“Printing” DNA Strand Patterns on Small Molecules with Control of Valency,Directionality, and Sequence

The incorporation of synthetic molecules as corner units in DNA structures has been of interest over the last two decades. In this work, we present a facile method for generating branched small molecule‐DNA hybrids with controllable valency, different sequences, and directionalities (5′–3′) using a “printing” process from a simple 3‐way junction structure. We also show that the DNA‐imprinted small molecule can be extended asymmetrically using polymerase chain reaction (PCR) and can be replicated chemically. This strategy provides opportunities to achieve new structural motifs in DNA nanotechnology and introduce new functionalities to DNA nanostructures.     

丙酮一步法合成甲基异丁基酮催化剂研究

用浸渍法制备了丙酮一步法合成甲基异丁基酮负载型催化剂，考察了载体的预处理温度、添加镧助剂对催化剂性能的影响；用BET法测定了催化剂的表面积；采用H2-O2滴定法测定Pd的分散度．结果发现，用经过1．023K焙烧过的Al2O3为载体的催化剂具有较好的催化性能，添加镧助剂后催化剂的分散度、活性有较大的提高．     

吡啶-BH~3相互作用复合物的理论研究

对吡啶-BH~3复合物分别用MP2/6-31+G^*和B3LYP/6-31+G^*进行理论计算以预测该复合物的构型及解离能，得到四种构型，在MP2优化构型基础上作CCSD/6-31+G^*单点能量计算以验证MP2与B3LYP结果的可靠性，然后用B3LYP作振动频率分析，计算了各构型的垂直电离势，最后用更大基组作单点能量计算和自然键轨道(NBO)分析。结果表明，N-B直接相连的构型最稳定，其解离能为141.50kJ/mol,MP2和B3LYP对N-H接近的构型结果相关较大，另外两种构型稳定性介于二者之间，解离能分别为15.18kJ/mol,14.06kJ/mol(MP2/6-31+G^*)。     

杯[6]芳烃-双金属卟啉仿P-450酶模型的研究Ⅳ.对异丙苯氧化的催化行为

研究了杯[6]芳烃-双金属卟啉在氧化异丙苯中的催化行为，结果表明杯[6]芳烃-双金属卟啉比之相应的金属卟啉具有更高的催化活性，并表现同样的选择性，生成苯乙酮和醇组份。此一结果同通常酞菁或其它如西弗碱大分子金属络合物催化下生成丙酮和酚不同。还考察了温度、轴向配体、催化剂用量及金属离子种类等对反应的影响，仔细地通过测定反应速度比较了反应的活性。     

Sun Exposure over a Lifetime in Australian Adults from Latitudinally Diverse Regions

Spatio‐temporal patterns in sun exposure underlie variations in skin cancer incidence and vitamin D deficiency, indicate effectiveness of sun protection programs and provide insights into future health risks. From 558 adults across four regions of Australia (Brisbane (27°S), Newcastle (33°S), Geelong and the Western Districts of Victoria (37°S) and Tasmania (43°S)), we collected: self‐report data on time‐in‐the‐sun from age 6 years; natural skin color and ethnicity; silicone skin casts (for cumulative skin damage); and serum for vitamin D status. Ambient ultraviolet radiation (UVR) at the location of residence, with time‐in‐the‐sun, was used to calculate a “UVR dose” for each year of life. Individuals maintained their ranking compared to their peers for time‐in‐the‐sun in summer compared to winter and across ages (Spearman rho 0.24–0.84, all P < 0.001). Time‐in‐the‐sun decreased with age in all birth cohorts, and over calendar time. Summer time‐in‐the‐sun increased with increasing latitude (P < 0.001). Seasonal variation in vitamin D status had greater amplitude and vitamin D deficiency increased with increasing latitude. Temporal patterns are consistent with effectiveness of sun protection programs. Higher relative time‐in‐the‐sun persists from childhood through adulthood. Lower summer time‐in‐the‐sun in the warmest location may have implications for predictions of UVR‐related health risks of climate change.     

Bioorganometallic chemistry: biocatalytic oxidation reactions with biomimetic NAD/NADH co-factors and [Cp*Rh(bpy)H] for selective organic synthesis

The biocatalytic, regioselective hydroxylation of 2-hydroxybiphenyl to the corresponding catechol was accomplished utilizing the monooxygenase 2-hydroxybiphenyl 3-monooxygenase (HbpA). The necessary natural 1,4-dihydronicotinamde adenine dinucleotide (NADH) co-factor for this biocatalytic process was replaced by a biomimetic co-factor, N-benzyl-1,4-dihydronicotinamide, 1b. The interaction between the flavin (FAD) containing HbpA enzyme and the corresponding biomimetic NADH compound, N-benzyl-1,4-dihdronicotinamide, 1b, for hydride transfer, was shown to readily occur. The in situ recycling of the reduced NADH biomimic 1b from 1a was accomplished with [Cp*Rh(bpy)H](Cl); however, productive coupling of this regeneration reaction to the enzymatic hydroxylation reaction was not totally successful, due to a deactivation process concerning the HbpA enzyme peripheral groups; i.e., -SH or -NH₂ possibly reacting with the precatalyst, [Cp*Rh(bpy)(H₂O)](Cl)₂, and thus inhibiting the co-factor regeneration process. The deactivation mechanism was studied, and a promising strategy of derivatizing these peripheral -SH or -NH₂ groups with a polymer containing epoxide was successful in circumventing the undesired interaction between HbpA and the precatalyst. This latter strategy allowed tandem co-factor regeneration using 1a or 2a, [Cp*Rh(bpy)(H₂O)](Cl)₂, and formate ion, in conjunction with the polymer bound, FAD containing HbpA enzyme to provide the catechol product.     

Electrochemical and spectroelectrochemical characterization of Ru(2)(4+) and Ru(2)(3+) complexes under a CO atmosphere

Eleven different Ru(2)(4+) and Ru(2)(3+) derivatives are characterized by thin-layer FTIR and UV-visible spectroelectrochemistry under a CO atmosphere. These compounds, which were in-situ electrogenerated from substituted anilinopyridine complexes with a Ru(2)(5+) core, are represented as Ru(2)(L)(4)Cl where L = 2-CH(3)ap, ap, 2-Fap, 2,3-F(2)ap, 2,4-F(2)ap, 2,5-F(2)ap, 3,4-F(2)ap, 3,5-F(2)ap, 2,4,6-F(3)ap, or F(5)ap. The Ru(2)(5+) complexes do not axially bind CO while mono- and bis-CO axial adducts are formed for the Ru(2)(4+) and Ru(2)(3+) derivatives, respectively. Six of the eleven investigated compounds exist in a (4,0) isomeric form while five adopt a (3,1) geometric conformation. These two series of compounds thus provide a large enough number of derivatives to examine trends and differences in the spectroscopic data of the two types of isomers in their lower Ru(2)(4+) and Ru(2)(3+) oxidation states. UV-visible spectra of the Ru(2)(4+) derivatives and IR spectra of the Ru(2)(3+) complexes under CO are both isomer dependent, thus suggesting that these data can be used to reliably predict the isomeric form, i.e., (3,1) or (4,0), of diruthenium complexes containing four unsymmetrical substituted anilinopyridinate bridging ligands; this was confirmed by X-ray crystallographic data for seven compounds whose structures were available.     

Solubility of Omeprazole Sulfide in Different Solvents at the Range of 280.35–319.65 K

Solubility data were measured for omeprazole sulfide in ethanol, 95 mass-% ethanol, ethyl acetate, isopropanol, methanol, acetone, n-butanol and n-propanol in the temperature range from 280.35 to 319.65 K by employing the gravimetric method. The solubilities increase with temperature and they are in good agreement with the calculated solubility of the modified Apelblat equation and the λh equation. The experimental solubility and correlation equation in this work can be used as essential data and model in the purification process of omeprazole sulfide. The thermodynamic properties of the solution process, including the Gibbs energy, enthalpy, and entropy were calculated using the van’t Hoff equation.