Circular dichroism and UV-Vis detection of UV-induced damage to nucleic acids.

In this report, we demonstrate that CD spectroscopy can be used as a tool to detect changes to DNA upon irradiation with UV light. We follow the spectroscopic response of DNA samples irradiated at selected exposure times with both CD and UV-Vis spectroscopy. We analyzed four different nucleic acids to evaluate the effect of the sequence on photodegradation. Only one polymer, calf thymus DNA, was a natural nucleic acid and contained all four nucleobases. The other three were synthetic polymers and contained only one type of base pair: poly (deoxyadenylic-deoxythymidylic) acid [poly (dA-dT)2 ] and poly (deoxyadenylic acid) · poly (deoxythymidylic acid) [poly (dA) · poly (dT)], which contained only adenine and thymine; poly (deoxyguanylic-deoxycytidylic) acid [poly (dG-dC)2 ], which contained only guanine and cytosine. CD and UV-Vis spectra showed sequence dependent changes. In particular, poly (dA) · poly (dT) undergoes changes more rapidly than the other sequences investigated. The CD spectrum of poly (dA) · poly (dT) gradually undergoes an inversion, suggesting a change in helicity, before disappearing due to the unfolding of the double strand.

Formaldehyde Reduction in an Operating Room Setting: Comparison of a Catalytic Surgical Vacuum Device With a Traditional Smoke Evacuator.

Introduction Electrosurgery exposes healthcare workers to volatile organic compounds (VOCs) including formaldehyde. Adopting electrosurgical devices that catalytically transform formaldehyde to benign substances has the potential to improve safety in surgical settings. Materials and methods We compared the efficiency of formaldehyde removal of two medical devices. The first was a novel surgical vacuum (SV) device containing ultra-low particulate air (ULPA) filtration, activated carbon and catalytic transition metal oxide. The second was a commonly utilized handpiece evacuator (HE) that contained only mechanical filtration and activated carbon granules. Both devices were exposed to formalin vapor. Results The time weighted average (TWA), median and peak concentrations of detected formaldehyde at the outflow of the SV unit were 90% lower than the corresponding values detected at the outflow of the HE device (p = 0.0034). When catalytic material was added to the HE device, the detected formaldehyde concentration at the outflow was reduced by 55% (p = 2.9 x 10-15). Conclusions The catalytic SV device has the potential to considerably reduce formaldehyde levels in operating room (OR) environments.

A Peripherally Located Air Recirculation Device Containing an Activated Carbon Filter Reduces VOC Levels in a Simulated Operating Room.

Electrosurgery procedures produce airborne contaminants including volatile organic compounds (VOCs). The effectiveness of commercial grade activated carbon at removing toluene, a typical VOC, from the air in an enclosed simulated operating room (OR) when interfaced with an air recirculation device was tested. The concentration of toluene in the air was measured using gas sensitive semiconductor VOC sensors. When the air recirculation device containing activated carbon was turned on, the concentration of toluene in the air decayed exponentially. When the device was off, the toluene concentration reduced much more slowly. After 130 min, a VOC sensor placed near the air recirculation device showed VOC reductions of approximately 30% when the device is on and less than 1% when the device is off. Changing the activated carbon filter after 22 h of constant use showed an abrupt increase in the rate of toluene removal.

Increased CO2 levels in the operating room correlate with the number of healthcare workers present: an imperative for intentional crowd control.

The air in an operating room becomes more contaminated as the occupancy of the room increases. Individuals residing in a room can potentially emit infectious agents. In order to inhibit and better understand the epidemiology of surgical site infections, it is important to develop procedures to track room occupancy level and respiration. Exhaled CO2 provides a respiratory byproduct that can be tracked with IR light and is associated with human occupancy. Exhaled CO2 can also be used as an indirect measure of the potential release and level of infectious airborne agents. We show that non-dispersive infrared CO2 sensors can be used to detect CO2 in operating room air flow conditions of 20 air changes per hour and a positive pressure of 0.03 in. H2O. The CO2 concentration increased consecutively for occupation levels of one to four individuals, from approximately 65 ppm above the background level when one individual occupied the operating room for twenty minutes to approximately 300 ppm above the background when four individuals were present for twenty minutes. The amount of CO2 detected increases as the number of occupants increase, the activity level increases, the residency time increases and when the ventilation level is reduced.

A portable negative pressure unit reduces bone cement fumes in a simulated operating room.

In this report, we demonstrate a versatile method for the removal of bone cement fumes from the vicinity of health care workers in a simulated operating room. The mixing of two component bone cement in the perimeter of an operating room releases volatile organic compounds (VOCs). The use of localized negative pressure within proximity of the mixing vessel is expected to reduce the concentration of VOCs dispersed near the airway of operating room personnel. A standard two component bone cement formulation was mixed in the perimeter of a simulated operating room. A median VOC concentration of 19 ppm was detected with a portable VOC detector. When a portable negative pressure unit was stationed near the mixing area at distances of 8 and 36 cm from the mixing vessel, the median VOC rise was reduced by approximately 97% and 83%, respectively, relative to the control. The use of a portable negative pressure unit provides a potential increase in the safety for all staff when working with materials that give off VOCs in the operating room.

Photochemical Immobilization of Polymers on a Surface: Controlling Film Thickness and Wettability.

In this manuscript, we demonstrate the control of film thickness and surface wettability in the photochemical immobilization of poly (vinyl alcohol) (PVA) to a self-assembled monolayer (SAM) containing a phthalimide chromophore. Surface attachment is characterized by ellipsometry and contact angle measurements. The wettability of the resulting films is shown to depend on the chemical composition of the polymer. The film thickness is shown to depend on the irradiation time and molecular weight of the polymer. Using a photomask, micropatterns of polymers can be grafted to the SAM. The photopatterned surface can be "developed" by coating with a thin layer of a mixture containing poly (styrene) (PS) and triphenylsulfonium triflate.

Electroless Deposition of Nickel on Photografted Polymeric Microscale Patterns.

This report demonstrates the electroless deposition of Ni onto micropatterns of poly (acrylic acid) (PAA) photografted to phthalimide-terminated self-assembled monolayers (SAMs). PAA is spin-coated onto phthalimide SAMs and covered with a photomask. UV irradiation selectively binds PAA to exposed regions of the surface, allowing PAA on unexposed regions to be rinsed off. A Pd catalyst is then selectively adsorbed to regions of the surface where PAA is bound. The adsorbed catalyst selectively initiates Ni plating upon immersion of the substrate into a Ni(SO4 ) bath.

Facile assembly of light-driven molecular motors onto a solid surface.

In order to improve the rotary motion of surface assembled light-driven molecular motors, tetra-acid-functionalized motors were bound to an amine-coated quartz surface without prior activation of the acid groups. In contrast to earlier bipodal motors, the tetravalent motor showed no significant reduction in the rotation speed when attached to a surface.

Tetrapodal molecular switches and motors: synthesis and photochemistry.

The design, synthesis, and dynamic behavior of a series of novel tetrapodal molecular switches and motors containing common functional groups for attachment to various inorganic and organic surfaces are presented. Using a Diels-Alder reaction, an anthracene unit with four functionalized alkyl substituents ("legs") was coupled to maleimide-functionalized molecular switches or motors under ambient conditions. Terminal functional groups at the "legs" include thioacetates and azides, making these switches and motors ideal candidates for attachment to metallic or alkyne-functionalized surfaces. UV/vis absorption spectroscopy shows that the molecular switches and motors retain their ability to undergo reversible photoinduced and/or thermally induced structural changes after attachment to the tetrapodal anthracene.

Control of surface wettability using tripodal light-activated molecular motors.

Monolayers of fluorinated light-driven molecular motors were synthesized and immobilized on gold films in an altitudinal orientation via tripodal stators. In this design the functionalized molecular motors are not interfering and preserve their rotary function on gold. The wettability of the self-assembled monolayers can be modulated by UV irradiation.

An ultrafast surface-bound photo-active molecular motor.

We report the synthesis and surface attachment of an ultrafast light-driven rotary molecular motor. Transient absorption spectroscopy revealed that the half-life of the rate determining thermal step of the rotary cycle in solution is 38 ± 1 ns, the shortest yet observed, making this the fastest molecular motor reported. Incorporation of acetylene legs into the structure allowed the motors to be grafted to azide-modified quartz and silicon substrates using the "click" 1,3-dipolar cycloaddition reaction.

Towards dynamic control of wettability by using functionalized altitudinal molecular motors on solid surfaces.

We report the synthesis of altitudinal molecular motors that contain functional groups in their rotor part. In an approach to achieve dynamic control over the properties of solid surfaces, a hydrophobic perfluorobutyl chain and a relatively hydrophilic cyano group were introduced to the rotor part of the motors. Molecular motors were attached to quartz surfaces by using interfacial 1,3-dipolar cycloadditions. To test the effect of the functional groups on the rotary motion, photochemical and thermal isomerization studies of the motors were performed both in solution and when attached to the surface. We found that the substituents have no significant effect on the thermal and photochemical processes, and the functionalized motors preserved their rotary function both in solution and on a quartz surface. Preliminary results on the influence of the functional groups on surface wettability are also described.

Silanization of quartz, silicon and mica surfaces with light-driven molecular motors: construction of surface-bound photo-active nanolayers.

The attachment of molecular rotary motors containing triethoxysilane functional groups to quartz, silicon and mica surfaces is described. Motors containing silane coupling agents in their structure form stable molecular layers on quartz and silicon surfaces. Motors attached to these surfaces were found to undergo photochemical and thermal isomerization steps similar to those observed in solution. Additionally, successful formation of molecular "carpets" on atomically flat mica extending micrometer-sized length scales is presented. These "carpets" were found to undergo morphological changes upon irradiation with UV-light.

Photoimmobilization of saccharides.

Interest in understanding the biological information content of carbohydrates has led to the development of a variety of methodologies for preparing carbohydrate microarrays. A key challenge is to find a general method to make carbohydrate molecules adhere to a solid chip in a stable manner while preserving the biorecognition properties present when in their native biological environment. The complexity of carbohydrates makes chemical modification prior to surface deposition rigorous when large libraries of surface-immobilized sugars are desired. In this report, we review a versatile photochemical method to carbohydrate immobilization that does not require premodification of the carbohydrate. The method utilizes surfaces modified with photoactive carbonyls that can insert into C-H bonds upon photoexcitation.

A chiroptical photoswitchable DNA complex.

The interesting structural, electronic, and optical properties of DNA provide fascinating opportunities for developing nanoscale smart materials by integrating DNA with opto-electronic components. In this article we demonstrate the electrostatic binding of an amine-terminated dithienylethene (DET) molecular switch to double-stranded synthetic polynucleotides. The DET switch can undergo photochemical ring-closure and opening reactions. Circular dichroism (CD) and UV-vis spectroscopy show that both the open, 1o, and the closed, 1c, forms of the switch bind to DNA. Upon addition of DNA to a solution of 1o or 1c, the UV-vis spectrum displays a hypochromic effect, indicative of an interaction between the switch and the DNA. The chirality of the DNA double-helix is transmitted to the switching unit which displays a well-defined CD signal upon supramolecular complexation to the DNA. Additionally, the CD signal of the DNA attenuates, demonstrating that both components of the complex mutually influence each other's structure; the DNA induces chirality in the switch, and the switch modifies the structure of the DNA. Modulation of the chiroptical properties of the complex is achieved by photochemically switching the DET between its ring open and closed isomers. A pH dependence study of the binding shows that when the pH is increased the switches lose their binding ability, indicating that electrostatic interactions between protonated amines and the negatively charged phosphate backbone are the dominant driving force for binding to the DNA. A comparison of poly(deoxyguanylic-deoxycytidylic) acid [poly(dGdC)(2)] polynucleotides with poly(deoxyadenylic-deoxythymidylic) acid [poly(dAdT)(2)] shows distinct differences in the CD spectra of the complexes.

Adhesion of photon-driven molecular motors to surfaces via 1,3-dipolar cycloadditions: effect of interfacial interactions on molecular motion.

We report the attachment of altitudinal light-driven molecular motors to surfaces using 1,3-dipolar cycloaddition reactions. Molecular motors were designed containing azide or alkyne groups for attachment to alkyne- or azide-modified surfaces. Surface attachment was characterized by UV-vis, IR, XPS, and ellipsometry measurements. Surface-bound motors were found to undergo photochemical and thermal isomerizations consistent with unidirectional rotation in solution. Confinement at a surface was found to reduce the rate of the thermal isomerization process. The rate of thermal isomerization was also dependent on the surface coverage of the motors. In solution, changes in the UV-vis signal that accompany thermal isomerization can be fit with a single monoexponential decay. In contrast, thermal isomerization of the surface-bound motors does not follow a single monoexponential decay and was found to fit a biexponential decay. Both one- and two-legged motors were attached to surfaces. The kinetics of thermal isomerization was not affected by the valency of attachment, indicating that the changes in kinetics from solution to surface systems are related to interactions between the surface-bound motors.

Patterning dewetting in thin polymer films by spatially directed photocrosslinking.

In this report we examine the dewetting of spin-cast poly (styrene) films in a confined geometry. We designed a platform for laterally confining PS by photo-patterning crosslinks in spin-coated thin films. Heating the patterned film above the glass transition temperature of PS results in localized dewetting patterns in regions that were not crosslinked, while the crosslinked pattern serves as a rigid barrier that confines the retraction of the uncrosslinked polymer in micron-sized domains. The barriers also provide a favorable surface that the liquid PS wets onto, forming a rim at the boundary of crosslinked and uncrosslinked polymer. The resulting patterns are shown to be dependent on the irradiation and annealing time, the dimensions of the uncrosslinked region and the thickness of the film.

Light-driven altitudinal molecular motors on surfaces.

A Cu(I)-catalyzed 1,3-dipolar cycloaddition was used to construct a monolayer of an altitudinal molecular motor on quartz and silicon substrates, which represents the fastest light-driven molecular motor, to date, grafted to a solid surface.

On/off photoswitching of the electropolymerizability of terthiophenes.

In this contribution the polymerization of terthiophene, to form an alkene bridged alpha,alpha-coupled sexithiophene polymer, is controlled by light; i.e. the electropolymerizability of the monomer 1F is switched off and on with UV and visible light, respectively. The system comprises of both bis-terthiophene and photochromic dithienylethene units. The presence of a light-switchable unit allows on-off switching of the electropolymerization of the monomer with light. Furthermore the incorporation of the dithienylethene in the polymer backbone increases dramatically the homogenity of the polymer formed (i.e., only sexithiophene units are formed). The derived films are robust and fully retain electrochromic behavior as has been demonstrated through cyclic voltammetry while spatial control (patterning) is readily achieved by applying simple optical masking techniques.

Photons to illuminate the universe of sugar diversity through bioarrays.

In this mini-review, we summarize the photochemical approaches for developing high-throughput carbohydrate microarray technologies. Newly established methods for photo-immobilizing unmodified monosaccharides, oligosaccharides and polysaccharides onto photoactive surfaces and coupling of photoactive carbohydrates onto polymer surfaces are reviewed.