Staphylococcus aureus Penicillin‐Binding Protein 2 Can Use Depsi‐Lipid II Derived from Vancomycin‐Resistant Strains for Cell Wall Synthesis

Vancomycin‐resistant Staphylococcus aureus (S. aureus) (VRSA) uses depsipeptide‐containing modified cell‐wall precursors for the biosynthesis of peptidoglycan. Transglycosylase is responsible for the polymerization of the peptidoglycan, and the penicillin‐binding protein 2 (PBP2) plays a major role in the polymerization among several transglycosylases of wild‐type S. aureus. However, it is unclear whether VRSA processes the depsipeptide‐containing peptidoglycan precursor by using PBP2. Here, we describe the total synthesis of depsi‐lipid I, a cell‐wall precursor of VRSA. By using this chemistry, we prepared a depsi‐lipid II analogue as substrate for a cell‐free transglycosylation system. The reconstituted system revealed that the PBP2 of S. aureus is able to process a depsi‐lipid II intermediate as efficiently as its normal substrate. Moreover, the system was successfully used to demonstrate the difference in the mode of action of the two antibiotics moenomycin and vancomycin.     

Efficient total synthesis of (+)-negamycin, a potential chemotherapeutic agent for genetic diseases

Herein, we describe an efficient strategy for the total synthesis of (+)-negamycin using commercially available achiral N-Boc-2-aminoacetaldehyde as starting material with 42% overall yield for a limited number of steps.     

Evaluation of gradient-index array alignment

Optical Review - A gradient-index (GRIN) array is used as an imaging unit in light-emitting diode (LED) printers. In this study, we measure tilts of GRINs in an array and analyze the intensity...     

Mg-promoted facile and selective intramolecular cyclization of aromatic δ-ketoesters

Treatment of various types of aromatic δ-ketoesters 2, 7, and 9 with Mg-turnings for Grignard reaction at −5 to 0 °C in N,N-dimethylformamide (DMF) containing trimethylsilyl chloride (TMSCl) brought about selective and reductive intramolecular cyclization to give the corresponding α-aryl-α-hydroxycyclopentanones 5, 8, and 10, respectively, in moderate to good yields. Similar reductive intramolecular cyclization of aromatic δ-ketodiesters 14, followed by acidic hydrolysis and decarboxylation easily gave the corresponding 2-aryl-2-cyclopenten-1-ones 15. The present facile coupling may be initiated through electron transfer from Mg metal to the aromatic carbonyl groups of 2, 7, 9, and 14 to generate the corresponding radical anions, followed by their intramolecular nucleophilic attack to the ester groups to give the corresponding five-membered ring compounds 5, 8, 10, and 15, respectively.     

Vibrational spectrum and specific heat of fine particles

The vibrational spectrum for a fine particle is obtained by exactly solving the wave equation for a homogeneous elastic sphere with free surface. In terms of this frequency spectrum, enhancements in the specific heat of fine particles are calculated and compared with the experiments at low temperatures. Qualitative features of the experimental results are consistently explained in our theory.     

Direct measurement of proton dissociation in thhe excited state of protonated 1-aminopyrene with picosecond pulses

Direct measurement of proton dissociation in the excited singlet state of protonated I-aminopyrene in a mixture of H₂O (or D₂O) and acetonitrile (1:1) has been carried out by means of picosecond time-resolved spectroscopy. The proton dissociation retes k¹₁ and k^D+₁ at about 300 K were determined tobe 3.7 (±0.6) * 10⁹ s^-1, respectively. These rates are in very good agreement with those obtained by nanosecond time-resolved spectroscopy with fluorometry. The excited singlet state ;K^*₂ value of l-aminopyrene was also determined by dynamic analyses.     

Distribution of 201Tl in the blood

Thallium-201 distribution in the blood was investigated both in vivo and in vitro. Thallium-201 was distributed into the erythrocytes and plasma with the ratio of 1.4 +/- 0.3 to 1.0, immediately after its administration. The uptake of 201Tl into the erythrocytes in vitro were affected by the incubation temperature and the presence of ouabain and KCl; indicating that the 201Tl was uptaken into cells partly through their membranes Na, K-ATPase. Erythrocytes could retain 201Tl in it, whereas 201Tl was present as free ion in the plasma. Thallium-201 was flew out of erythrocytes into the plasma, keeping the ratio of 201Tl in erythrocytes/plasma to be 1.9 +/- 0.2/1.0.     

A new reforming process based on CH4 decomposition using a hydrogen-permeating membrane reactor

A new reforming process was studied using Ni/SiO₂ with a hydrogen-permeating membrane reactor. Nickel catalyst supported on SiO₂ is highly active for CH₄-H₂O-O₂ reaction in membrane reactor and the reaction close to CH₄ + 0.35O₂ + 1.3H₂O → CO₂ + 3.3H₂ proceeds at 873 K. Since the selectivity to carbon and CO₂ increased and decreased with decreasing contact time respectively, it is considered that the reaction was started by decomposition of CH₄ followed by oxidation of C and water shift reaction. Therefore, the reaction mechanism was different from so-called autothermal reforming (ATR) reaction.     

Transfer hydrogenation and transfer hydrogenolysis—21 : Dehydrogenation of alcohols by quinones

Dehydrogenation of benzyl-type alcohols and hydroaromatic compounds by 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and tetrachloro-p-benzoquinone were examined, and the hydrogen transfer from 1-phenyl-1-propanol to DDQ was investigated in detail. The yield of the propiophenone increased when solvents which would be expected to increase the concentration of the charge transfer complex between the alcohol and DDQ were used. Initial rates of the reaction in dioxane were proportional to the concentration of the hydrogen donor and that of the hydrogen acceptor. In the dehydrogenation of several para- or meta-substituted 1-phenyl-1-propanols at 60°, ?3.30 was obtained as a value of reaction constant. Relative rates of the reaction of PhCH(OH)Et, PhCH(OD)Et, PhCD(OH)Et, and PhCD(OD)Et were 8.9,9.1,1.0 and 1, respectively. This result suggests that the transfer of the H atom attached to the α-carbon of the alcohol is the rate-determining step. This and some other results support a two-step ionic mechanism for the dehydrogenation of alcohols.