Isolation and purification of uremic middle molecules by multi-step liquid chromatography

Isolation and comparison of uremic sera and urine and normal sera and urine were performed by gel permeation chromatography, anion exchange chromatography and re-versed-phase high performance liquid chromatography. Two uremic middle molecular fractions (A and B) were obtained from uremic sera and urine and normal urine by gel permeation chromatography, but not from normal sera. The anion exchange chromatographic results of fraction A from different origins demonstrate that subfraction A-3 could be excreted in urine by healthy subject, but accumulated in uremic serum for renal failure of patient with uremia. After desalinization subfraction A-3 was analyzed by MALDI-TOF-MS. The results show that subfraction A-3 consists of six compounds with molecular weight 839, 873, 1007.94, 1106, 1680 and 2015 respectively. Finally, by reversed-phase high performance liquid chromatography, subfraction A-3 was further resolved into six independent fractions. Thus, the isolation and purification of six middle molecular c     

Electrochemical functionalization of organic compounds by “small” molecules

The author's results and published data on the electrochemical insertion of small molecules (CO₂, SO₂, CS₂, NO) into organic substrates are reviewed. Special attention is paid to the cathodic carboxylation of halogen-containing aliphatic and aromatic compounds, polymers, and olefins, the sulfonylation and dithiocarboxylation of Freons, and anodic nitrosation of amines. The probable mechanisms of such processes and the effects of the nature of the reagents and the electrolysis conditions on the composition and yields of the final reaction products are examined.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, No. 2, pp. 97–114, March–April, 1992.     

Does compressibility affect the results obtained by small angle neutron scattering?

Recently a few papers have been devoted to the scattering by polymer solutions and blends^(1,2) assuming that the systems under investigation are compressible, contrarily to what is usually done. This is motivated by the fact that if one uses the theory of incompressible mixtures in scattering experiments, one obtains values of the Flory⁽³⁾ χ parameter which are inconsistent with the values obtained by other techniques. In this paper we would like to show that, contrarily to what has been said, the effect of compressibility can be easily evaluated; it is very small and already corrected in the classical treatment of the data used in light or neutron scattering experiments.     

Superstructure based on β-CD self-assembly induced by a small guest molecule

The size, shape and surface chemistry of nanoparticles play an important role in cellular interaction. Thus, the main objective of the present study was the determination of the β-cyclodextrin (β-CD) self-assembly thermodynamic parameters and its structure, aiming to use these assemblies as a possible controlled drug release system. Light scattering measurements led us to obtain the β-CD's critical aggregation concentration (cac) values, and consequently the thermodynamic parameters of the β-CD spontaneous self-assembly in aqueous solution: Δ(agg)G(o) = -16.31 kJ mol(-1), Δ(agg)H(o) = -26.48 kJ mol(-1) and TΔ(agg)S(o) = -10.53 kJ mol(-1) at 298.15 K. Size distribution of the self-assembled nanoparticles below and above cac was 1.5 nm and 60-120 nm, respectively. The number of β-CD molecules per cluster and the second virial coefficient were identified through Debye's plot and molecular dynamic simulations proposed the three-fold assembly for this system below cac. Ampicillin (AMP) was used as a drug model in order to investigate the key role of the guest molecule in the self-assembly process and the β-CD:AMP supramolecular system was studied in solution, aiming to determine the structure of the supramolecular aggregate. Results obtained in solution indicated that the β-CD's cac was not affected by adding AMP. Moreover, different complex stoichiometries were identified by nuclear magnetic resonance and isothermal titration calorimetry experiments.     

Single domain antibody–quantum dot conjugates for ricin detection by both fluoroimmunoassay and surface plasmon resonance

The combination of stable biorecognition elements and robust quantum dots (QDs) has the potential to yield highly effective reporters for bioanalyses. Llama-derived single domain antibodies (sdAb) provide small thermostable recognition elements that can be easily manipulated using standard DNA methods. The sdAb was self-assembled on dihydrolipoic acid (DHLA) ligand-capped CdSe–ZnS core–shell QDs made in our laboratory through the polyhistidine tail of the protein, which coordinated to zinc ions on the QD surface. The sdAb–QD bioconjugates were then applied in both fluorometric and surface plasmon resonance (SPR) immunoassays for the detection of ricin, a potential biothreat agent. The sdAb–QD conjugates functioned in fluoroimmunoassays for the detection of ricin, providing equivalent limits of detection when compared to the same anti-ricin sdAb labeled with a conventional fluorophore. In addition, the DHLA-QD–sdAb conjugates were very effective reporter elements in SPR sandwich assays, providing more sensitive detection with a signal enhancement of ∼10-fold over sdAb reporters and 2–4 fold over full sized antibody reporters. Commercially prepared streptavidin-modified polymer-coated QDs also amplified the SPR signal for the detection of ricin when applied to locations where biotinylated anti-ricin sdAb was bound to target; however, we observed a 4-fold greater amplification when using the DHLA-QD–sdAb conjugates in this format.     

Determination of phosphorus in small amounts of protein samples by ICP–MS

Inductively coupled plasma mass spectrometry (ICP-MS) is used for phosphorus determination in protein samples. A small amount of solid protein sample (down to 1 micro g) or digest (1-10 micro L) protein solution was denatured in nitric acid and hydrogen peroxide by closed-microvessel microwave digestion. Phosphorus determination was performed with an optimized analytical method using a double-focusing sector field inductively coupled plasma mass spectrometer (ICP-SFMS) and quadrupole-based ICP-MS (ICP-QMS). For quality control of phosphorus determination a certified reference material (CRM), single cell proteins (BCR 273) with a high phosphorus content of 26.8+/-0.4 mg g(-1), was analyzed. For studies on phosphorus determination in proteins while reducing the sample amount as low as possible the homogeneity of CRM BCR 273 was investigated. Relative standard deviation and measurement accuracy in ICP-QMS was within 2%, 3.5%, 11% and 12% when using CRM BCR 273 sample weights of 40 mg, 5 mg, 1 mg and 0.3 mg, respectively. The lowest possible sample weight for an accurate phosphorus analysis in protein samples by ICP-MS is discussed. The analytical method developed was applied for the analysis of homogeneous protein samples in very low amounts [1-100 micro g of solid protein sample, e.g. beta-casein or down to 1 micro L of protein or digest in solution (e.g., tau protein)]. A further reduction of the diluted protein solution volume was achieved by the application of flow injection in ICP-SFMS, which is discussed with reference to real protein digests after protein separation using 2D gel electrophoresis.The detection limits for phosphorus in biological samples were determined by ICP-SFMS down to the ng g(-1) level. The present work discusses the figure of merit for the determination of phosphorus in a small amount of protein sample with ICP-SFMS in comparison to ICP-QMS.     

Improved interfacial property by small molecule ethanediamine for high performance inverted planar perovskite solar cells

We report a simple and effective method to realize desirable interfacial property for inverted planar perovskite solar cells(PSCs)by using small molecule ethanediamine for the construction of a novel polyelectrolyte hole transport material(P3CT-ED HTM).It is found that P3CT-ED can not only improve the hole transport property of P3CT-K but also improve the crystallinity of adjacent perovskite film.In addition,the introduction of ethanediamine into P3CT realigns the conduction and valence bands upwards,passivates surface defects and reduces nonradiative recombination.As a consequence,compared to P3CT-K hole transport layer(HTL)based devices,the average power conversion efficiency(PCE)is boosted from17.2% to 19.6% for the counterparts with P3CT-ED,with simultaneous enhancement in open circuit voltage and fill factor.The resultant device displays a champion PCE of 20.5% with negligible hysteresis.     

Characterization and application of quantum dot nanocrystal–monoclonal antibody conjugates for the determination of sulfamethazine in milk by fluoroimmunoassay

Quantum dot (Qdot) nanocrystals have been increasingly used as fluorescence labels in fluoroimmunoassays recently because of their excellent optical characteristics. In this paper, a new monoclonal antibody (MAb) against sulfamethazine (SMZ) was successfully produced and linked to Qdot nanocrystals by covalent coupling. The Qdot–MAb conjugates were characterized by SDS-PAGE and high-performance capillary electrophoresis (HPCE). An enzyme-linked immunosorbent assay (ELISA) method was utilized to evaluate the antigen–antibody binding affinity and then a novel direct competitive fluorescence-linked immunosorbent assay (cFLISA) for the detection of SMZ in milk by using Qdots as fluorescent labels was evaluated. The results showed that the 50% inhibition values (IC₅₀) of the cFLISA were 4.3 ng/mL in milk and 5.2 ng/mL in PBS, and the limits of detection (LODs) were 0.6 ng/mL in milk and 0.4 ng/mL in PBS, respectively. The recoveries of SMZ from spiked milk samples at levels of 10–100 ng/mL ranged from 94 to 106%, with coefficients of variation (CVs) of 2.1–9.2%. Figure Shematic diagram of the direct cFLISA procedure Jianzhong Shen and Fei Xu contributed equally to this work.     

95Tc and96Tc production by (γ, xn) reactions

The⁹⁹Tc (, 3n)⁹⁶Tc and⁹⁹Tc (, 4n)⁹⁵Tc reactions were studied by irradiation of target⁹⁹Tc with bremsstrahlung from the linear electron accelerator of Tohoku University, up to 50 MeV -energy. The resulting⁹⁶Tc (4.3 d) and⁹⁵Tc (20 h) activities were determined by -spectrometry. The -flux was monitored by the⁹⁹Tc (, )^99mTc reaction. Metallic copper and gold foils were used as additional flux monitors in front of and behind the samples. Their measured radioactivity was utilized for normalizing bremsstrahlung flux calculations, in order to determine reaction cross sections. Cross sections were also determined theoretically, performing calculations in the framework of a neutron cascade evaporation model. Above the (, 3n) and (, 4n) threshold energies the neutron emission channel was supposed to be the only open channel for deexcitation following photoabsorption. The preeguilibrium contribution was considered negligible. The experimental results obtained for the integrated cross section at 30 and 50 MeV fit reasonably well the calculated curves.     

High-Capacity Zinc Anode with 96 % Utilization Rate Enabled by Solvation Structure Design

Aqueous zinc-ion batteries (AZBs) show promises for large-scale energy storage. However, the zinc utilization rate (ZUR) is generally low due to side reactions in the aqueous electrolyte caused by the active water molecules. Here, we design a novel solvation structure in the electrolyte by introduction of sulfolane (SL). Theoretical calculations, molecular dynamics simulations and experimental tests show that SL remodels the primary solvation shell of Zn²⁺, which significantly reduces the side reactions of Zn anode and achieves high ZUR under large capacities. Specifically, the symmetric and asymmetric cells could achieve a maximum of ∼96 % ZUR at an areal capacity of 24 mAh cm⁻². In a ZUR of ∼67 %, the developed Zn−V₂O₅ full cell can be stably cycled for 500 cycles with an energy density of 180 Wh kg⁻¹ and Zn-AC capacitor is stable for 5000 cycles. This electrolyte structural engineering strategy provides new insight into achieving high ZUR of Zn anodes for high performance AZBs.     

Controlling adsorption and release of drug and small molecules by organic functionalization of mesoporous materials

A series of mesoporous nanosphere materials that are functionalized with various terminal and bridging organic groups were synthesized. They have improved adsorption capacity and different release properties for drug and small molecules. The materials contained terminal vinyl, 3-mercaptopropyl, 3-aminopropyl, and secondary amine functional groups and bridging ethane, ethene, and benzene groups within their mesopore channel walls. The samples containing mercaptopropyl and vinyl groups showed greater adsorption capacity and better controlled release behavior for rhodamine 6G molecules. On the other hand, mesoporous matrices containing amine functional groups showed higher adsorption capacity and better release properties for ibuprofen molecules. Further studies revealed that the bridging organic groups in the mesopore channel walls also improved the adsorption capacity and release properties of the materials compared to the corresponding samples containing no bridging organic groups. Such improved adsorption and controlled release properties of molecules by simple changes of functional groups on mesoporous materials are important for the development of nanomaterial drug delivery vehicles and for controlled release of drugs over long time periods at specific targeted sites in the body. By judicious choice of organic groups and by systematic design and synthetic approaches, nanoporous materials having different adsorption capacity and release properties for many other drug molecules can also be achieved.     

Improving current and mitigating energy loss in ternary organic photovoltaics enabled by two well-compatible small molecule acceptors

Ternary organic photovoltaic(OPV)strategy is an effective but facile approach to enhance the photovoltaic performance for single-junction devices.Herein,a series of ternary OPVs were fabricated by employing a wide bandgap donor(PBDB-TF)and two acceptor-donor-acceptor(A-D-A)-type nonfullerene small molecule acceptors(NF-SMAs,called F-2 Cl and 3 TT-OCIC).As the third component,the near-infrared SMA,3 TT-OCIC,has complementary absorption spectrum,narrow bandgap and wellcompatible crystallization property to the host acceptor(F-2 Cl)for efficient ternary OPVs.With these,the optimal ternary devices yield significantly enhanced power conversion efficiency of 15.23%,one of the very few examples with PCE higher than15%other than Y6 systems.This is mainly attributed to the increased short-circuit current density of 24.92 m A cm^-2 and dramatically decreased energy loss of 0.53 e V.This work presents a successful example for simultaneously improving current,minimizing energy loss and together with modifying the morphology of active layers in OPVs,which will contribute to the further construction of high performance ternary OPVs.     

Electronic structure analysis of small gold clusters Au m (m?��?16) by density functional theory

Small gold clusters Au _m (m????16) were analyzed step by step using the density functional theory at B3LYP level with a Lanl2DZ pseudopotential to understand the rules governing the structures obtained for the most stable clusters. After a characterization by means of the NBO population analysis and spin densities, the particular electronic structure of such species was confronted to their structural parameters and stability. It appears that the most stable structures can be described in an original way through resonance structures resulting from an analysis of Au _m clusters into dimeric Au₂ subunits. These are arranged so as to promote: 1. A good overlap between bonding ?? and anti-bonding ??* areas belonging to different Au₂ units. 2. A cyclic flow of electrons over the whole cluster. This model uses relatively simple chemical concepts in order to justify most of the structures already found in the literature as well as to establish a new approach explaining the structural transition from two- to three-dimensional configurations.     

Graphene quantum dot–based electrochemical biosensing for early cancer detection

Electrochemical biosensing systems coupled with graphene quantum dots (GQDs) have demonstrated suitability for cancer diagnostic strategies, particularly to identify the changes facilitating the early phases of tumorigenesis as well as to detect ultralow concentrations of biomarkers that distinguish between normal and malignant cells. GQDs, known as a novel class of zero-dimensional semiconductor nanocrystals, are tiny graphene particles arranged in a honeycomb structure with a size range of 1–50 nm. The size of these GQDs is comparable with the size of biomolecules, thereby providing an ideal platform to study biomolecules such as proteins, cells, and viruses. GQDs are a superior platform for specific and sensitive recognition of cancer biomarkers; they are highly synergistic with electrochemical sensors. This review will shed light on the recent advancements made in the field of GQD-based electrochemical sensors for early cancer detection, with the aim of highlighting the prospects for further development in cancer diagnostics.     

Fluorescence detection of pesticides using quantum dot materials – A review

High pesticide use, especially in agriculture, can lead to environmental pollution and potentially adverse health effects. As result, pesticide residues end up in different media, including water and food products, which may serve as direct routes for human exposure. There is thus a continuous drive to develop analytical methods for screening and quantification of these compounds in the different environmental media in which they may occur. Development of quantum dot (QD) based sensors for monitoring pesticides has gained momentum in recent years. QD materials have excellent and unique optical properties and have high fluorescence quantum yields compared to other fluorophores. They have thus been used in numerous studies for the development of probes for organic pollutants. In this paper we specifically review their application as fluorescence probes for pesticide detection in different media including water and in fruits and vegetables. The low detection limits reported demonstrate the potential use of these methods as alternatives to expensive and time-consuming conventional techniques. We also highlight potential limitations that these probes may present when it comes to routine application. Finally we discuss possible future improvements to enhance the selectivity and robustness of these sensors. We note that there is still a need for researchers to develop standardized QD based sensors which could lead to their commercialization and routine application.     

Allosteric regulation of protein kinase PKCζ by the N-terminal C1 domain and small compounds to the PIF-pocket

Protein kinases are key mediators of cellular signaling, and therefore, their activities are tightly controlled. AGC kinases are regulated by phosphorylation and by N- and C-terminal regions. Here, we studied the molecular mechanism of inhibition of atypical PKCζ and found that the inhibition by the N-terminal region cannot be explained by a simple pseudosubstrate inhibitory mechanism. Notably, we found that the C1 domain allosterically inhibits PKCζ activity and verified an allosteric communication between the PIF-pocket of atypical PKCs and the binding site of the C1 domain. Finally, we developed low-molecular-weight compounds that bind to the PIF-pocket and allosterically inhibit PKCζ activity. This work establishes a central role for the PIF-pocket on the regulation of PKCζ and allows us to envisage development of drugs targeting the PIF-pocket that can either activate or inhibit AGC kinases.     

The possibility of semiconductor–metal transition in a spherical quantum dot

We observe an abrupt change in diamagnetic susceptibility at critical donor concentration for an $\text{ Al }_\mathrm{x}\text{ Ga }_\mathrm{1-x}\text{ As/GaAs }$ Al x Ga 1 ? x As/GaAs quantum dot system in the effective mass approximation indicating a possible semiconductor metal transition. The effect of confining potential and the laser intensity on the abrupt change in diamagnetic susceptibility has also been studied. The effect of nonparabolicity of the conduction band has been included in our calculations. Results are presented and discussed.     

Diketopyrrolopyrrole-derived organic small molecular dyes for tumor phototheranostics

Cancer is one of the leading causes of human death around the world. Phototherapy, including photodynamic therapy(PDT) and photothermal therapy(PTT), is an emerging light-triggered cancer treatment and shows the advantages of non-invasiveness and low side effects. The design and preparation of efficient phototherapeutic agents are of great significance for phototherapy. Diketopyrrolopyrrole(DPP) is a small molecular organic dye featuring outstanding photophysical properties, facile tuning of str...