Surface Functionalization of Green-synthesized Reduced Graphene Oxide with PPIX Enhances Photosensitization of Cancer Cells

Photosensitizer-functionalized reduced graphene oxide (rGO) nanoparticles are promising materials for photodynamic therapy in cancer management. In this study, rGO is synthesized by a green route employing glucose as the reducing agent and functionalized with photosensitizer, protoporphyrin IX (PPIX) in a convenient, single-step procedure. PPIX-functionalized rGO exhibits photodynamic effect against cancer cells (HeLa) at 0.001 mg mL⁻¹ under visible light illumination (635 nm). A 50% elimination of HeLa cells after 5 min irradiation is observed while very low phototoxicity (80% cell viability) is noted against normal dermal fibroblast cells. A positive correlation with ROS accumulation and increased expression of caspase-3 in PPIX-functionalized rGO-treated cancer cells is also established. The results evidence a simple and cost-effective route for developing photosensitizer-functionalized rGO for effective and selective killing of cancer cells.     

Highly Converged Valence Bands and Ultralow Lattice Thermal Conductivity for High-Performance SnTe Thermoelectrics

A two-step optimization strategy is used to improve the thermoelectric performance of SnTe via modulating the electronic structure and phonon transport. The electrical transport of self-compensated SnTe (that is, Sn_1.03Te) was first optimized by Ag doping, which resulted in an optimized carrier concentration. Subsequently, Mn doping in Sn_1.03−xAg_xTe resulted in highly converged valence bands, which improved the Seebeck coefficient. The energy gap between the light and heavy hole bands, i.e. ΔE_v decreases to 0.10 eV in Sn_0.83Ag_0.03Mn_0.17Te compared to the value of 0.35 eV in pristine SnTe. As a result, a high power factor of ca. 24.8 μW cm⁻¹ K⁻² at 816 K in Sn_0.83Ag_0.03Mn_0.17Te was attained. The lattice thermal conductivity of Sn_0.83Ag_0.03Mn_0.17Te reached to an ultralow value (ca. 0.3 W m⁻¹ K⁻¹) at 865 K, owing to the formation of Ag₇Te₄ nanoprecipitates in SnTe matrix. A high thermoelectric figure of merit (z T≈1.45 at 865 K) was obtained in Sn_0.83Ag_0.03Mn_0.17Te.     

Various scattering properties of a new PT-symmetric non-Hermitian potential

We complexify a 1-d potential V(x)=V₀cosh²μ{tanh[(x−μd)/d]+tanh(μ)}²$V\left(x\right)=V_0{cosh}^2\mu {\{tanh[(x-\mu d)/d]+tanh\left(\mu \right)\}}^2$ which exhibits bound, reflecting and free states to study various properties of a non-Hermitian system. This potential turns out a PT-symmetric non-Hermitian potential when one of the parameters (μ,d)$(\mu ,d)$ becomes imaginary. For the case of μ→iμ$\mu \to i\mu$, we have an entire real bound state spectrum. Explicit scattering states are constructed to show reciprocity at certain discrete values of energy even though the potential is not parity symmetric. Coexistence of deep energy minima of transmissivity with the multiple spectral singularities (MSS) is observed. We further show that this potential becomes invisible from the left (or right) at certain discrete energies. The penetrating states in the other case (d→id$d\to id$) are always reciprocal even though it is PT-invariant and no spectral singularity (SS) is present in this case. The presence of MSS and reflectionlessness is also discussed for the free states in the later case.     

Gold‐Iron Bimetallic Nanoparticles Impregnated Reduced Graphene Oxide Based Nanosensor for Label‐free Detection of Biomarker Related to Non‐alcoholic Fatty Liver Disease

We report for the first time a microwave assisted, one pot, direct, and facile synthesis of monodispersed iron‐gold bimetallic nanoparticles (BNP_Au‐Fe) using glucose as a reducing agent in merely 90 s. The as such synthesized BNP_Au‐Fe were thoroughly characterized using UV‐Vis, XRD, TEM, EDX, elemental mapping, and raman spectroscopy. These BNP_Au‐Fe were further impregnated with reduced graphene oxide (rGO) and coated onto glassy carbon electrode (GCE) to develop a sensor probe for label free electrochemical detection of acetaminophen, which is considered to be a most potent biomarker related to non‐alcoholic fatty liver disease. The sensor probe was systematically characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The BNP_Au‐Fe‐rGO nanocomposite matrix showed the sensing of acetaminophen with a wide dynamic range between 50 and 800 nM with detection limit (DL) of 0.14 nM (±0.05) nM (RSD<4.12 %) that was lower compared to previously reported acetaminophen sensors. To show the practical application of the sensor probe, acetaminophen was detected in human urine samples, which showed the percentage recovery between 86.65 % and 91.32 %. To the best of our knowledge, this is the first report where BNP_Au‐Fe impregnated rGO was used to detect acetaminophen. Interferences due to various molecules such as glucose, serum albumin, glycine, glutamic acid, alanine, citric acid, and ascorbic acid were tested individually and in mixed sample. Long‐term stability of sensor probe was examined which was found to be stable up to 12 weeks. The sensor fabricated using BNP_Au‐Fe‐rGO nanocomposite has many attractive features such as; simplicity, rapidity, and label free detection, hence it could be a method of choice for acetaminophen detection in clinical settings.     

Engineered modular heterocyclic-diamidines for sequence-specific recognition of mixed AT/GC base pairs at the DNA minor groove

This report describes a breakthrough in a project to design minor groove binders to recognize any sequence of DNA. A key goal is to invent synthetic chemistry for compound preparation to recognize an adjacent GG sequence that has been difficult to target. After trying several unsuccessful compound designs, an N-alkyl-benzodiimidazole structure was selected to provide two H-bond acceptors for the adjacent GG-NH groups. Flanking thiophenes provide a preorganized structure with strong affinity, DB2831, and the structure is terminated by phenyl-amidines. The binding experimental results for DB2831 with a target AAAGGTTT sequence were successful and include a high ΔT_m, biosensor SPR with a K_D of 4 nM, a similar K_D from fluorescence titrations and supporting competition mass spectrometry. MD analysis of DB2831 bound to an AAAGGTTT site reveals that the two unprotonated N of the benzodiimidazole group form strong H-bonds (based on distance) with the two central G-NH while the central –CH of the benzodiimidazole is close to the –C O of a C base. These three interactions account for the strong preference of DB2831 for a -GG- sequence. Surprisingly, a complex with one dynamic, interfacial water is favored with 75% occupancy.

This report describes a breakthrough in a project to design minor groove binders to recognize any sequence of DNA.     

Orientational self-sorting in cuboctahedral Pd cages

Cuboctahedral coordination cages of the general formula [Pd₁₂L₂₄]²⁴⁺ (L = low-symmetry ligand) were analyzed theoretically and experimentally. With 350 696 potential isomers, the structural space of these assemblies is vast. Orientational self-sorting refers to the preferential formation of particular isomers within the pool of potential structures. Geometric and computational analyses predict the preferred formation of cages with a cis arrangement at the metal centers. This prediction was corroborated experimentally by synthesizing a [Pd₁₂L₂₄]²⁴⁺ cage with a bridging 3-(4-(pyridin-4-yl)phenyl)pyridine ligand. A crystallographic analysis of this assembly showed exclusive cis coordination of the 3- and the 4-pyridyl donor groups at the Pd²⁺ ions.

Cuboctahedral [Pd₁₂L₂₄]²⁴⁺ cages based on low-symmetry ligands can potentially form a vast number of isomers, but the self-assembly process was found to be highly selective.     

Small Sequence-Sensitive Compounds for Specific Recognition of the G⋅C Base Pair in DNA Minor Groove

A series of small diamidines with thiophene and modified N-alkylbenzimidazole σ-hole module represent specific binding to single G⋅C base pair (bp) DNA sequence. The variation of N-alkyl or aromatic rings were sensitive to microstructures of the DNA minor groove. Thirteen new compounds were synthesized to test their binding affinity and selectivity. The dicyanobenzimidazoles needed to synthesize the target diamidines were made via condensation/cyclization reactions of different aldehydes with different 3-amino-4-(alkyl- or phenyl-amino) benzonitriles. The final diamidines were synthesized using lithium bis-trimethylsilylamide (LiN[Si(CH₃)₃]₂) or Pinner methods. The newly synthesized compounds showed strong binding and selectivity to AAAGTTT compared to similar sequences AAATTT and AAAGCTTT investigated by several biophysical methods including biosensor-SPR, fluorescence spectroscopy, DNA thermal melting, ESI-MS spectrometry, circular dichroism, and molecular dynamics. The binding affinity results determined by fluorescence spectroscopy are in accordance with those obtained by biosensor-SPR. These small size single G⋅C bp highly specific binders extend the compound database for future biological applications.     

Synthesis of conformationally diverse tetrathiacalix[4]arene(amido)crowns and tetrathiacalix[4]arene amides with pendant amine functions

A series of conformationally diverse novel tetrathiacalix[4]arene(amido)crowns and amides from tetrakis((ethoxycarbonyl)methoxy)p-tert-butyl tetrathiacalix[4]arene and its debutylated analog have been prepared by their reaction with diamines [H₂N(CH₂)_nNH₂; n=2,3,4, and 6] and polyamines. It has been determined that the length of the alkyl spacer in diamines is pivotal for the formation of either the tetrathiacalix[4]arene bis(amido)crowns or tetrathiacalix[4]arene amides with pendant amine functions. The synthesized compounds represent potential building blocks for achieving sophisticated molecular assemblies for molecular organization and recognition. Single crystal X-ray analysis of tetrathiacalix[4]arene bis(amido)crown 6a revealed that it has a 1,3-alternate conformation, which forms supramolecular complexes with chloroform.     

Two‐Dimensional Crystals from Reduced Symmetry Analogues of Trimesic Acid

The two‐dimensional assembly of multicarboxylated arenes is explored at the liquid–graphite interface using scanning tunneling microscopy. Symmetry variations were introduced via phenylene spacer addition and the influence of these perturbations on the formation of hydrogen‐bonded motifs from an alkanoic acid solvent is observed. This work demonstrates the importance of symmetry in 2D crystal formation and draws possible links of this behavior to prediction of coordination modes in three‐dimensional coordination polymers.