Catalyst screening: Refinement of the origin of the volcano curve and its implication in heterogeneous catalysis

Understanding the overall catalytic activity trend for rational catalyst design is one of the core goals in heterogeneous catalysis. In the past two decades, the development of density functional theory (DFT) and surface kinetics make it feasible to theoretically evaluate and predict the catalytic activity variation of catalysts within a descriptor-based framework. Thereinto, the concept of the volcano curve, which reveals the general activity trend, usually constitutes the basic foundation of catalyst screening. However, although it is a widely accepted concept in heterogeneous catalysis, its origin lacks a clear physical picture and definite interpretation. Herein, starting with a brief review of the development of the catalyst screening framework, we use a two-step kinetic model to refine and clarify the origin of the volcano curve with a full analytical analysis by integrating the surface kinetics and the results of first-principles calculations. It is mathematically demonstrated that the volcano curve is an essential property in catalysis, which results from the self-poisoning effect accompanying the catalytic adsorption process. Specifically, when adsorption is strong, it is the rapid decrease of surface free sites rather than the augmentation of energy barriers that inhibits the overall reaction rate and results in the volcano curve. Some interesting points and implications in assisting catalyst screening are also discussed based on the kinetic derivation. Moreover, recent applications of the volcano curve for catalyst design in two important photoelectrocatalytic processes (the hydrogen evolution reaction and dye-sensitized solar cells) are also briefly discussed.

Morphology and compression behaviour of biodegradable scaffolds produced by the sintering process

Porous poly(L-lactic acid) (PLA) scaffolds of 85 per cent and 90 per cent porosity are prepared using polymer sintering and porogen leaching method. Different weight fractions of 10 per cent, 30 per cent, and 50 per cent of hydroxyapatite (HA) are added to the PLA to control the acidity and degradation rate. The three-dimensional (3D) morphology and surface porosity are tested using micro-computer tomography (micro-CT), optical microscopy, and scanning electron microscopy (SEM). Results indicate that the surface porosity does not change on the addition of HA. The micro-CT examinations show a slight decrease in the pore size and increase in the wall thickness accompanied by reduced anisotropy for the scaffolds containing HA. Scanning electron micrographs show detectable interconnected pores for the scaffold with pure PLA. Addition of the HA results in agglomeration of the HA particles and reduced leaching of the porogen. Compression tests of the scaffold identify three stages in the stress-strain curve. The addition of HA results in a reduction in the modulus of the scaffold at the first stage of elastic bending of the wall, but this is reversed for the second and third stages of collapse of the wall and densification in the compression tests. In the scaffolds with 85 per cent porosity, the addition of a high percentage of HA could result in 70 per cent decrease in stiffness in the first stage, 200 per cent increase in stiffness in the second stage, and 20 per cent increase in stiffness in the third stage. The results of these tests are compared with the Gibson cellular material model that is proposed for prediction of the behaviour of cellular material under compression. The pH and molecular weight changes are tracked for the scaffolds within a period of 35 days. The addition of HA keeps the pH in the alkaline region, which results in higher rate of degradation at an early period of observation, followed by a reduced rate of degradation later in the process. The final molecular weight is higher for the scaffolds with HA than for scaffolds of pure PLA. The manufactured scaffolds offer acceptable properties in terms of the pore size range and interconnectivity of the pores and porosity for non-load-bearing bone graft substitute; however, improvement to the mixing of the phases of PLA and HA is required to achieve better integrity of the composite scaffolds. © 2008 IMechE.

Seasonal differences in the effects of oscillatory and uni-directional flow on the growth and nitrate-uptake rates of juvenile Laminaria digitata (Phaeophyceae)

The influence of oscillatory versus unidirectional flow on the growth and nitrate-uptake rates of juvenile kelp, Laminaria digitata, was determined seasonally in experimental treatments that simulated as closely as possible natural environmental conditions. In winter, regardless of flow condition (oscillatory and unidirectional) or water velocity, no influence of water motion was observed on the growth rate of L. digitata. In summer, when ambient nitrate concentrations were low, increased water motion enhanced macroalgal growth, which is assumed to be related to an increase in the rate of supply of nutrients to the blade surface. Nitrate-uptake rates were significantly influenced by water motion and season. Lowest nitrate-uptake rates were observed for velocities <5 cm · s−1 and nitrate-uptake rates increased by 20%–50% under oscillatory motion compared to unidirectional flow at the same average speed. These data further suggested that the diffusion boundary layer played a significant role in influencing nitrate-uptake rates. However, while increased nitrate-uptake in oscillatory flow was clear, this was not reflected in growth rates and further work is required to understand the disconnection of nitrate-uptake and growth by L. digitata in oscillatory flow. The data obtained support those from related field-based studies, which suggest that in summer, when insufficient nitrogen is available in the water to saturate metabolic demand, the growth rate of kelps will be influenced by water motion restricting mass transfer of nitrogen.

Thermo-Mechanical Properties of Poly ε-Caprolactone/Poly L-Lactic Acid Blends: Addition of Nalidixic Acid and Polyethylene Glycol Additives Journal of the Mechanical Behavior of Biomedical Materials

The search for ideal biomaterials is still on-going for tissue regeneration. In this study, blends of Poly ε-caprolactone (PCL) with Poly l-lactic acid (PLLA), Nalidixic Acid (NA) and Polyethylene glycol (PEG) were prepared. Mechanical and thermal properties of the blends were investigated by tensile and flexural analysis, DSC, TGA, WXRD, MFI, BET, SEM and hot stage optical microscopy. Results showed that the loading of PLLA caused a significant decrease in tensile strength and almost total eradication of the elongation at break of PCL matrix, especially after PEG and NA addition. Increased stiffness was also noted with additional NA, PEG and PLLA, resulting in an increase in the flexural modulus of the blends. <br/>Isothermal degradation indicated that bulk PCL, PLLA and the blends were thermally stable at 200°C for the duration of 2h making extrusion of the blends at this temperature viable. Morphological study showed that increasing the PLLA content and addition of the very low viscosity PEG and powder NA decreased the Melt Flow Indexer and increased the viscosity. <br/>At the higher temperature the PLLA begins to soften and eventually melts allowing for increased flow and, coupling this with, the natural increase in MFI caused by temperature is enhanced further. The PEG and NA addition increased dramatically the pore volume which is important for cell growth and flow transport of nutrients and metabolic waste.<br/>

Identification of human neutrophil defensins (HNPs1-3) in biopsies of squamous cell carcinomas of the human tongue

It has previously been reported that the a-defensins, found in the granules of polymorphonuclear leukocytes (neutrophils/ PMNs), are cytolytic for human tumour cells in vitro. Objective: To identify and quantify the a- defensins, HNP-1, HNP-2 and HNP-3 in healthy and tumour tissue from patients with oral squamous cell carcinoma using HPLC, mass spectrometry and amino acid sequencing. Methods: All patients (n=5) were diagnosed with oral squamous cell carcinoma of the tongue.Biopsy tissue from the site of the tumour (n=5) and a non-affected region of the tongue (n=5) was snap frozen and subsequently stored at -70 ºC until analysed. Peptides were extracted from the 10 tissue biopsies using acidified ethanol. Peptide extracts were separated by reverse-phase HPLC . All tumour and control tissue samples were individually analysed under identical conditions with a flow rate of l ml/min, ambient column temperature and absorbance detection at 214 and 280 nm. Fractions (1ml) were collected automatically. HPLC fractions were analysed by MALDI-MS using a linear time-of-flight Voyager DE-mass spectrometer (PerSeptive Biosystems, UK). Using this system the detection limit was 10 fmol. Peptides with molecular masses corresponding to those reported for the a-defensins were deemed of interest and were further subject to complete structural analysis by automated Edman degradation using an Applied Biosystems 491 Procise microsequencer. Results: MALDI-MS revealed a triad of peptides of molecular masses 3442 Da, 3371 Da and 3486 Da in both healthy and tumour tissue. Full length sequence data were obtained for the three a-defensins, unequivocally identifying their presence in both tumour and healthy tissue. Analysis of the MALDI-MS and sequence data indicated that the a-defensins were overexpressed (up to 12 fold) in tumour tissue. Conclusion: This study demonstrates the feasibility of screening tumour tissue for novel peptides/proteins using HPLC and MALDI-MS.The role of a-defensins in oral squamous cell carcinoma of the tongue requires further investigation.

Failure to Achieve PSA Level ≤I ng/ml Following Neo-Adjuvant LHRHa Therapy Predicts for a Lower Biochemical Control Rate and Overall Survival in Localized Prostate Cancer Treated with Radiotherapy

PURPOSE: To investigate whether failure to suppress the prostate-specific antigen (PSA) level to /=2 months of neoadjuvant luteinizing hormone-releasing hormone agonist therapy in patients scheduled to undergo external beam radiotherapy for localized prostate carcinoma is associated with reduced biochemical failure-free survival. METHODS AND MATERIALS: A retrospective case note review of consecutive patients with intermediate- or high-risk localized prostate cancer treated between January 2001 and December 2002 with neoadjuvant hormonal deprivation therapy, followed by concurrent hormonal therapy and radiotherapy was performed. Patient data were divided for analysis according to whether the PSA level in Week 1 of radiotherapy was 1 ng/mL in 52. At a median follow-up of 49 months, the 4-year actuarial biochemical failure-free survival rate was 84% vs. 60% (p = 0.0016) in favor of the patients with a PSA level after neoadjuvant hormonal deprivation therapy of 1 ng/mL at the beginning of external beam radiotherapy after &gt;/=2 months of neoadjuvant luteinizing hormone-releasing hormone agonist therapy have a significantly greater rate of biochemical failure and lower survival rate compared with those with a PSA level of

Crystallization and phase transformation behaviour of electroless nickel-phosphorus deposits with low and medium phosphorus contents under continuous heating

Electroless nickel-phosphorus deposits with 5-8 wt% P and 3-5 wt% P were analysed for the effects of continuous heating on the crystallization kinetics and phase transformation behaviour of the deposits. The as-deposited coatings consist of a mixture of amorphous and microcrystalline nickel phases, featuring in their X-ray diffraction patterns. Continuous heating processes to 300C-800C at 20C/min were carried out on the deposits in a differential scanning calorimetric apparatus. The subsequent X-ray diffraction analyses show that the sequence of phase transformation process was: amorphous phase + microcrystalline nickel, f.c.c. nickel + Ni3P stable phases. Preferred orientation of nickel {200} plane developed in the deposits after the heating processes. Differential scanning calorimetry of the deposits indicates that the crystallization temperatures increased with decreasing phosphorus content, and increasing heating rate. Crystallization activation energies of the deposits (230 and 322 kJ/mol, respectively) were calculated using the peak temperatures of crystallization process, from the differential scanning calorimetric curves at the heating rates ranging from 5 to 50C/min. It was found that the deposit with lower phosphorus content has higher activation energy.