Achieving Molecular Recognition of Structural Analogues in Surface-Enhanced Raman Spectroscopy: Inducing Charge and Geometry Complementarity to Mimic Molecular Docking

Molecular recognition of complex isomeric biomolecules remains challenging in surface-enhanced Raman scattering (SERS) spectroscopy due to their small Raman cross-sections and/or poor surface affinities. To date, the use of molecular probes has achieved excellent molecular sensitivities but still suffers from poor spectral specificity. Here, we induce “charge and geometry complementarity” between probe and analyte as a key strategy to achieve high spectral specificity for effective SERS molecular recognition of structural analogues. We employ 4-mercaptopyridine (MPY) as the probe, and chondroitin sulfate (CS) disaccharides with isomeric sulfation patterns as our proof-of-concept study. Our experimental and in silico studies reveal that “charge and geometry complementarity” between MPY's binding pocket and the CS sulfation patterns drives the formation of site-specific, multidentate interactions at the respective CS isomerism sites, which “locks” each CS in its analogue-specific complex geometry, akin to molecular docking events. Leveraging the resultant spectral fingerprints, we achieve > 97 % classification accuracy for 4 CSs and 5 potential structural interferences, as well as attain multiplex CS quantification with < 3 % prediction error. These insights could enable practical SERS differentiation of biologically important isomers to meet the burgeoning demand for fast-responding applications across various fields such as biodiagnostics, food and environmental surveillance.     

分光光度法在制备负载型多糖吸附污水中铅的应用

本文用不同活性炭制备了负载型多糖（活性炭改良）,多糖的负载率用硫酸苯酚法测定,标准曲线回归方程为Y=0.005906X+0.1234（ r=0.9998）,RSD为0.7%,线性范围为5~50.0mg/L,耶壳活性炭多糖负载率最高为65.71%。用自制负载型多糖清除污水中的铅,以甲基百里香酚蓝为显色剂,用光度法测定铅吸附率,测定条件为,室温、波长为610nm、甲醇为增敏剂、pH为6、显色剂用量为1.5mg/L,反应时间50min,方法的标准曲线回归方程为Y=0.0682X+0.1825（r=0.9999）,线性范围为0～8.0mg/L。平均6次的检出限为0.2mg/L,加标回收率在96.8%～102.3%,RSD为0.39%～3.2%,同时作了共存离子的干扰。结果不同负载型多糖对铅离子的吸附不同,其中椰壳活性炭负载多糖对铅的吸附最大为28.61%,比相应活性炭对铅的吸附高了16.08%。将多糖负载在活性炭上,可明显提高对铅离子的吸附,所以该研究为清除实际污水乃至土壤中的铅提供依据。     

高频燃烧红外吸收法测定铅精矿中的硫

利用高频燃烧红外吸收碳硫仪测定铅精矿中的硫含量。低硫含量(S<5%)铅精矿样品直接称样测定;高硫含量(S>5%)铅精矿样品添加稀释剂后称样测定。对样品称样量、助熔剂类型及用量等条件进行了研究,获得最佳分析条件。通过空白实验测得方法检出限为0.0010%,利用铅精矿有证标准物质进行精密度和准确度验证,方法的标准偏差在0.295%~1.3%之间,结果表明该方法精密度高、准确度好,能够满足铅精矿中硫含量的快速准确测定。     

Coupled heat and mass transfer in mixed convection over a vertical flat plate embedded in saturated porous media: PST/PSC or PHF/PMF

A boundary layer analysis is used to investigate the heat and mass transfer characteristics of mixed convection about a vertical flat plate embedded in a saturated porous medium under the coupled effects of thermal and mass diffusion. The plate is maintained at prescribed surface temperature/concentration (PST/PSC) or prescribed heat/mass flux (PHF/PMF). The nonsimilar governing equations are obtained by using a suitable transformation and solved by Keller box method. Numerical results for the local heat transfer rate and the local mass transfer rate are presented for various parameters. The local heat and mass transfer rates increase with increasing n and m and buoyancy parameter ξ. When buoyancy parameter ξ is very small (large) the value of local Nusselt and the local Sherwood number correspond with the pure forced (free) convection, respectively. Increasing buoyancy ratio N (or N ^*) increases the local heat and mass transfer rates. It is apparent that Lewis number has a pronounced effect on the local mass transfer rate than it does on the local heat transfer rate. Furthermore, increasing Lewis number decreases (increases) the local heat (mass) transfer rate. Received on 8 December 1997     

The effect of cocurrent and countercurrent gas shear on entrance region mass transfer in turbulent falling liquid films

Predictions of average film thickness and mass transfer coefficients in the entrance region of gas absorption with high cocurrent and countercurrent gas flow in a turbulent falling film are presented. The model used is a modified van Driest eddy diffusivity in the inner wall region and an interface damping eddy diffusivity in the outher region of the film modified to include the effect of interfacial shear. The calculations show that the entrance length for mass transfer decreases with increasing film Reynolds number and interfacial shear for cocurrent flow. Also the model predicts a decrease in mass transfer coefficient with an increase in Schmidt number in accordance with experimental data. On the other hand, for counterflow and at a fixedRe, an increase in upward gas shear increases the film thickness and eventually leads to rising film flow. The entrance length for mass transfer decreases with increasing Reynolds number but slightly increases with countercurrent interfacial shear. The calculations show that, in practice, the entrance region for mass transfer for gas absorption with shear-thinned film can be neglected for cocurrent shear but often cannot be neglected for countercurrent shear with a shear-thickened film.Es werden Berechnungen für die mittlere Film-dicke und die Stoffübertragungs-Koeffizienten in der Eintrittsregion der Gasabsorption mit starkem Gleich- und Gegenstrom von Gas in einem turbulent fließenden Film aufgestellt. Das benutzte Modell ist ein modifizierter van Driest-Wirbel-Diffuser für die Innenwand und ein gedämpfter Grenzflächen-Wirbel-Diffuser in der Außenregion des Filmes, der so modifiziert ist, daß die Effekte der Grenzschichtschubspannungen berücksichtigt werden. Die Berechnungen zeigen, daß die Eintrittslänge für die Stoffübertragung mit zunehmender Grenzflächenschubspannung für Gleichstrom abnimmt. Das Modell sagt ebenso ein Sinken des Stoffübertragungs-Koeffizienten mit einer Zunahme der Schmidt-Zahl in Übereinstimmung mit den experimentellen Daten voraus. Auf der anderen Seite führt im Falle von Gegenstrom und einer konstanten Reynolds-Zahl ein Ansteigen der Gasschubspannung zu einem Anwachsen der Filmdicke und eventuell zu wachsender Filmströmung. Die Eintrittslänge für die Stoffübertragung sinkt mit zunehmender Reynolds-Zahl, steigt aber langsam bei Grenzflächenschubspannungen in Gegenstromrichtung. Die Berechnungen zeigen, daß in der Praxis die Eintrittsregion für die Stoffübertragung bei der Gasabsorption mit verdünntem Film für Gleichstromschubspannung vernachlässigt werden kann, bei Gegenstromschubspannung mit verdicktem Film diese jedoch meist berücksichtigt werden muß.     

General solution for interaction of solitary waves including head-on collisions

A general solution of the Boussinesq equation is presented which solves the problem of interaction of any number of right-going and left-going solitary waves. The solution relies on the exact solution of Gardner, Greene, Kruskal, and Miura (1967), and has the same degree of accuracy as that solution, but has a wider scope of application. It is much simpler than, but as accurate as, Hirota's exact solution (1973) of the Boussinesq equation, to which the present solution is compared for the simplest case of two solitary waves in head-on collision.     

Serum pharmacochemistry combined with multiple data processing approach to screen the bioactive components and their metabolites in Mutan Cortex by ultra‐performance liquid chromatography tandem mass spectrometry

Root cortex of Paeonia suffruticosa Andrews (Paeoniaceae), known as Moutan Cortex (MC), is known to have anti‐allergic and anti‐inflammatory properties. However, the constituents absorbed into blood after oral administration of MC remain unknown. A sensitive and rapid method by ultra‐high‐pressure liquid chromatography–electrospray ionization–quadrupole‐time‐of‐flight mass spectrometry (UPLC‐ESI‐Q‐TOF‐MS) technology and the MetaboLynx^TM software combined with multiple data processing approach (Mdpa) was established to investigate the absorbed constituents in rats after oral administration of MC, providing unique high‐throughput capabilities for drug metabolism study. A hyphenated electrospray ionization and quadrupole‐time‐of‐flight analyzer was used for the determination of accurate mass of the fragment ion in negative mode, with excellent MS mass accuracy and enhanced data acquisition. This rapid automated analysis method was successfully applied for screening and identification of the constituents absorbed and metabolized studies of MC after oral administration to rats. A total of 46 peaks were obtained from MC, 41 of which were tentatively characterized. In the VIP‐plot of orthogonal partial least‐squares discriminant analysis, 23 interesting ions in serum samples were extracted, and 16 parent components and seven metabolites were detected in vivo. The integrative serum pharmacochemistry technique, UPLC‐ESI‐Q‐TOF‐MS, and Mdpa method were successfully applied for rapid discovery of multiple components from MC. Copyright © 2013 John Wiley & Sons, Ltd.     

Preparation and Optical Limiting Properties of Polyurethane Containing Long Conjugated Chromophores

Two functional polyurethanes (P1 and P2) bearing a large π electron conjugated chromophoric pendant were synthesized and characterized by FT‐IR, ¹H‐NMR and UV‐Vis absorption spectra. Their optical limiting properties were evaluated. The results show that P1 and P2 show novel optical limiting properties, which are assigned to a long π electron conjugated chromophoric pendant. It was found that their optical limiting properties were affected simultaneously by solution concentration and P2 displays a better optical limiting property than P1 at the same solution transmittance, although that P1 has larger χ⁽³⁾ (4.28×10^?11 esu) than P2 (0.87×10^?11 esu), and their optical limiting mechanism is investigated.     

Synthesis and Crystal Structures of the Molybdenum(II) Complexes with the N,N‐dimethylthiocarbamoyl Containing Ligand: Crystal Structures of [Mo(CO)2(η2‐S2COEt)(η2‐SCNMe2)(PPh3)] and [Mo(CO)2(η2‐S2CNC4H8)(η2‐SCNMe2)(PPh3)]

The reaction of the thiocarbamoyl‐molybdenum complex [Mo(CO)₂(η²‐SCNMe₂)(PPh₃)₂Cl] 1 , with EtOCS2K and C4H8NCS2NH4 in dichloromethane at room temperature yielded the seven coordinated ethyldithiocarbonate thiocarbamoyl‐molybdenum complex [Mo(CO)₂(η²‐S₂COEt)(η²‐SCNMe₂)(PPh₃)] 2 , and the dithiocarbamate thiocarbamoyl‐molybdenum complex [Mo(CO)₂(η²‐S₂CNC₄H₈)(η²‐SCNMe₂)(PPh₃)] 3 . The geometry around the metal atom of compounds 2 and 3 are capped octahedrons as revealed by X‐ray diffraction analyses. The thiocarbamoyl and ethyldithiocarbonate or pyrrolidinyldithiocarbamate ligands coordinate to the molybdenum metal center through the carbon and sulfur and two sulfur atoms, respectively. Structure parameters, NMR, IR and Mass spectra are in agreement with the crystal chemistry of the two compounds.