criteria (NICS indices). Carbo‐terphenyls (n=2) are reversibly reduced at ca. ?0.42 V/SCE, i.e. 0.41 V more readily than the corresponding carbo‐benzene (?0.83 V/SCE), thus revealing efficient inter‐ring π‐conjugation. An accurate linear fit of E_1/2^red1 vs. the DFT LUMO energy suggests a notably higher value (?0.30 V/SCE) for a carbo‐quaterphenyl congener (n=3). Increase with n of the effective π‐conjugation is also evidenced by a red shift of two of the three main visible light absorption bands, all being assigned to TDDFT‐calculated excited states, one of them restricting to a HOMO→LUMO main one‐electron transition.