Search

A core-shell strategy was developed to protect synthetic DNA in organosilica particles encompassing dithiol linkages allowing for a DNA loading of 1.1 wt %. DNA stability tests involving bleach as an oxidant showed that following the procedure DNA was sandwiched between core particles of ca. 450 nm size and a protective outer layer, separating the DNA from the environment. Rapid aging tests at 60 °C and 50% relative humidity revealed that the DNA protected within this material was significantly more stable than nonprotected DNA, with an expected ambient temperature half-life of over 60 years. Still, and due to the presence of the dithiol linkages in the backbone of the organosilica material, the particles degraded in the presence of reducing agents (TCEP and glutathione) and disintegrated within several days in a simulated compost environment, which was employed to test the biodegradability of the material. This is in contrast to DNA encapsulated following state of the art procedures in pure SiO

DNA has emerged as an attractive medium for archival data storage due to its durability and high information density. Scalable parallel random access to information is a desirable property of any storage system. For DNA-based storage systems, however, this still needs to be robustly established. Here we report on a thermoconfined polymerase chain reaction, which enables multiplexed, repeated random access to compartmentalized DNA files. The strategy is based on localizing biotin-functionalized oligonucleotides inside thermoresponsive, semipermeable microcapsules. At low temperatures, microcapsules are permeable to enzymes, primers and amplified products, whereas at high temperatures, membrane collapse prevents molecular crosstalk during amplification. Our data show that the platform outperforms non-compartmentalized DNA storage compared with repeated random access and reduces amplification bias tenfold during multiplex polymerase chain reaction. Using fluorescent sorting, we also demonstrate sample pooling and data retrieval by microcapsule barcoding. Therefore, the thermoresponsive microcapsule technology offers a scalable, sequence-agnostic approach for repeated random access to archival DNA files.

The resilience of ancient DNA (aDNA) in bone gives rise to the preservation of synthetic DNA with bioinorganic materials such as calcium phosphate (CaP). Accelerated aging experiments at elevated temperature and humidity displayed a positive effect of co-precipitated, crystalline dicalcium phosphate on the stability of synthetic DNA in contrast to amorphous CaP. Quantitative PXRD in combination with SEM and EDX measurements revealed distinct CaP phase transformations of calcium phosphate dihydrate (brushite) to anhydrous dicalcium phosphate (monetite) influencing DNA stability., Chemical Communications, 58 (19), ISSN:1359-7345, ISSN:1364-548X

Molecular manipulation and analysis are the cornerstone of life sciences. With the recent advances in molecular data storage and computing, it has become an increasingly exciting and viable alternative for the post-CMOS scaling era. Widespread use of molecular manipulation/analysis and data storage/computing requires a scalable and low-cost platform for hybrid molecular-electronics systems. This enables us to build on the best of what molecular and electronics systems can offer. In this article, we present PurpleDrop, a full-stack digital microfluidic platform for hybrid molecular-electronic systems in multiple domains, and focus on DNA data storage as a use case. We describe its design principles and relevant aspects such as closed-loop operation with computer vision and capacitive sensing, on-board magnetic bead extraction, and polymerase chain reaction, among other primitives. Importantly, we emphasize the ability to express and execute protocols and computation that include molecular and computational components.

Using DNA as a durable, high-density storage medium with eternal format relevance can address a future data storage deficiency. The proposed storage format incorporates dehydrated particle spots on glass, at a theoretical capacity of more than 20 TB per spot, which can be efficiently retrieved without significant loss of DNA. The authors measure the rapid decay of dried DNA at room temperature and present the synthesis of encapsulated DNA in silica nanoparticles as a possible solution. In this form, the protected DNA can be readily applied to digital microfluidics (DMF) used to handle retrieval operations amenable to full automation. A storage architecture is demonstrated, which can increase the storage capacity of today's archival storage systems by more than three orders of magnitude: A DNA library containing 7373 unique sequences is encapsulated and stored under accelerated aging conditions (4 days at 70 °C, 50% RH) corresponding to 116 years at room temperature and the stored information is successfully recovered., Small, 18 (15), ISSN:1613-6810, ISSN:1613-6829

Description, A demonstration of DNA synthesis control at over 1000x higher density shows the path to large scale DNA data storage., Synthetic DNA is an attractive medium for long-term data storage because of its density, ease of copying, sustainability, and longevity. Recent advances have focused on the development of new encoding algorithms, automation, preservation, and sequencing technologies. Despite progress in these areas, the most challenging hurdle in deployment of DNA data storage remains the write throughput, which limits data storage capacity. We have developed the first nanoscale DNA storage writer, which we expect to scale DNA write density to 25 × 106 sequences per square centimeter, three orders of magnitude improvement over existing DNA synthesis arrays. We show confinement of DNA synthesis to an area under 1 square micrometer, parallelized over millions of nanoelectrode wells and then successfully write and decode a message in DNA. DNA synthesis on this scale will enable write throughputs to reach megabytes per second and is a key enabler to a practical DNA data storage system.

While the majority of reported paired electrochemical reactions involve carefully matched cathodic and anodic reactions, the precise matching of half reactions in an electrolysis cell is not generally necessary. During a constant current electrolysis almost any oxidation and reduction reaction can be paired, and in the presented work we capitalize on this observation by examining the coupling of anodic oxidation reactions with the production of hydrogen gas for use as a reagent in remote, Pd-catalyzed hydrogenation and hydrogenolysis reactions. To this end, an alcohol oxidation, an oxidative condensation, intramolecular anodic olefin coupling reactions, an amide oxidation, and a mediated oxidation were all shown to be compatible with the generation and use of hydrogen gas at the cathode. This pairing of an electrolysis reaction with the production of a chemical reagent or substrate has the potential to greatly expand the use of more energy efficient paired electrochemical reactions.

Both normal and tumorous stem cells can arrest cell division, avoid apoptosis, and then regenerate lost daughter cells following acute genotoxic insult. This protective, reversible proliferative arrest, known as “quiescence,” is still poorly understood. Here, we show that mTOR-regulated mitophagy is required for radiation insult-induced quiescence in Drosophila germline stem cells (GSCs). In GSCs, depletion of mito-fission (Drp1) or mitophagy (Pink1 and Parkin) eliminates entry into quiescence, while depletion of mitochondrial biogenesis (PGC1α) or fusion (Mfn2) eliminates exit from quiescence. We also find that mitophagy-dependent quiescence is under epigenetic control; knockdown of Jarid2 (PRC2) or Pc or Sce (PRC1) stabilizes the mitochondria and locks GSCs out of quiescence, while knockdown of PRC2-specific demethylase, Utx, prevents re-accumulation of the mitochondria and locks GSCs in quiescence. These data suggest that mitochondrial number coordinates reversible quiescence. We further identify that the mechanism of quiescence in both GSCs and human induced pluripotent stem cells (iPSCs) relies on mitophagy to deplete the mitochondrial pool of CycE and limit cell cycle progression. This alternative method of G1/S regulation may present new opportunities for therapeutic purposes.

Synthetic DNA has recently risen as a viable alternative for long‐term digital data storage. To ensure that information is safely recovered after storage, it is essential to appropriately preserve the physical DNA molecules encoding the data. While preservation of biological DNA has been studied previously, synthetic DNA differs in that it is typically much shorter in length, it has different sequence profiles with fewer, if any, repeats (or homopolymers), and it has different contaminants. In this paper, nine different methods used to preserve data files encoded in synthetic DNA are evaluated by accelerated aging of nearly 29 000 DNA sequences. In addition to a molecular count comparison, the DNA is also sequenced and analyzed after aging. These findings show that errors and erasures are stochastic and show no practical distribution difference between preservation methods. Finally, the physical density of these methods is compared and a stability versus density trade‐offs discussion provided.

Synthetic DNA has recently risen as a viable alternative for long-term digital data storage. To ensure that information is safely recovered after storage, it is essential to appropriately preserve the physical DNA molecules encoding the data. While preservation of biological DNA has been studied previously, synthetic DNA differs in that it is typically much shorter in length, it has different sequence profiles with fewer, if any, repeats (or homopolymers), and it has different contaminants. In this paper we evaluate nine different methods used to preserve data files encoded in synthetic DNA by accelerated aging of nearly 29,000 DNA sequences. In addition to a molecular count comparison, we also sequence and analyze the DNA after aging. Our findings show that errors and erasures are stochastic and show no practical distribution difference between preservation methods. Finally, we compare the physical density of these methods and provide a stability versus density trade-offs discussion.

Year-round ultraviolet exposure silently causes skin damage that goes unnoticed until sunburn. Current personal wearables for monitoring UV exposure have not seen significant uptake, which may be attributed to their one-size-fits-all aesthetic or inapplicability to people with different skin tones. We present EcoPatches, inkjet-printable chemical patches that mediate a person's relationship with their environment by allowing them to create designs and formulations that resonate with them. Supporting human- and machine-interpretability for EcoPatches' visual changes means that users can glance at their EcoPatch during the day to see large exposure changes or take a picture of their EcoPatch with a smartphone app for more accurate and precise readings. We conducted an online survey to elicit visual design recommendations that support these features. We also evaluated both interpretation methods, finding that they achieved strong Pearson correlation coefficients with the \projectnames' known exposure levels (human: 0.79, app: 0.90).

Rapid aging tests (70 °C, 50% RH) of solid state DNA dried in the presence of various salt formulations, showed the strong stabilizing effect of calcium phosphate, calcium chloride and magnesium chloride, even at high DNA loadings (>20 wt%). A DNA-based digital information storage system utilizing the stabilizing effect of MgCl2 was tested by storing a DNA file, encoding 115 kB of digital data, and the successful readout of the file by sequencing after accelerated aging., Chemical Communications, 56 (25), ISSN:1359-7345, ISSN:1364-548X

Affordably tracking the transmission of respiratory infectious diseases in urban transport infrastructures can inform individuals about potential exposure to diseases and guide public policymakers to prepare timely responses based on geographical transmission in different areas in the city. Towards that end, we designed and tested a method to detect SARS-CoV-2 RNA in the air filters of public buses, revealing that air filters could be used as passive fabric sensors for the detection of viral presence. We placed and retrieved filters in the existing HVAC systems of public buses to test for the presence of trapped SARS-CoV-2 RNA using phenol-chloroform extraction and RT-qPCR. SARS-CoV-2 RNA was detected in 14% (5/37) of public bus filters tested in Seattle, Washington, from August 2020 to March 2021. These results indicate that this sensing system is feasible and that, if scaled, this method could provide a unique lens into the geographically relevant transmission of SARS-CoV-2 through public transit rider vectors, pooling samples of riders over time in a passive manner without installing any additional systems on transit vehicles., Graphical abstract Unlabelled Image

Microfluidic devices promise to automate wetlab procedures by manipulating small chemical or biological samples. We are developing a full-stack microfluidic automation platform that allows and allows users to scale up the complexity of microfluidic programming, encouraging them to mix fluidic manipulations with traditional programming. Puddle is a runtime system that provides a high-level API for microfluidic manipulations. It manages fluidic resources dynamically, allowing programmers to freely mix regular computation with microfluidics, resulting in more expressive programs. It also provides real-time error correction through a computer vision system, allowing robust execution on cheaper digital microfluidic hardware. We have been running Puddle on PurpleDrop, a new digital microfluidic device that is affordable and has novel features such as fully automated input/output of fluids. With this combination, we have demonstrated PCR with automated replenishment, a DNA sequencing preparation protocol, and the complete retrieval of digital data stored in dehydrated spots of DNA on the device's surface. Going forward, we see Puddle and PurpleDrop as part of a platform for further research. PurpleDrop is affordable and extensible, which makes a compelling case for adding new periferials or even scaling out by connecting multiple devices. And Puddle provides a flexible and abstract programming model that could enable microfluidic programs to run on different hardware targets (DMF or liquid handling robots), or even a combination thereof.

Microfluidic devices promise to automate wetlab procedures by manipulating small chemical or biological samples. This technology comes in many varieties, all of which aim to save time, labor, and supplies by performing lab protocol steps typically done by a technician. However, existing microfluidic platforms remain some combination of inflexible, error-prone, prohibitively expensive, and difficult to program. We address these concerns with a full-stack digital microfluidic automation platform. Our main contribution is a runtime system that provides a high-level API for microfluidic manipulations. It manages fluidic resources dynamically, allowing programmers to freely mix regular computation with microfluidics, which results in more expressive programs than previous work. It also provides real-time error correction through a computer vision system, allowing robust execution on cheaper microfluidic hardware. We implement our stack on top of a low-cost droplet microfluidic device that we have developed. We evaluate our system with the fully-automated execution of polymerase chain reaction (PCR) and a DNA sequencing preparation protocol. These protocols demonstrate high-level programs that combine computational and fluidic operations such as input/output of reagents, heating of samples, and data analysis. We also evaluate the impact of automatic error correction on our system's reliability.

Synthetic DNA has emerged as a novel substrate to encode computer data with the potential to be orders of magnitude denser than contemporary cutting edge techniques. However, even with the help of automated synthesis and sequencing devices, many intermediate steps still require expert laboratory technicians to execute. We have developed an automated end-to-end DNA data storage device to explore the challenges of automation within the constraints of this unique application. Our device encodes data into a DNA sequence, which is then written to a DNA oligonucleotide using a custom DNA synthesizer, pooled for liquid storage, and read using a nanopore sequencer and a novel, minimal preparation protocol. We demonstrate an automated 5-byte write, store, and read cycle with a modular design enabling expansion as new technology becomes available.

In electrochemical processes, an oxidation half-reaction is always paired with a reduction half-reaction. Although systems for reactions such as the reduction of CO2 can be coupled to water oxidation to produce O2 at the anode, large-scale O2 production is of limited value. One may replace a low-value half-reaction with a compatible half-reaction that can produce a valuable chemical compound and operate at a lower potential. In doing so, both the anodic and cathodic half-reactions yield desirable products with a decreased energy demand. Here we demonstrate a paired electrolysis in the case of the oxidative condensation of syringaldehyde and o-phenylenediamine to give 2-(3,5-dimethoxy-4-hydroxyphenyl)benzimidazole coupled with the reduction of CO2 to CO mediated by molecular electrocatalysts. We also present general principles for evaluating current–voltage characteristics and power demands in paired electrolyzers.

DNA promises to be a high density data storage medium, but physical storage poses a challenge. To store large amounts of data, pools must be physically isolated so they can share the same addressing scheme. We propose the storage of dehydrated DNA spots on glass as an approach for scalable DNA data storage. The dried spots can then be retrieved by a water droplet using a digital microfluidic device. Here we show that this storage schema works with varying spot organization, spotted masses of DNA, and droplet retrieval dwell times. In all cases, the majority of the DNA was retrieved and successfully sequenced. We demonstrate that the spots can be densely arranged on a microfluidic device without significant contamination of the retrieval. We also demonstrate that 1 TB of data could be stored in a single spot of DNA and successfully retrieved using this method., DNA as a high density storage medium is receiving increasing attention, but long term physical storage is an unsolved problem. Here the authors show that up to 1 TB of data stored as dehydrated DNA spots on a glass cartridge can be retrieved in a spot of water using digital microfluidics with minimal data loss and contamination.

Either aldehyde or cinnamyl ether products can be selectively extracted from raw sawdust by controlling the temperature and pressure of a solvolysis reaction. These materials have been used as platform chemicals for the synthesis of 15 different synthetic substrates. The conversion of the initial sawdust-derived materials into electron-rich aryl substrates often requires the use of oxidation and reduction chemistry, and the role electrochemistry can play as a sustainable method for these transformations has been defined.

The combination of visible light, photovoltaics, and electrochemistry provides a convenient, inexpensive platform for conducting a wide variety of sustainable oxidation reactions. The approach presented in this article is compatible with both direct and indirect oxidation reactions, avoids the need for a stoichiometric oxidant, and leads to hydrogen gas as the only byproduct from the corresponding reduction reaction.

200 MB of digital data is stored in DNA, randomly accessed and recovered using an error-free approach. Synthetic DNA is durable and can encode digital data with high density, making it an attractive medium for data storage. However, recovering stored data on a large-scale currently requires all the DNA in a pool to be sequenced, even if only a subset of the information needs to be extracted. Here, we encode and store 35 distinct files (over 200 MB of data), in more than 13 million DNA oligonucleotides, and show that we can recover each file individually and with no errors, using a random access approach. We design and validate a large library of primers that enable individual recovery of all files stored within the DNA. We also develop an algorithm that greatly reduces the sequencing read coverage required for error-free decoding by maximizing information from all sequence reads. These advances demonstrate a viable, large-scale system for DNA data storage and retrieval.

We present EarthTones, cosmetic-inspired wearable chemical sensing powders to detect and display harmful environmental factors through color change. We seek to create an analog display experience through chemical reactions that overcome current constraints of rigid, battery-laden wearable displays. We designed three unique chemical changing powders to reflect elevated levels of carbon monoxide (CO), ultraviolet (UV) rays, and ozone (O3). The powders achieve color changes distinguishable to the human eye, while maintaining an aesthetic appeal to the wearer. Our technical evaluations confirmed the performance of the powders to detect and display elevated levels. An 18-person exploratory study provided insight to the perceptions, possibilities, and challenges of a powder form factor for wearable environmental visualization. Through this paper, we intend to enable the use of colorimetric chemical displays for HCI researchers and designers. More generally, we seek to encourage the research and use of chemical-based sensors and interdisciplinary research in HCI.

Current storage technologies can no longer keep pace with exponentially growing amounts of data. 1 Synthetic DNA offers an attractive alternative due to its potential information density of ~ 1018 B/mm3, 107 times denser than magnetic tape, and potential durability of thousands of years.2 Recent advances in DNA data storage have highlighted technical challenges, in particular, coding and random access, but have stored only modest amounts of data in synthetic DNA. 3,4,5 This paper demonstrates an end-to-end approach toward the viability of DNA data storage with large-scale random access. We encoded and stored 35 distinct files, totaling 200MB of data, in more than 13 million DNA oligonucleotides (about 2 billion nucleotides in total) and fully recovered the data with no bit errors, representing an advance of almost an order of magnitude compared to prior work. 6 Our data curation focused on technologically advanced data types and historical relevance, including the Universal Declaration of Human Rights in over 100 languages,7 a high-definition music video of the band OK Go,8 and a CropTrust database of the seeds stored in the Svalbard Global Seed Vault.9 We developed a random access methodology based on selective amplification, for which we designed and validated a large library of primers, and successfully retrieved arbitrarily chosen items from a subset of our pool containing 10.3 million DNA sequences. Moreover, we developed a novel coding scheme that dramatically reduces the physical redundancy (sequencing read coverage) required for error-free decoding to a median of 5x, while maintaining levels of logical redundancy comparable to the best prior codes. We further stress-tested our coding approach by successfully decoding a file using the more error-prone nanopore-based sequencing. We provide a detailed analysis of errors in the process of writing, storing, and reading data from synthetic DNA at a large scale, which helps characterize DNA as a storage medium and justify our coding approach. Thus, we have demonstrated a significant improvement in data volume, random access, and encoding/decoding schemes that contribute to a whole-system vision for DNA data storage.

Oxidation reactions are powerful tools for synthesis because they allow for the functionalization of molecules. Here, we present a general method for conducting these reactions on a microelectrode array in a site-selective fashion. The reactions are run as a competition between generation of a chemical oxidant at the electrodes in the array and reduction of the oxidant by a "confining agent" in the solution above the array. The "confining agent" does not need to be more reactive than the substrate fixed to the surface of the array. In many cases, the same substrate placed on the surface of the array can also be used in solution as the confining agent.

Inexpensive, readily available photovoltaic cells have been used to conduct indirect electrochemical oxidation reactions. The reactions retain the efficiency of the solar-electrochemical method while capitalizing on the unique opportunities for selectivity afforded by a chemical oxidant. The versatility of the electrochemical method allowed for the recycling of Os(VIII)-, TEMPO-, Ce(IV)-, Pd(II)-, Ru(VIII)-, and Mn(V)-oxidants all with the same very simple reaction apparatus.

In this paper the practical density of long‐term DNA storage is increased. Specifically, the DNA weight loading of silica sphere DNA storage is increased to 3.4 wt%, a ten‐fold increase compared to the previous state‐of‐the‐art. By applying a Layer‐by‐Layer (LbL) design with alternating layers of DNA and a polycationic molecule, namely polyethyleneimine (PEI), another dimension to DNA surface binding onto magnetic nanoparticles is added. A protective silica layer is grown on top of the multilayered nanoparticles to shield the DNA from external sources of damage. Accelerated aging experiments of the nanoparticles and the subsequent quantification of DNA stability via qPCR show a significantly lower degradation rate compared to unprotected DNA. The novel material is compared to previous DNA storage technologies, outperforming those in DNA storage density as well as stability. Finally, the storage of an 83 kB digital file in DNA through a successful readout of a 4991 oligonucleotide pool is demonstrated from particle encapsulation, through accelerated aging, to sequencing.

Nat. Biotechnol. 36, 242–248 (2018); published online 19 February 2018; corrected after print 8 March 2018 In the version of this article initially published, the references in the reference list were in the wrong order; the references have been renumbered as follows: 3 as 2; 5 as 3; 6 as 8; 7 as 9;8 as 11; 9 as 6; 10 as 12; 11 as 5; 12 as 13; 13 as 7; 16 as 10; and no.

Several computational methods were evaluated for determining the gas-phase reaction mechanisms of lithium dimethylcuprate and dimethylcuprate anion with chloromethane and vinyl chloride. These methods include the B3LYP and M06 density functional theory (DFT) methods, the unscaled and spin-component-scaled Moller-Plesset perturbation theory (MP2, SCS-MP2, and SCSC-MP2), CCSD, and CCSD(T). The reaction of interest is an oxidative addition of the alkyl or vinyl halide to the Cu(I) species, resulting in a Cu(III) intermediate, which undergoes reductive elimination with coupling of the two alkyl fragments. Three possible oxidative addition pathways were examined, a concerted addition to Cu(I), an S(N)2-like reaction of Cu on the alkyl halide, and a radical mechanism. A concerted reductive elimination step was also investigated.

When evaluating the sustainability of an electrochemical synthesis, the source and efficient use of electricity, the generation of waste byproducts, and the source of chemicals used should be considered in the development of a greener process. Constant current electrochemical oxidation reactions increase functionality of a molecule but are limited in scope based on oxidation potential. This shortcoming disappears when using a chemical oxidant, which can select based on steric hindrance, chirality, chelation control, and other factors. However, a major pitfall of any stoichiometric chemical oxidation reaction is the generation of a stoichiometric reduction byproduct, oftentimes a metal waste product. To circumvent this problem, chemical oxidants can be recycled directly at the anode while generating only H­2 gas at the cathode and can be powered by a simple photovoltaic power supply.1,2 From a green chemistry standpoint, the substrates used in anodic oxidations should have their origins from renewable feedstocks. Lignin, a biopolymer found in wood, has been disassembled into small monomers and converted into substrates for synthesis of heterocyles and quinones.3 Ideally, to maximize efficiency of these and other electrochemical processes, one wants to perform a useful oxidation at the anode simultaneously with a useful reduction at the cathode. Using this idea of a paired electrolysis, electrochemical oxidation of lignin-derived substrates has been coupled with CO2 reduction. In this presentation, the recycling of a variety of chemical oxidants at an electrode using simple photovoltaics as the source of electricity will be discussed. Furthermore, breakdown of lignocellulosic biomass into chemical building blocks for use in paired electrolyses will be explored (Figure 1). References: Nguyen, B. H.; Redden, A.; Moeller, K. D. “Sunlight, Electrochemistry, and Sustainable Oxidation Reactions.” Green Chem. 2014, 16, 69-72. Anderson, L. A.; Redden, A.; Moeller, K. D. “Connecting the Dots: Using Sunlight to Drive Electrochemical Oxidations.” Green Chem. 2011, 13, 1652-1654. Unpublished results with Robert Perkins, Jake Smith and Kevin Moeller. Figure 1

Microelectrode arrays provide a potentially powerful method form monitoring the interactions between small molecules and biological receptors in “real-time” as the events happen. This is accomplished by placing or building small molecules proximal to the individually addressable electrodes in the array. Central to this effort is the availability of porous reaction layers that can be used to coat the arrays and provide attachment points for fixing molecules to surface of the electrodes. The porous reaction layers must be stable with respect to time, chemically inert, compatible with both the synthetic and analytical methods to be performed on the arrays, and resistant to non-specific binding events with biological receptors. One approach to addressing these issues is to take advantage of diblock copolymers with the general structure shown in Figure 1.1The polymer contains a 2-methylacrylate block functionalized with a cinnamate group and a substituted polystyrene block. The polymer can be spin coated onto the arrays and then photolyzed in order to crosslink the cinnamate groups. This provides stability to the surface. The degree of crosslinking allows for control of the pore size in the polymer. The styrene groups can then be used as attachement points for adding molecules to the surface of the array. The first polymer studied was the 4-bromostyrene derivative (R = Br). The polymer was stable and compatible with a variety of synthetic methods. Both Pd(0) and Cu(I)-based coupling reactions involving nucleophiles and the arylbromide were successful. In addition, the diblock copolymer was compatible with electrochemical impedance experiments, and therefore the analytical studies necessary for monitoring small molecule – receptor interactions. The bromostyrene derived diblocck copolymer was used to conduct a number of “proof-of-principle” studies that helped establish the overall utility of the arrays. The porous reaction layer based on the diblock copolymer was a vast improvement over the sugar-based surfaces originally used as coatings for the arrays. However, use of the bromostyrene based diblock copolymer was not without issues. Its use led to relatively high levels of non-specific binding with protein targets during the analytical studies. What we needed was a new surface that could be tuned to reduce such non-specific interactions. To that end, a second generation diblock copolymer containing borate ester substituted styrene block (R = B(OR)2) was synthesized. This polymer currently shows great promise. The initial polymer used a pinacol to establish the borate ester. The pinacol borate ester can be used as a handle to covalent attach small molecules to the electrodes in the array in an irreversible fashion. This can be done with the use of Pd(0), Cu(I), or a modified Chan-Lam procedure using Cu(II) (Scheme 1). In addition, the pinacol group can be reversibly exchanged for an alternative diol with the use of acid. The result is a chance to place molecules irreversibly on the surface of the for study while retaining the ability to vary the rest of the surface at will. This allows the surface of the array to be tuned so that non-specific binding events on the array can be minimized. In the talk to be presented, the chemistry of this new surface will be discussed. Topics to be addressed will include preparation of the polymer, stability studies, compatibility of the polymer with electrochemical signaling efforts, and the development of site-selective synthetic methods that take advantage of the borate esters. In addition, an application of the arrays and the new surface to a biological study will be presented. References: 1. Hu, L.; Graff, M. D.; Moeller, K. D. J. Electrochem. Soc. 2013, 160, G3020.