A Switch in the Hydrophobic/Hydrophilic Gas-Adsorption Character of Prussian Blue Analogues: An Affinity Control for Smart Gas Sorption

Porous coordination polymers are molecule-based materials presenting a high degree of tunability, which offer many advantages for targeted applications over conventional inorganic materials. This work demonstrates that the hydrophilic/hydrophobic character of Prussian blue analogues having a lipophilic feature may be tuned to optimize the gas adsorption properties. The role of the coordinatively unsaturated metal sites is emphasized through a combination of theoretical and experimental study of water, ethanol, and n-hexane adsorption.     

Volumetric and infrared measurements on amorphous ice structure

We have simultaneously used adsorption isotherm volumetry and Fourier transform infrared spectroscopy in order to take the investigations on amorphous ice structure a step further, especially concerning porosity and annealing-induced modifications. We have studied surface reorganization during annealing and found that the number of surface sites decreases before crystallization, their relative ratios being different for amorphous and crystalline ice. We also present results confirming that ice can have a large specific surface area and nevertheless be non-microporous.     

Quantitative Comparison of REAPDOR and TRAPDOR Experiments by Numerical Simulations and Determination of H–Al Distances in Zeolites

Quantitative H–Al distances in acid sites of two zeolites with MFI and IFR framework topology were obtained by numerical simulation of ¹H{²⁷Al} rotational echo adiabatic passage double resonance (REAPDOR) experiments. A ²⁷Al offset-dependent data set yields for each resolved ¹H NMR line a corresponding nuclear electric quadrupole coupling constant of the neighboring ²⁷Al site. This information is used for analyzing a second data set for on-resonance irradiation, where the dipolar evolution time (number of rotor cycles) was varied, to yield the ¹H–²⁷Al dipolar coupling constant. Numerical simulations indicate that the REAPDOR method does not depend significantly on the polar angles, defining the orientation of the electric field gradient tensor of ²⁷Al with respect to the Al–H dipolar vector. In contrast, the transfer of populations in double resonance sequence is sensitive to these angles, and it can be thus used to measure them.     

Time-resolved fluorescence spectra of a bichromophoric molecule, 2-methyl-1,2,3,4-tetrahydroisoquinoline in various media

Time-resolved fluorescence spectra of a title molecule (with benzene and aliphatic amine parts) in various media, after excitation by several lasers were observed to complement the previous work by conventional spectroscopy [N. Kanamaru, J. Tanaka, J. Phys. Chem. 95 (1991) 6441]. Though complex with many new features, the results were roughly consistent with the previous ones. The significant conclusions are as follows: (1) The emission to be ascribed to the amine (N) part, with more than one component (of nN and aN types) is observed not only for the acetonitrile solution (as previously reported) but also for all the other media. (2) Contrary to the case of a nonpolar hexane solution, both of N fluorescences in the other media reveal unusually long-lived decay components. This can be interpreted by assuming the so-called charge-transfer-to-solvent (CTTS) state that is nonfluorescent and lies just below the fluorescent state. (3) This observation in the protic media can also be taken as another evidence of the peculiar hydrogen bonding between this amine and the protic solvent molecules [N. Kanamaru, J. Tanaka, J. Phys. Chem. 95 (1991) 6441]. (4) Thus, the unexpectedly large quantum yields of N fluorescences in the polar media are now interpreted as arising due to the slow S₁^N→(CTTS)→S₀ internal conversions.     

Conversion of acids to benzimidazoles with transition metal/zeolites

Transition metal/Y zeolites were prepared using microwave solid state and aqueous solution ion exchange methods. The activity of these zeolites was investigated in a conversion of acids to benzimidazoles reaction between 4-methyl-1, 2-phenylenediamine and 3-nitrobenzoic acid. The yield of these reactions increased in order of CuY < Fe²⁺Y < NiY < CoY < NaY < CrY < MnY < ZnY for both methods. The solid state ion-exchanged zeolites showed higher activity in comparison to the aqueous solution exchange. Yields of products in the presence of the ZnY zeolite were of the order of 69–83%. It seems that the Lewis sites are better sites compared to the Bronsted sites for this reaction.     

Ω型分子筛脱铝的核磁共振研究

在不同投料比（ＳｉＯ２／Ａｌ２Ｏ３＝１３．８，１９及２１）条件下，合成了三种Ω型分子筛原粉．对投料比为１３．８的原粉样品进行了四种不同方式的脱铝处理，即水热、ＳｉＣｌ４、ＥＤＴＡ和（ＮＨ４）２ＳｉＦ６处理，而形成了系列脱铝Ω型分子筛样品．对原粉及其脱铝样品进行了２９Ｓｉ和２７ＡｌＭＡＳＮＭＲ测试，确定出样品骨架硅铝比和铝在两种晶体学不等价Ｔ位上的占据比率，以探索四种脱铝方法的效果．实验结果与分析表明：在所有样品中，铝原子的占据具有择优Ｂ位的倾向；且铝在ＴＡ与ＴＢ位上的占据比率与合成条件有关；四种处理方式对Ω型分子筛的脱铝效果不尽相同．     

predForm-Site: Formylation site prediction by incorporating multiple features and resolving data imbalance

Formylation is one of the newly discovered post-translational modifications in lysine residue which is responsible for different kinds of diseases. In this work, a novel predictor, named predForm-Site, has been developed to predict formylation sites with higher accuracy. We have integrated multiple sequence features for developing a more informative representation of formylation sites. Moreover, decision function of the underlying classifier have been optimized on skewed formylation dataset during prediction model training for prediction quality improvement. On the dataset used by LFPred and Formator predictor, predForm-Site achieved 99.5% sensitivity, 99.8% specificity and 99.8% overall accuracy with AUC of 0.999 in the jackknife test. In the independent test, it has also achieved more than 97% sensitivity and 99% specificity. Similarly, in benchmarking with recent method CKSAAP_FormSite, the proposed predictor significantly outperformed in all the measures, particularly sensitivity by around 20%, specificity by nearly 30% and overall accuracy by more than 22%. These experimental results show that the proposed predForm-Site can be used as a complementary tool for the fast exploration of formylation sites. For convenience of the scientific community, predForm-Site has been deployed as an online tool, accessible at http://103.99.176.239:8080/predForm-Site.     

IR study of heterogeneity of OH groups in zeolite HY-splitting of OH and OD bands

We have been studying the problem of heterogeneity of OH groups in zeolites HY for a long time. The heterogeneity was suggested by the shift of the IR band of OH groups restoring upon ammonia desorption and also by the fact that the band of OH groups forming hydrogen bonds was relatively broad (broader than for homogeneous acidic OH). In the present study we present another important argument for heterogeneity: the splitting of the IR band of free OH and OD groups in a zeolite of Si/Al=8.3 dealuminated by (NH₄)₂SiF₆ treatment. Such a splitting is the best seen in low temperature spectra of OD groups. We found less acidic 3640 cm⁻¹ (AlO)(SiO)₂SiO₁HAl(OSi)₃ and more acidic 3625 cm⁻¹ (SiO)₃SiO₁HAl(OSi)₃ groups. The presence of these two kinds of hydroxyls corresponds to the presence of Si(2Al) and Si(1Al), respectively, detected in ²⁹Si MAS NMR spectra. We also found a small amount of strongly acidic 3599 cm⁻¹ hydroxyls interacting with extraframework Al species.     

Chemisorption of SO2 and Cl2 on indium oxide

The mutual influence of SO₂ and Cl₂ during their consecutive chemisorption on the In₂O₃ surface has been investigated. It was found that SO₂ is chemisorbed in the uncharged form, and the amount of chemisorption decreases as the temperature increases. The preliminary chemisorption of Cl₂ results in a dramatic decrease in the amount of SO₂ sorbed and in a change in the character of the bonding of SO₂ with the oxide surface. When SO₂ is sorbed first, the temperature of the formation of chlorides during subsequent chemisorption of Cl₂ decreases.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1718–1721, October, 1994.     

K2O对Pt—Sn／Al2O3催化剂表面酸性及MCH脱氢稳定性的影响

利用吡啶吸附－ＩＲ，ＮＨ３吸附－脱附，原位热重积炭，ＤＳＣ等技术并结合甲基环己烷（ＭＣＨ）脱氢活性试验，研究了Ｋ２Ｏ对工业Ｐｔ－Ｓｎ／Ａｌ２Ｏ３催化剂的表面酸性及ＭＣＨ脱氢稳定性的影响，结果表明，Ｋ２Ｏ能有效地调变催化剂的表面酸性，降低其表面酸中心特别是强酸中心的数目；ＭＣＨ脱氢反应的积炭量随Ｋ２Ｏ含量的增加而减少，但催化剂的高温脱氢稳定性与Ｋ２Ｏ含量并不完全呈顺变关系，Ｋ２Ｏ含量应严格控制，当Ｋ