The kernel method and systems of functional equations with several conditions

We generalize the kernel method to equation systems in which the number of unknowns is allowed to exceed the number of equations. With this generalization, we derive the generating functions for several kinds of sequences and generating trees whose recursions are dependent on the parity of the indices.     

Creation of bioorthogonal redox systems depending on nicotinamide flucytosine dinucleotide

Many enzymes catalyzing biological redox chemistry depend on the omnipresent cofactor, nicotinamide adenine dinucleotide (NAD). NAD is also involved in various nonredox processes. It remains challenging to disconnect one particular NAD-dependent reaction from all others. Here we present a bioorthogonal system that catalyzes the oxidative decarboxylation of l-malate with a dedicated abiotic cofactor, nicotinamide flucytosine dinucleotide (NFCD). By screening the multisite saturated mutagenesis libraries of the NAD-dependent malic enzyme (ME), we identified the mutant ME-L310R/Q401C, which showed excellent activity with NFCD, yet marginal activity with NAD. We found that another synthetic cofactor, nicotinamide cytosine dinucleotide (NCD), also displayed similar activity with the ME mutants. Inspired by these observations, we mutated d-lactate dehydrogenase (DLDH) and malate dehydrogenase (MDH) to DLDH-V152R and MDH-L6R, respectively, and both mutants showed fully active with NFCD. When coupled with DLDH-V152R, ME-L310R/Q401C required only a catalytic amount of NFCD to convert l-malate. Our results opened the window to engineer bioorthogonal redox systems for a wide variety of applications in systems biology and synthetic biology.     

Fast and simple methods for the optimization of kurtosis used as a projection pursuit index

As a powerful method for exploratory data analysis, projection pursuit (PP) often outperforms principal component analysis (PCA) to discover important data structure. PP was proposed in 1970s but has not been widely used in chemistry largely because of the difficulty in the optimization of projection indices. In this work, new algorithms, referred as "quasi-power methods", are proposed to optimize kurtosis as a projection index. The new algorithms are simple, fast, and stable, which makes the search for the global optimum more efficient in the presence of multiple local optima. Maximization of kurtosis is helpful in the detection of outliers, while minimization tends to reveal clusters in the data, so the ability to search separately for the maximum and minimum of kurtosis is desirable. The proposed algorithms can search for either with only minor changes. Unlike other methods, no optimization of step size is required and sphering or whitening of the data is not necessary. Both univariate and multivariate kurtosis can be optimized by the proposed algorithms. The performance of the algorithms is evaluated using three simulated data sets and its utility is demonstrated with three experimental data sets relevant to analytical chemistry.     

Synthesis of high-silica EU-1 zeolite in the presence of hexamethonium ions: a seeded approach for inhibiting ZSM-48

A seeded approach was developed to synthesize high-silica EU-1 zeolite via inhibiting the co-crystallization of ZSM-48 in the presence of hexamethonium (HM) ions. A systematic study was carried out to determine factors such as seed content and SiO(2)/Al(2)O(3) ratio, which influenced the crystallization of high-silica EU-1 and transformation of EU-1 into ZSM-48. Using EU-1 seeds, not only well-crystallized pure EU-1 zeolites with SiO(2)/Al(2)O(3) ratios more than 500 were synthesized, but also the co-crystalline of ZSM-48/EU-1 or pure ZSM-48 was obtained in control from silica-rich mixture gels. Furthermore, the kinetic features of the seeded synthesis of EU-1 zeolites with SiO(2)/Al(2)O(3) ratios of 55, 190, and 500 were examined. It was found that seeds played crucial roles in the decrease of apparent activation energy of EU-1 nucleation and inhibiting the transformation of EU-1 into ZSM-48. The HM and Al species performed synergistic roles to inhibit the formation ZSM-48 during high-silica EU-1 nucleation and crystal growth.     

The influence of acid demineralization on surface characteristics of black carbon and its sorption for pentachlorophenol

Acid treatment is a routine demineralization process to obtain black carbon (BC), but there has been little systematic research about its influence on BC's characteristics. In this study, elemental analysis, SEM, FTIR, and Boehm titration were used to investigate that effect. Our results showed that the acid treatment had little influence on the sorption of fly ash and soot to pentachlorophenol (PCP), but it greatly increased the sorption of rice chars to PCP. There were two competing effects of acid demineralization on the adsorption capacity of BC. On one hand, it increased the amount of the acidic functional groups, which decreased the adsorption capacity. On the other hand, it increased the surface and pore volume of BC and caused the emergence of hidden carbon enclosed by minerals, which in turn increased the sorptivity significantly. Especially for rice chars (600°C), after acid treatment, their surface area increased from 3.52 to 235 m(2) g(-1) and the sorption capacity coefficient increased from 2.12 to 4.10.     

Synthesis of 3D porous ferromagnetic NiFe2O4 and using as novel adsorbent to treat wastewater

Three dimensions (3D) porous NiFe(2)O(4) is synthesized by a sol-gel method using egg white. The obtained NiFe(2)O(4) shows both good ferromagnetic properties and high adsorption capacity. The porous NiFe(2)O(4) shows good adsorption properties for organic dyes (Methylene Blue (138.50 mg/g), Fuchsine Red (14.61 mg/g), Methyl Violet (19.06 mg/g)) and heavy metal ions (Cu (II) (55.83 mg/g), Cr (VI) (36.95 mg/g) and Ni (II) (37.02 mg/g)) due to its 3D interconnected porous structure. The maximum adsorption of Methylene Blue (MB) fit the pseudo-second-order model and Langmuir isotherm equation well. More interestingly, the ferromagnetic NiFe(2)O(4) can be separated under a magnetic field conveniently and keeps high removal efficiency (>97%) during seven reusable cycles. These results suggest that the porous NiFe(2)O(4) is a promising favorable and reusable adsorbent.     

Multifunctional NO-delivery vessel derived from aminopropyl-modified mesoporous zeolites

A new strategy, releasing nitric oxide (NO) and adsorbing nitrosamines simultaneously by zeolitic materials in the digestive system, is validated in this paper. Three types of moisture-saturated molecular sieves, HZSM-5 zeolite, mesoporous zeolite, and mesoporous silica MCM-41, are used as NO-delivery vessels in mimic gastric juice after modification of γ-aminopropyltriethoxysilane (APTES). APTES modification dramatically increased the capability of zeolite and mesoporous silica in NO release in acidic solution, because more NO can be adsorbed in the composite and stored in the form of nitrite. Some composites released the NO 10 times more than their parent materials, and synchronously captured the carcinogen nitrosamines in mimic gastric juice. The influences of APTES modification on the porous structure and surface state of zeolite and mesoporous silica were investigated by XRD, N(2) adsorption, and FTIR tests, through which the mesoporous zeolite is proven to be the optimal support. With this hierarchical material a controllable APTES modification is realized in which a lot of aminopropyl groups are grafted in mesopores while the zeolitic structure is maintained, so the resulting sample exhibits a high capability in releasing NO and adsorbing nitrosamines. This investigation provides a clue for elevating the efficiency of zeolites in the application of life science.     

Controlling the primary particle evolution process towards silica monoliths with tunable hierarchical structure

In order to establish the hierarchical structure in multiple levels on mesoporous silica, this article reports a new strategy to prepare the monolith with the pore configuration in nanometer scale, micro-morphology in micrometer level and macroscopic shape in millimeter or larger grade. These hierarchical monoliths are synthesized in a weak acidic condition by using triblock copolymer P123, hydroxyl carboxylic acid and tetramethyl orthosilicate (TMOS), and the textural properties of the mesostructure can be facilely adjusted by simply controlling the synthesis condition without any additive. During the synthesis, the primary particles can be selectively synthesized as monodispersed sphere, noodle, prism, straight rods with different size or irregular bars, and their connection plus arrangement in 3D directions can be also regulated. Therefore, various textural properties of mesopore are able to be altered including pore size (5.5-10.6 nm), total pore volume (0.48-1.2 cm(3) g(-1)), micropore surface area (47-334 m(2) g(-1)), and pore shape (from 2D or 3D straight channel to plugged channel). Moreover, these monoliths exhibit a considerable mechanical strength; they are also applied in eliminating particulate matters and tobacco special nitrosamines (TSNA) in tobacco smoke, exhibiting various morphology-assisted functions.     

Plasma-electrolysis synthesis of TiO2 nano/microspheres with optical absorption extended into the infra-red region

A novel plasma-electrolysis method is introduced to synthesize high-quality TiO(2) nano/microspheres that exhibited excellent optical absorption covering the range from ultraviolet to infra-red. Both experimental and theoretical results show that the oxygen vacancies in the TiO(2) spheres are primarily responsible for this wide absorption.     

Reversible single crystal to single crystal transformation with anion exchange-induced weak Cu2+···I⁻ interactions and modification of the structures and properties of MOFs

{[Cu(6)(TTTMB)(8)(OH)(4)(H(2)O)(6)]·8(NO(3))·34.5H(2)O}(n) can reversibly transform to {[Cu(6)(TTTMB)(8)I(3)]·9I·26H(2)O}(n) upon a single crystal to single crystal process. The transformation is accompanied by the formation of weak Cu(2+)I(-) interactions and changes in the coordination numbers, as well as modulation in their properties.