Clean coupling of unfunctionalized porphyrins at surfaces to give highly oriented organometallic oligomers

The direct coupling of complex, functional organic molecules at a surface is one of the outstanding challenges in the road map to future molecular devices. Equally demanding is to meet this challenge without recourse to additional functionalization of the molecular building blocks and via clean surface reactions that leave no surface contamination. Here, we demonstrate the directional coupling of unfunctionalized porphyrin molecules--large aromatic multifunctional building blocks--on a single crystal copper surface, which generates highly oriented one-dimensional organometallic macromolecular nanostructures (wires) in a reaction which generates gaseous hydrogen as the only byproduct. In situ scanning tunneling microscopy and temperature programmed desorption, supported by theoretical modeling, reveal that the process is driven by C-H bond scission and the incorporation of copper atoms in between the organic components to form a very stable organocopper oligomer comprising organometallic edge-to-edge porphyrin-Cu-porphyrin connections on the surface that are unprecedented in solution chemistry. The hydrogen generated during the reaction leaves the surface and, therefore, produces no surface contamination. A remarkable feature of the wires is their stability at high temperatures (up to 670 K) and their preference for 1D growth along a prescribed crystallographic direction of the surface. The on-surface formation of directional organometallic wires that link highly functional porphyrin cores via direct C-Cu-C bonds in a single-step synthesis is a new development in surface-based molecular systems and provides a versatile approach to create functional organic nanostructures at surfaces.     

Comparison of subcellular responses for the evaluation and prediction of the chemotherapeutic response to cisplatin in lung adenocarcinoma using Raman spectroscopy

Confocal Raman Micro-spectroscopy (CRM) is employed to examine the chemical and physiological effects of anticancer agents, using cisplatin and A549 adenocarcinoma cells as a model compound and test system respectively. Spectral responses of the membrane and cytoplasm of the cell are analysed independently and the results are compared to previously reported spectroscopic studies of the nucleus. Moreover, Raman spectra from the proteins extracted from the control and exposed samples are acquired and analysed to confirm the origin of the molecular changes of the cell membrane and cytoplasm of the A549 cells. Multivariate data analysis techniques including Principal Component Analysis (PCA) and Partial Least Squares Regression (PLSR) along with PLS-Jackknifing are used to analyse the data measured from the cell membrane and cytoplasm of the A549 cells and results are correlated with parallel measurements from the cytotoxicity assay MTT. A PLSR model is used to differentiate between the chemical effect of the chemotherapeutic agent and the physiological response of the A549 cells and to identify regions of the spectrum that are associated with these processes respectively. The PLSR model is also employed to predict, on the basis of the Raman spectra, the effective dose as well as the level of physiological response, using spectra data from the cytoplasmic and cell membrane regions. The effectiveness of the models based on spectral datasets from the cell membrane and cytoplasm is compared to similar models constructed using spectral data from the nuclear region as well as one combining spectral data from all regions. In all cases, higher prediction accuracy is found for regression against the cisplatin dose, and for both regression against the dose and the physiological response, nuclear data yield higher precision.     

Boronic acid functionalized fibrous cellulose for the selective enrichment of glycopeptides

Enrichment of glycoproteins has been important because of their dynamicity and role in biological systems. Study of glycoproteins is complex because of the simultaneous glycosylation and deglycosylation inside the body. Often employed affinities for glycopeptides are hydrazide, boronic acid, or physiosorbed lectin on support materials. Cellulose, a natural polysaccharide, has rich surface chemistry, stable structure, low cost and availability in different variants. In present study, fibrous cellulose is oxidized using periodate to modify with boronic acid. Attachment of boronic acid is confirmed by Fourier transform infrared spectroscopy. Particle size and morphology of boronic acid@fibrous cellulose is studied by scanning electron microscopy. The enrichment efficiency is evaluated by using horseradish peroxidase as model protein. Boronic acid@fibrous cellulose is selective up to 1:250 for spiked horseradish peroxidase in bovine serum albumin digest, sensitive down to 0.1 femtomol and recovering 88.15% glycopeptides. Moreover, protein binding capacity is determined as 213 mg/g and 41% sequence coverage of horseradish peroxidase protein with all eight glycosylation sites detected. Total of 18 glycopeptides are enriched from immunoglobulin digest showing ability of boronic acid@fibrous cellulose to enrich glycoproteins from multiglycoforms. Enrichment from human serum recovers 18% extracellular and 72% secreted glycoproteins via bottom‐up approach and online tools.     

The diamagnetic susceptibilities of succinic acid and succinic anhydride

Proceedings - Mathematical Sciences -     

Single-step laser deposition of functionally graded coating by dual ‘wire-powder’ or ‘powder-powder’ feeding—A comparative study

The creation of iron-copper (Fe-Cu) alloys has practical application in improving the surface heat conduction and corrosion resistance of, for example, conformal cooling channels in steel moulds, but is difficult to achieve because the elements have got low inter-solubility and are prone to solidification cracking. Previous work by these authors has reported a method to produce a graded iron-nickel-copper coating in a single-step by direct diode laser deposition (DLD) of nickel wire and copper powder as a combined feedstock. This work investigates whether dual powder feeds can be used in that process to afford greater geometric flexibility and compares attributes of the ‘nickel wire and copper powder’ and ‘nickel powder and copper powder’ processes for deposition on a H13 tool steel substrate.In wire-powder deposition, a higher temperature developed in the melt pool causing a clad with a smooth gradient structure. The nickel powder in powder-powder deposition did not impart much heat into the melt pool so the melt pool solidified with sharp composition boundaries due to single metal melting in some parts. In wire-powder experiments, a graded structure was obtained by varying the flow rates of wire and powder. However, a graded structure was not realised in powder-powder experiments by varying either the feed or the directions. Reasons for the differences and flow patterns in the melt pools and their effect on final part properties of parts produced are discussed.     

Dinuclear monointercalating RuII complexes that display high affinity binding to duplex and quadruplex DNA

The DNA duplex binding properties of previously reported dinuclear Ru(II) complexes based on the ditopic ligands tetrapyrido[3,2-a:2',3'-c:3',2'-h:2',3'-j]phenazine (tppz) and tetraazatetrapyrido[3,2-a:2'3'-c:3',2'-l:2',3'-n]pentacene (tatpp) are reported. Photophysical and biophysical studies indicate that, even at high ionic strengths, these complexes bind to duplex DNA, through intercalation, with affinities that are higher than any other monointercalating complex and are only equalled by DNA-threaded bisintercalating complexes. Additional studies at high ionic strengths using the 22-mer d(AG(3)[T(2)AG(3)](3)) [G3] human telomeric sequence reveal that the dinuclear tppz-based systems also bind with high affinity to quadruplex DNA. Furthermore, for these complexes, quadruplex binding is accompanied by a distinctive blue-shifted "light-switch" effect, characterized by higher emission enhancements than those observed in the analogous duplex effect. Calorimetry studies reveal that the thermodynamics of duplex and quadruplex binding is distinctly different, with the former being entirely entropically driven and the latter being both enthalpically and entropically favored.     

7,8-Dihydropyrido[2,3-d]pyrimidin-2-one; a bicyclic cytosine analogue capable of enhanced stabilisation of DNA duplexes

Incorporation of a bicyclic cytosine analogue, 3-beta-D-(2'-deoxyribofuranosyl)-7,8-dihydropyrido[2,3-d]pyrimidine, into synthetic DNA duplexes results in a greatly enhanced thermal stability (3-4 degrees C per modification) compared to the corresponding unmodified duplex.