Organic sonochemistry. Ultrasound-promoted coupling of organic halides in the presence of lithium wire

Alkyl, aromatic, benzylic and benzoyl halides have been successfully coupled in good yields using lithium wire suspended in tetrahydrofuran and ultrasound.     

Dispersion state of CuO on CeO2

XRD and XPS are used to study the dispersion state of CuO on ceria surface. The dispersion capacity values of CuO measured by the two methods are consistent, which are of 1.20 mmol CuO/100 m² CeO₂. In addition, the results reveal that highly dispersed Cu²⁺ ions are formed at low CuO loadings and that increasing the CuO content to a value higher than its dispersion capacity produces crystalline CuO after the surface vacant sites on CeO₂ are filled. The atomic composition of the outermost layer of the CuO/CeO₂ samples has been probed by using static secondary ion mass spectroscopy (SSIMS), and the ratim of Cu/Ce are found to be 0.93 and 0.46 for the 1.22 and 0.61 mmol CuO/CeO₂ samples respectively. Temperature-programmed reduction (TPR) profile with two reduction peaks at 156 and 165°C suggests that the reduction of highly dispersed Cu²⁺ ions consists of two steps and is easier than that of CuO crystallites, in which the TPR profile has only one reduction peak at about 249°C. The above experimental results are in good agreement with the prediction of the incorporation model. Project supported by the National Natural Science Foundation of China.     

Effect of some factors on the energy band structure of proteins

The effects of four factors (different side chains, side-chain disorder, conformational change, and ions and water) on the energy band structures of proteins have been investigated with the aid of the CNDO/2 crystal orbital method. The results indicate that these factors are very important. The consequences of these effects on the semiconductive properties of proteins are discussed.     

Micranoic acids A and B: two new octanortriterpenoids from Schisandra micrantha

Two novel octanortriterpenoids, micranoic acids A (1) and B (2), along with three known compounds, kadsuric acid (3), 3beta-hydroxy-lanost-9(11),24(25)-dien-26-oic acid (4) and schizandronic acid (5), were isolated from the leaves and stems of Schisandra micrantha. The structures of 1 and 2 were determined by 1D and 2D NMR spectroscopic analysis. Micranoic acids A and B represent a new group of triterpenes in which the entire C-17 side chain has lost. This is the first report of octanortriterpenoids isolated from the family Schisandraceae.     

Reversible replication between ordered mesoporous silica and mesoporous carbon

Highly ordered mesoporous silica can be regenerated from a mesoporous carbon CMK-3 that is a negative replica of mesoporous silica SBA-15, indicating reversible replication between carbon and inorganic materials.     

Subsolidus phase relations and crystal structure of compounds in the PrOx-CaO-CuO system

The subsolidus phase relations of the PrO_x-CaO-CuO pseudo-ternary system sintered at 950-1000°C have been investigated by X-ray powder diffraction. In this system, there exist one compound Ca₁₀Pr₄Cu₂₄O₄₁, one Ca₂Pr₂Cu₅O₁₀-based solid solution, seven three-phase regions and two two-phase regions. The crystal structures of Ca₁₀Pr₄Cu₂₄O₄₁ and Ca₂Pr₂Cu₅O₁₀-based solid solution have been determined. Compound Ca₁₀Pr₄Cu₂₄O₄₁ crystallizes in an orthorhombic cell with space group D_2h²⁰−Cccm, Z=4. Its lattice parameters are a=11.278(2) Å, b=12.448(3) Å and c=27.486(8) Å. The crystal structure of Ca₂Pr₂Cu₅O₁₀-based solid solution is an incommensurate phase based on the orthorhombic NaCuO₂ type subcell. The lattice parameters of the subcell of the Ca_2.4Pr_1.6Cu₅O₁₀ are a₀=2.8246(7) Å, b₀=6.3693(5) Å, c₀=10.679(1) Å, and those of the orthorhombic superstructure are with a=5a₀, b=b₀, c=5c₀. The Ca_2.4Pr_1.6Cu₅O₁₀ structure can also be determined by using a monoclinic supercell with space group C_2h⁵−P2₁/c, Z=4, a=5a₀, b=b₀, and β=104.79(1)° or 136.60(1)°, V=5a₀b₀c₀.     

Etude des propriétés cristallographiques,diélectriques et d'optique non linéaire de quelques nouvelles phases de composition BaxLi5−2xNb5(1−y)Ta5yO15 et de structure bronzes oxygénés de tungstène quadratiques

Two series of phases with tetragonal bronze-like structure and composition Ba_xLi_5?2xT₅O₁₅ (T = Nb, Ta) have been isolated in the systems BaNb₂O₆LiNbO₃ and BaTa₂O₆LiTaO₃. All these phases show ferroelectric-paraelectric transitions. The Curie temperature increases with the lithium content. The value of T_C for Ba_2.03Li_0.94Nb₅O₁₅ is the highest ever observed for this type of structure: the obtained phases are potentially good materials for the harmonic generation of the 0.53-μm radiation. The optical yield of the niobate Ba_2.14Li_0.71Nb₅O₁₅ is about 2.5 times that of Ba₂NaNb₅O₁₅ and 250 times that of the K.D.P. The crystallographic and dielectric data of the system Ba_2.14Li_0.71Nb₅O₁₅Ba_2.14Li_0.71Ta₅O₁₅ characterize three domains, which are respectively antiferroelectric, ferroelectric, and paraelectric. The Curie temperature and the optical yield decrease with increasing tantalum content.     

Co-C bond dissociation energy and reaction volume change of 2',5'-dideoxyadenosylcobalamin studied by laser-induced time-resolved photoacoustic calorimetry

Time resolved photoacoustic calorimetry (PAC) was applied to a study of the photolysis of a coenzyme B(12) analog 2',5'-dideoxyadenosylcobalamin, which lacks an -OH group at the 2' position of ribofuranose ring. In aqueous solution, we report for the first time the quantum yield Phi(d) (0.25+/-0.02), Co-C bond dissociation energy (BDE; 31.8+/-2.5 kcal mol(-1)) and reaction volume change deltaV(R) (6.5+/-0.5 ml mol(-1)) due to conformation changes of the corrin ring and its side chains accompanying the cleavage of the Co-C bond. These values for the analog are very similar to those for the natural cofactor. Based our results and previous studies, a possible explanation for the similarity in their structure and properties versus the large difference in their enzymatic activity is discussed.     

Single molecule force spectroscopy reveals the context dependent folding pathway of the C-terminal fragment of Top7

Top7 is a de novo designed protein with atomic level accuracy and shows a folded structure not found in nature. Previous studies showed that the folding of Top7 is not cooperative and involves various folding intermediate states. In addition, various fragments of Top7 were found to fold on their own in isolation. These features displayed by Top7 are distinct from those of naturally occurring proteins of a similar size and suggest a rough folding energy landscape. However, it remains unknown if and how the intra-polypeptide chain interactions among the neighboring sequences of Top7 affect the folding of these Top7 fragments. Here we used single-molecule optical tweezers to investigate the folding–unfolding pathways of full length Top7 as well as its C-terminal fragment (CFr) in different sequence environments. Our results showed that the mechanical folding of Top7 involves an intermediate state that likely involves non-native interactions/structure. More importantly, we found that the folding of CFr is entirely dependent upon its sequence context in which it is located. When in isolation, CFr indeed folds into a cooperative structure showing near-equilibrium unfolding–folding transitions at ∼6.5 pN in OT experiments. However, CFr loses its autonomous cooperative folding ability and displays a folding pathway that is dependent on its interactions with its neighboring sequence/structure. This context-dependent folding dynamics and pathway of CFr are distinct from those of naturally occurring proteins and highlight the critical importance of intra-chain interactions in shaping the overall energy landscape and the folding pathway of Top7. These new insights may have important implications on the de novo design of proteins.

Optical tweezers experiments reveal that the folding of the C-terminal fragment of Top7 (cFr) is context-dependent. Depending on its neighboring sequence, cFr shows very different folding pathways and folding kinetics.      

Synthesis of (4S,9aS)-hexahydro-4-methyl-1H,5H-pyrrolo[2,1-c][1,4]-thiazepine-1,5-dione,A potent angiotensin converting enzyme inhibitor

Synthesis of (4S,9aS)-hexahydro-4-methyl-1H,5H-pyrrolo[2,1-c][1,4]thiazepine-1,5-dione, an orally active potent angiotensin converting enzyme inhibitor is described.