Highly efficient antibody-catalyzed deuteration of carbonyl compounds

Antibody 38C2 efficiently catalyzes deuterium-exchange reactions at the alpha position of a variety of ketones and aldehydes, including substrates that have a variety of sensitive functional groups. In addition to the regio- and chemoselectivity of these reactions, the catalytic rates (kcat) and rate-enhancement values (kcat/kun) are among the highest values ever observed with catalytic antibodies. Comparison of the substrate range of the catalytic antibody with highly evolved aldolase enzymes, such as rabbit-muscle aldolase, highlights the much broader practical scope of the antibody, which accepts a wide range of substrates. The hydrogen-exchange reaction was used for calibration and mapping of the antibody active site. Isotope-exchange experiments with cycloheptanone reveal that the formation of the Schiff base species (as concluded from the 16O/18O exchange rate at the carbonyl oxygen) is much faster than the formation of the enamine intermediate (as concluded from the H/D exchange rate), and both steps are faster than the antibody-catalyzed aldol addition reaction.     

A recommended and verified procedure for in situ tryptic digestion of formalin‐fixed paraffin‐embedded tissues for analysis by matrix‐assisted laser desorption/ionization imaging mass spectrometry

Matrix‐assisted laser desorption/ionization imaging mass spectrometry (MALDI IMS) is a molecular imaging technology uniquely capable of untargeted measurement of proteins, lipids, and metabolites while retaining spatial information about their location in situ. This powerful combination of capabilities has the potential to bring a wealth of knowledge to the field of molecular histology. Translation of this innovative research tool into clinical laboratories requires the development of reliable sample preparation protocols for the analysis of proteins from formalin‐fixed paraffin‐embedded (FFPE) tissues, the standard preservation process in clinical pathology. Although ideal for stained tissue analysis by microscopy, the FFPE process cross‐links, disrupts, or can remove proteins from the tissue, making analysis of the protein content challenging. To date, reported approaches differ widely in process and efficacy. This tutorial presents a strategy derived from systematic testing and optimization of key parameters, for reproducible in situ tryptic digestion of proteins in FFPE tissue and subsequent MALDI IMS analysis. The approach describes a generalized method for FFPE tissues originating from virtually any source.     

Seasonal Minimum and Maximum Solar Ultraviolet Exposure Measurements of Classroom Teachers Residing in Tropical North Queensland,Australia

The risk of keratinocyte skin cancer, malignant melanoma and ultraviolet radiation (UVR)‐induced eye disease is disproportionately higher in Australia and New Zealand compared to equivalent northern hemisphere latitudes. While many teachers are aware of the importance of reinforcing sun safety messages to students, many may not be aware of the considerable personal exposure risk while performing outdoor duties in locations experiencing high to extreme ambient UVR year‐round. Personal erythemally effective exposure of classroom teachers in tropical Townsville (19.3°S) was measured to establish seasonal extremes in exposure behavior. Mean daily personal exposure was higher in winter (91.2 J m^‐2, 0.91 Standard Erythema Dose [SED]) than summer (63.3 J m^?2, 0.63 SED). The range of exposures represents personal exposures that approximate current national guidelines for Australian workers at the study latitude of approximately 1.2 SED (30 J m^?2 effective to the International Commission on Non‐Ionizing Radiation Protection). Similar proportions of teachers spent more than 1 h outdoors per day in winter (28.6%) and summer (23.6%) as part of their teaching duties with seasonal differences having little effect on the time of exposure. Personal exposures for teachers peaked during both seasons near school meal break times at 11:00 am and 1:00 pm, respectively.     

Copper + nickel-in-charcoal (Cu-Ni/C): a bimetallic, heterogeneous catalyst for cross-couplings

A new heterogeneous catalyst composed of copper and nickel oxide particles supported within charcoal has been developed. It catalyzes cross-couplings that traditionally use palladium, nickel, or copper, including Suzuki-Miyaura reactions, Buchwald-Hartwig aminations, vinylalane alkylations, etherifications of aryl halides, aryl halide reductions, asymmetric conjugate reductions of activated olefins, and azide-alkyne "click" reactions.     

Copolymerization of ethylene and non-conjugated diene using homogenous catalyst

Ethylene and different amounts of 1,7-octadiene were copolymerized using the metallocene catalyst system ethylidene-bis(fluorenyl) zirconium dichloride and methylaluminoxane (MAO) at both 50 and 90 °C. The catalyst activity has slightly increased with the addition of low amounts of the diene in relation to the homopolymerization of ethylene. The obtained polymers were characterized according to their melting temperature (T_m) and crystallinity degree (x_c) by differential scanning calorimetry (DSC). Weight-average molecular weight (M_w) and polydispersity were determined by gel permeation chromatography (GPC). Diene contents in the copolymer were obtained through the FTIR spectroscopy. The results indicated that at polymerization temperature of 90 °C, crosslinking bonds in the obtained copolymers were low, differently from what was observed at 50 °C. The diene content in the copolymer achieved more than 3 mol% and the comonomer conversion was around 15%. Moreover, the obtained copolymers have M_w around 100,000 and large polydispersity.     

Molecular structure of Hf(BH4)4 investigated by quantum mechanical calculations and gas-phase electron diffraction

The structure of the gaseous hafnium tetrakis(tetrahydroborate) molecule, Hf(BH4)4, has been investigated by detailed quantum mechanical calculations and by analysis of its gas electron-diffraction (GED) pattern. The ground-state geometry possesses T symmetry with all of the triply-bridged BH4 groups twisted equally about the Hf...B-H axes. Salient structural parameters (ra distances, r angles) deduced from the GED pattern by the SARACEN method were: r(Hf...B) 231.4(2), r(Hf-Hb) 221.5(7), r(B-Hb) 127.6(5), r(B-Ht) 121(1) pm, Hf...B-Hb 69.4(3), Hb-B-Hb 108.4(4), Hb-B-Ht 110.6(3), B...Hf...B-Hb 166(1) degrees. A notable feature is the large magnitude of the Hf...B and Hf-Hb anharmonicity parameters, attributed to the fluxional hydrogen atom exchange process. The properties are compared with those of related tetrahydroborates..     

Reactions of lignin in chlorine dioxide bleaching of kraft pulps

The reactions between chlorine dioxide and the residual lignin in oxygen-bleached softwood kraft pulps have been studied. In a first series, isolated lignin samples have been subjected to chlorine dioxide oxidation at different pH values and subsequently analysed by oxidative degradation and elemental analysis. Different analytical techniques have also been employed to follow the gradual chemical changes in lignins isolated from kraft pulps after each of the bleaching stages in the OD(EOP)DD sequence. The results demonstrate that, in order to minimize chlorination of the lignin, the first chlorine dioxide stage should be carried out at a pH around or above three. At this pH level, a high degree of lignin oxidation is also achieved. A certain (mono)-chlorination of the lignin in the first D stage cannot be avoided, but this chlorine is to a large extent removed in the later bleaching stages. The efficient and non-selective oxidation of the various phenolic lignin end groups by chlorine dioxide is clearly illustrated by the analytical data. Moreover,¹³C NMR reveals that reduced lignin structures formed during the kraft cook survive the oxidative bleaching stages to a large extent.     

Mean exposure fractions of human body solar UV exposure patterns for application in different ambient climates

In this research, the erythemally effective UV measured using miniaturized polysulphone dosimeters to over 1250 individual body sites and collected over a 4-year period is presented relative to the total exposed skin surface area (SSA) of a life-size manikin model. A new term is also introduced, the mean exposure fraction (MEF). The MEF is used to weight modeled or measured horizontal plane UV exposures to the total unprotected SSA of an individual and is defined as the ratio of exposure per unit area received by the unprotected skin surfaces of the body relative to the exposure received on a horizontal plane. The MEF has been calculated for a range of solar zenith angles (SZA) to provide a sunburning energy data set weighted to the actual SSA of a typically clothed individual. For this research, the MEF was determined as 0.15, 0.26 and 0.41 in the SZA ranges 0°-30°, 30°-50° and 50°-80° providing information that can be used in a variety of different ambient, latitudinal and seasonal climates where total human body UV exposure information is not available.     

A four coordinate parent imide via a titanium nitridyl

Treatment of d(1) [(nacnac)TiCl(Ntol(2))] with NaN(3) results in NaCl formation and N(2) ejection to yield the first four coordinate, parent imide [(nacnac)Ti=NH(Ntol(2))] (nacnac(-)=[ArNC(CH(3))](2)CH, Ar = 2,6-iPr(2)C(6)H(3), tol = 4-CH(3)C(6)H(4)).     

Boronate Ligands in Materials: Determining Their Local Environment by Using a Combination of IR/Solid‐State NMR Spectroscopies and DFT Calculations

Boronic acids (R‐B(OH)₂) are a family of molecules that have found a large number of applications in materials science. In contrast, boronate anions (R‐B(OH)₃^?) have hardly been used so far for the preparation of novel materials. Here, a new crystalline phase involving a boronate ligand is described, Ca[C₄H₉‐B(OH)₃]₂, which is then used as a basis for the establishment of the spectroscopic signatures of boronates in the solid state. The phase was characterized by IR and multinuclear solid‐state NMR spectroscopy (¹H, ¹³C, ¹¹B and ⁴³Ca), and then modeled by periodic DFT calculations. Anharmonic OH vibration frequencies were calculated as well as NMR parameters (by using the Gauge Including Projector Augmented Wave—GIPAW—method). These data allow relationships between the geometry around the OH groups in boronates and the IR and ¹H NMR spectroscopic data to be established, which will be key to the future interpretation of the spectra of more complex organic–inorganic materials containing boronate building blocks.