Materials and Wireless Microfluidic Systems for Electronics Capable of Chemical Dissolution on Demand

Electronics that are capable of destroying themselves, on demand and in a harmless way, might provide the ultimate form of data security. This paper presents materials and device architectures for triggered destruction of conventional microelectronic systems by means of microfluidic chemical etching of the constituent materials, including silicon, silicon dioxide, and metals (e.g., aluminum). Demonstrations in an array of home‐built metal‐oxide‐semiconductor field‐effect transistors that exploit ultrathin sheets of monocrystalline silicon and in radio‐frequency identification devices illustrate the utility of the approaches.     

Transient spectroscopic characterization of the ring‐opening reaction of tetrahydrochromeno[2,3‐dimethyl]indole

Tetrahydrochromeno is a structural variant of spiropyran that undergoes a reversible ring‐opening to generate a colored nitrophenolate intermediate. Earlier work confirmed this intermediate through trimethylsilyl cyanide trapping under continuous irradiation. We have performed transient absorption spectroscopy to further characterize the mechanism of the ring‐opening reaction. Excitation at 355 nm produced a transient species with an absorption maximum at 445 nm, which we assign to the nitrophenolate unit of the ring‐opened product. The transient absorption decays after ~970 ns with small optical density changes corresponding to a 0.15 quantum yield. Exposure to oxygen did not exhibit a significant deleterious effect on the photoisomerization of the chromeno dye. Time‐dependent density functional theory corroborated spectroscopic assignments of the starting chromeno and the putative ring‐opened intermediate. The excited state behavior of this system parallels the structurally similar oxazine system reported by Raymo and coworkers. The one significant difference is the longer lifetime of the photochemically generated intermediate from chromeno. Copyright © 2015 John Wiley & Sons, Ltd.     

The anxiolytic effects of midazolam during anticipation to pain revealed using fMRI

BACKGROUND AND PURPOSE: Functional neuroimaging can distinguish components of the pain experience associated with anticipation to pain from those associated with the experience of pain itself. Anticipation to pain is thought to increase the suffering of chronic pain patients. Inappropriate anxiety, of which anticipation is a component, is also a cause of disability. We present a pharmacological functional magnetic resonance imaging (fMRI) study in which we investigate the selective modulation by midazolam of brain activity associated with anticipation to pain compared to pain itself. METHODS: Eight right-handed male volunteers underwent fMRI combined with a thermal pain conditioning paradigm and midazolam (30 mug/kg) or saline administration on different occasions, with order randomized across volunteers. Volunteers learned to associate a colored light with either painful, hot stimulation or nonpainful, warm stimulation to the back of the left hand. RESULTS: Comparison of the period during thermal stimulation (pain-warm) revealed a network of brain activity commonly associated with noxious stimulation, including activities in the anterior cingulate cortex (ACC), the bilateral insular cortices (anterior and posterior), the thalamus, S1, the motor cortex, the brainstem, the prefrontal cortex and the cerebellum. Comparison of the periods preceding thermal stimulation (anticipation to pain-anticipation to warm) revealed activity principally in the ACC, the contralateral anterior insular cortex and the ipsilateral S2/posterior insula. Detected by a region-of-interest analysis, midazolam reduced the activity associated specifically with anticipation to pain while controlling for anticipation to warm. This was most significant in the contralateral anterior insula (P<.05). There were no significant drug effects on the activity associated with pain itself. CONCLUSION: In identifying a pharmacological effect on activity preceding but not during pain, we have successfully demonstrated an fMRI assay that can be used to study the action of anxiolytic agents in a relatively small cohort of humans.     

Quantum Dot-Catalyzed Photoreductive Removal of Sulfonyl-Based Protecting Groups

This Communication describes the use of CuInS₂/ZnS quantum dots (QDs) as photocatalysts for the reductive deprotection of aryl sulfonyl-protected phenols. For a series of aryl sulfonates with electron-withdrawing substituents, the rate of deprotection for the corresponding phenyl aryl sulfonates increases with decreasing electrochemical potential for the two electron transfers within the catalytic cycle. The rate of deprotection for a substrate that contains a carboxylic acid, a known QD-binding group, is accelerated by more than a factor of ten from that expected from the electrochemical potential for the transformation, a result that suggests that formation of metastable electron donor–acceptor complexes provides a significant kinetic advantage. This deprotection method does not perturb the common NHBoc or toluenesulfonyl protecting groups and, as demonstrated with an estrone substrate, does not perturb proximate ketones, which are generally vulnerable to many chemical reduction methods used for this class of reactions.     

Quantum Dot‐Catalyzed Photoreductive Removal of Sulfonyl‐Based Protecting Groups

This Communication describes the use of CuInS₂/ZnS quantum dots (QDs) as photocatalysts for the reductive deprotection of aryl sulfonyl‐protected phenols. For a series of aryl sulfonates with electron‐withdrawing substituents, the rate of deprotection for the corresponding phenyl aryl sulfonates increases with decreasing electrochemical potential for the two electron transfers within the catalytic cycle. The rate of deprotection for a substrate that contains a carboxylic acid, a known QD‐binding group, is accelerated by more than a factor of ten from that expected from the electrochemical potential for the transformation, a result that suggests that formation of metastable electron donor–acceptor complexes provides a significant kinetic advantage. This deprotection method does not perturb the common NHBoc or toluenesulfonyl protecting groups and, as demonstrated with an estrone substrate, does not perturb proximate ketones, which are generally vulnerable to many chemical reduction methods used for this class of reactions.     

Glycoconjugated Metallohelices have Improved Nuclear Delivery and Suppress Tumour Growth In Vivo

Monosaccharides are added to the hydrophilic face of a self‐assembled asymmetric Fe^II metallohelix, using CuAAC chemistry. The sixteen resulting architectures are water‐stable and optically pure, and exhibit improved antiproliferative selectivity against colon cancer cells (HCT116 p53^+/+) with respect to the non‐cancerous ARPE‐19 cell line. While the most selective compound is a glucose‐appended enantiomer, its cellular entry is not mainly glucose transporter‐mediated. Glucose conjugation nevertheless increases nuclear delivery ca 2.5‐fold, and a non‐destructive interaction with DNA is indicated. Addition of the glucose units affects the binding orientation of the metallohelix to naked DNA, but does not substantially alter the overall affinity. In a mouse model, the glucose conjugated compound was far better tolerated, and tumour growth delays for the parent compound (2.6 d) were improved to 4.3 d; performance as good as cisplatin but with the advantage of no weight loss in the subjects.     

Molecular modeling of polymers, 14 quantitative structure-property relationship analyses of multicomponent systems containing polymers

One general class of polymer modeling applications involves materials which are large, in terms of molecular degrees of freedom, and poorly defined in terms of composition and morphology. Such materials are often multicomponent with respect to number of distinct polymers, fillers, additives, etc. Two obstacles limit the modeling of these materials. First, one normally does not have any idea about the key physicochemical molecular properties governing the system. Second, the functional dependence of the target properties of the material upon the key physicochemical molecular properties is usually totally unknown. Torsion angle unit (TAU) theory, a molecular decomposition technique, permits an arbitrarily large number of physicochemical properties to be computed in an open-ended fashion, and thus addresses the first problem. Genetic function approximation (GFA) analysis tackles the second problem by efficiently exploring any desired number of functional relationships between target properties and physicochemical molecular properties. Case studies of (TAU theory)-(GFA analysis) applications to estimate glass, Tg, and crystal-melt, Tm, transition temperatures will be described.     

Hydrogenation enthalpimetry--I: microcomputer-assisted calibration and data-acquisition

A calorimetric device is described which permits enthalpimetric determination of unsaturated hydrocarbons through the enthalpy change for their catalytic hydrogenation. Samples with weights from < 1 to about 20 mg can be analysed with a mean error of about 2%. The method makes extensive use of digital electronics and is well suited to routine automated determination of unsaturation. The principal drawback is lack of specificity.     

Designing Thin,Ultrastretchable Electronics with Stacked Circuits and Elastomeric Encapsulation Materials

Many recently developed soft, skin‐like electronics with high performance circuits and low modulus encapsulation materials can accommodate large bending, stretching, and twisting deformations. Their compliant mechanics also allows for intimate, nonintrusive integration to the curvilinear surfaces of soft biological tissues. By introducing a stacked circuit construct, the functional density of these systems can be greatly improved, yet their desirable mechanics may be compromised due to the increased overall thickness. To address this issue, the results presented here establish design guidelines for optimizing the deformable properties of stretchable electronics with stacked circuit layers. The effects of three contributing factors (i.e., the silicone interlayer, the composite encapsulation, and the deformable interconnects) on the stretchability of a multilayer system are explored in detail via combined experimental observation, finite element modeling, and theoretical analysis. Finally, an electronic module with optimized design is demonstrated. This highly deformable system can be repetitively folded, twisted, or stretched without observable influences to its electrical functionality. The ultrasoft, thin nature of the module makes it suitable for conformal biointegration.     

Optical neural networks

Classical optical information processing and classical neural networks can be adapted and combined to create optical neural networks which offer significant and fundamental advantages over electronic neural networks in various well-defined cases. A systematic morphology of optical neural networks is presented. Special problems they create are discussed. The state of the art of their implementation is indicated, and some supportable speculations on their future are given