Generation, Characterization, and Impact of Mesopores in Zeolite Catalysts

Amongst the current developments in the field of hierarchical pore structures, the creation of mesopores in zeolite crystals is the most frequently employed way to combine micropores with mesopores in one material. In this review an overview is presented of the different approaches to generate and characterize mesopores in zeolite crystals and establish their impact on the catalytic action. Mesopores can be created via several routes from which steaming and acid leaching are the most frequently applied. Novel approaches using secondary carbon templates that are removed after synthesis have recently been launched. For the characterization of mesopores, nitrogen physisorption and electron microscopy are commonly used. More recently, it was shown that electron tomography, a form of three-dimensional transmission electron microscopy, is able to reveal the three-dimensional shape, size, and connectivity of the mesopores. The effect of the presence of mesopores for catalysis is demonstrated for several industrially applied processes that make use of zeolite catalysts: the cracking of heavy oil fractions over zeolite Y, the production of cumene and hydroisomerization of alkanes over mordenite, and synthesis of fine chemicals over Y, ZSM-5, and Beta. For these processes, the mesopores ensure an optimal accessibility and transport of reactants and products, while the zeolite micropores induce the preferred shape-selective properties.     

A Compact Model for Valence-Band Electron Tunneling Current in Partially Depleted SOI MOSFETs

The valence-band electron (EVB) tunneling current in partially depleted silicon-on-insulator (SOI) MOSFETs increases as the gate oxide gets thinner and affects the dynamic behavior of devices and circuits. We present an engineering model of EVB tunneling current based on the surface-potential formulation. The new model is implemented in a SOI MOSFET compact model and is used to study the impact of EVB tunneling on circuit performance. Simulations of stacked logic gates show that the EVB tunneling current not only boosts circuit switching speed but also mitigates the history dependence of propagation delays     

Electrochemical oxidation by square-wave potential pulses in the imitation of oxidative drug metabolism

Electrochemistry combined with mass spectrometry (EC-MS) is an emerging analytical technique in the imitation of oxidative drug metabolism at the early stages of new drug development. Here, we present the benefits of electrochemical oxidation by square-wave potential pulses for the oxidation of lidocaine, a test drug compound, on a platinum electrode. Lidocaine was oxidized at constant potential and by square-wave potential pulses with different cycle times, and the reaction products were analyzed by liquid chromatography-mass spectrometry [LC-MS(/MS)]. Application of constant potentials of up to +5.0 V resulted in relatively low yields of N-dealkylation and 4-hydroxylation products, while oxidation by square-wave potential pulses generated up to 50 times more of the 4-hydroxylation product at cycle times between 0.2 and 12 s (estimated yield of 10%). The highest yield of the N-dealkylation product was obtained at cycle times shorter than 0.2 s. Tuning of the cycle time is thus an important parameter to modulate the selectivity of electrochemical oxidation reactions. The N-oxidation product was only obtained by electrochemical oxidation under air atmosphere due to reaction with electrogenerated hydrogen peroxide. Square-wave potential pulses may also be applicable to modulate the selectivity of electrochemical reactions with other drug compounds in order to generate oxidation products with greater selectivity and higher yield based on the optimization of cycle times and potentials. This considerably widens the scope of direct electrochemistry-based oxidation reactions for the imitation of in vivo oxidative drug metabolism.     

Laparoscopic-assisted bowel resections in inflammatory bowel disease: state of the art

The objectives of this paper are to review the rational, the present results and future of laparoscopic-assisted bowel surgery in patients with inflammatory bowel disease (IBD). Only a few centres in the world report on laparoscopic bowel resection in IBD that include stoma surgery, ileocolic resection, left, right and (sub)total colectomy for Crohn's disease, and subtotal or restorative total proctocolectomy (ileal pouch anal procedures). The combined series report conversion rates between 2.5% and 22.2%. Ileocolic resection, stoma creation, stricturoplasty and segmental small bowel resection are associated with an acceptable length of surgery, but laparoscopic(-assisted) total colectomy or restorative proctocolectomy still demand up to 4-6 hours of operative time. The few randomised studies addressing laparoscopic-assisted (segmental) bowel surgery versus conventional surgery demonstrated significantly less pain, a quicker return to self-care and a shorter hospital stay. The results of the series reporting on laparoscopic-assisted (ileo)colectomy in IBD are similar to those from these randomised studies. Laparoscopic-assisted subtotal colectomy and restorative proctocolectomy have no benefit compared with conventional surgery other than superior cosmesis. Morbidity of laparoscopic (ileo)colectomy in IBD is low, that of laparoscopic-assisted subtotal colectomy and restorative proctocolectomy remains to be seen. The various laparoscopic bowel resections done in IBD are all feasible. The first series describing laparoscopic surgery for IBD indicate that laparoscopic-assisted segmental (ileo)colectomy is safe and is the preferred approach provided it is done in a centre specialised in the treatment of IBD and by skilled laparoscopic surgeons beyond the learning curve. Until now, laparoscopic-assisted subtotal colectomy and restorative proctocolectomy do not have the same short-term benefits as seen in other laparoscopic colorectal procedures. Patients with inflammatory bowel disease (IBD) have a high life-time risk of having abdominal surgery and reoperations. The proposed advantages of laparoscopic surgery in this group of young patients might be higher than in patients with other colorectal diseases. Minimal physiologic insult in patients who already are under significant physiologic stress, less adhesion formation and superior cosmesis are important benefits over time. In a time where patient's demands will increase, the future of laparoscopic colonic surgery in IBD looks assured.     

A model for post-occlusive reactive hyperemia as measured with laser-Doppler perfusion monitoring

To facilitate the quantitative analysis of post-occlusive reactive hyperaemia (PORH), measured with laser-Doppler perfusion monitoring (LDPM) on extremities, we present a flow model for the dynamics of the perfusion of the tissue during PORH, based on three parameters: two time constants (tau1 and tau2) and the ratio of the maximum flux and the resting flux. With these three constants quantitative comparisons between experiments will be possible and, therefore, we propose to adopt this approach as future standard. For this reason, we also developed a computer program to perform the fit of the model to measured data.     

Cross-sector collaboration within Dutch flood risk governance: historical analysis of external triggers

ABSTRACT

This article synthesizes the literature on Dutch flood risk governance to analyze how external conditions shaped past and present dynamics of cross-sector collaboration for integrated flood risk management in the Netherlands. It traces the extent to which policy and legal frameworks, socio-economic circumstances, political realities, power relations and conflict situations have influenced attempts at collaboration between flood safety, spatial planning, environmental protection and other sectors. Despite the growing interdependences, existing power relations between the sectors are characterized by the dominance of the water sector. Hence, cross-sector collaboration can develop as long as it does not compromise flood safety.     

Scalar diffraction modeling in optical disk recording using wave function assembling

A new scalar diffraction modeling method for simulating the readout signal of optical disks is described. The information layer is discretized into pixels that are grouped in specific ways to form written and unwritten areas. A set of 2D wave functions resulting from these pixels at the detection aperture is established. A readout signal is obtained via the assembly of wave functions from this set according to the content under the scanning spot. The method allows efficient simulation of jitter noise due to edge deformation of recorded marks, which is important at high densities. It is also capable of simulating a physically irregular mark, thereby helping to understand and optimize the recording process.     

Growth and stability of ZnTe magic-size nanocrystals

A synthetic method for ZnTe magic-sized clusters (MSCs) is reported, and the stability and growth kinetics of these clusters are investigated. Four distinct MSC families, with lowest-energy absorption peaks at 330, 354, 378, and 392 nm, are observed. The stability and growth kinetics of the MSCs are strongly influenced by the reaction temperature, precursor concentration, and nature of the ligands used as the coordinating solvent. High precursor concentrations result in faster growth and MSC formation at lower temperatures. Higher temperatures accelerate the growth kinetics and lead to a gradual shift from the stepwise MSC growth regime to a continuous growth regime. For temperatures above 260 °C, only continuous growth of nanocrystals is observed. The nature of the ligands also influences the stability and growth of ZnTe MSCs, which are formed with primary alkylamines as ligands, but not when trioctylphosphine, trioctylphosphine oxide, or trioctylamine are used as the sole ligands. This demonstrates the crucial role of ligands in the formation of stable ZnTe MSCs using colloidal synthetic methods. Under optimal synthetic conditions (200 °C, hexadecylamine as ligand, and suitable precursor concentrations), the method presented here allows the synthesis and isolation of a single MSC family absorbing at 330 nm.